th July 2016, Helsinki, Finland book_ICOMF16_L… · · 2016-07-18th July 2016, Helsinki,...

Organizers

L B2 016

th International Conference on

Organized Molecular Films

25th

– 29th

July 2016, Helsinki, Finland

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Index

3

CONTENTS

Opening address page 5

Committees page 7

General information page 9

Scientific program pge 19

Plenary lecture abstracts page 31

Invited lecture abstracts page 37

Oral presentation abstracts page 51

Poster abstracts page 127

Author list page 203

Index

4

Opening Address

5

Opening address

Dear Colleagues

Welcome to the 16th International Conference on Organized Molecular Films! The 16th conference is a continuation of highly successful biennial conferences organized in various countries and continents. The conference is for the first time organized in Nordic countries and we are delighted that Helsinki and Finland have been given the opportunity to host this event. Especially, as we are on the advent of reaching a historical milestone, which has been the foundation for this conference series. Namely, in the year 2017 it will be 100 years since Irving Langmuir published his pioneering work on studying the properties of insoluble monolayers on the air-water interface (JACS 39 (1917) pp. 1848). Much has happened since then, and we are pretty sure that Irving Langmuir would have been delighted to see the legacy he has left behind in the field of organized molecular films. Triggered by Langmuir´s and many others groundbreaking works on monomolecular films the ICOMF-LB conference series was established in Durham, UK in 1982 as a conference focusing solely on Langmuir-Blodgett Films. However, as with all scientific fields, research on organized molecular films advances fast and with the help of new fundamental knowledge the scientists continuously develop and produce new applications and innovations within this field. Thus, organized molecular films have become one of the cornerstones in many research fields such as fundamental chemistry and physics, nanoscience- and –technology, and biomimicking systems, just to mention a few. The cross-disciplinary nature of studying organized molecular films requires scientists from various fields to collaborate with each other. The ICOMF-LB conference is an excellent forum for chemists, physicists, biologists, material scientists, polymer scientists, chemical engineers, and researchers in related fields to gather and discuss their latest results in the field of molecular thin films, nano-objects, nanostructures, and bio-inspired systems. We expect the ICOMF16 to be a very stimulating experience, and a valuable opportunity for the participants to develop and extend their international collaborations. We are extremely grateful to all of our supporters and sponsors who have made this conference possible, as well as to all of you for participating in the conference. We are pleased to welcome you to the ICOMF16-LB16 conference and we wish all of you an excellent conference and stay in Helsinki. On behalf of the local organizing committee, Tapani Viitala

Conference chair

Opening Address

6

Committees

7

ICOMF16 Committee members

Local organizing committee:

Tapani Viitala, conference chair (University of Helsinki, Helsinki)

Marjo Yliperttula (University of Helsinki, Helsinki)

Elina Vuorimaa-Laukkanen (Tampere Univ. of Technology, Tampere)

Helge Lemmetyinen (Tampere University of Technology, Tampere)

Lasse Murtomäki (Aalto University, Espoo)

Jouko Peltonen (Åbo Akademi University, Turku)

Leena Viitala (Secretary)

Frank Grunfeld (JFG Science and Education Ltd)

International advisory committee:

Carlos Constantino, Brazil

Christine DeWolf, Canada

Xi Zhang, China

Agnès Girard-Egrot, France

Michel Goldmann, France

Andreas Terfort, Germany

Mitsumasa Iwamoto, Japan

Masatsugu Shimomura, Japan

Hoon-Kyu Shin, Korea

Piotr Cyganik, Poland

Rigoberto Advincula, USA

General Information

8

General Information

9

General Information Location of the meeting

The main venue for the conference is the main building of the University of Helsinki and its surrounding. Address to the main building is Fabianinkatu 33, 00100 Helsinki, Finland.

Host city. Compared to most major metropolises, the beat of Helsinki is laid-back and relaxed. Most of the city's attractions and hot-spots are within walking distance from each other. The public transport system is comfortable and reliable and has been ranked among the best in Europe. A third of Helsinki is covered by green areas. They offer great possibilities for outdoor activities and recreation, such as Central Park and numerous forests just outside the city centre. The number of parks and waterside hangouts are ideal for downshifting in the heart of the city. On the other hand, scores of urban events, restaurants, bars, and nightclubs make Helsinki a vibrant capital with cultural offerings.

For travels within Helsinki City it is possible to buy a Helsinki travel card that can be used for bus, tram, train and Suomenlinna ferry. 1-hour or 1-day tickets can be purchased on buses and trams. A 1-hour ticket costs EUR 3 and a 1 day ticket costs EUR 8. For more information, please visit the Helsinki Regional Transportation website.

Taxi service in Helsinki can be requested by phone: +358 0100 0700.

Electricity: Electricity AC in Finland is 220 volts. Neither current nor plug sizes are the same around the world!

Time zone: Finland is located in the Eastern European time zone. April to September: Greenwich GMT+3 and October to March: Greenwich GMT +2.

Weather: The temperature in Helsinki in July ranges between 14 to 22°C with ca. 18 hours of sunlight. For weather forecast click here.

Currency: The official currency in Finland is EUR. Exchange of foreign currency is available at private bureaux de change called Forex (located at the airport, at the main railway station and around Helsinki, see www.forex.fi/en). At Forex you can also get Amex´s travellers´ cheques exchanged to EUR. Please note that most banks do not exchange currency or travellers´ cheques in Finland.

http://www.virtualhelsinki.net/helsinkipanoraama/historia/eng/yliopisto.html

https://www.google.fi/maps/place/Fabianinkatu+33,+00100+Helsinki/@60.1694398,24.9493141,17z/data=!3m1!4b1!4m2!3m1!1s0x46920bce5e37459b:0x2b8173b28bf9aef

https://www.google.fi/maps/place/Fabianinkatu+33,+00100+Helsinki/@60.1694398,24.9493141,17z/data=!3m1!4b1!4m2!3m1!1s0x46920bce5e37459b:0x2b8173b28bf9aef

https://www.hsl.fi/en

https://www.hsl.fi/en

http://www.yr.no/place/Finland/Southern_Finland

http://www.forex.fi/en

General Information

10

Credit Cards: All major credit cards are accepted for payments in most hotels, restaurants and shops.

Passport, Visa and Invitation Letter: Participants are advised to make their own arrangements with respect to entering Finland. All delegates are requested to investigate what necessary documents and/or applications are required when travelling to Finland.

Visa Requirements and Travel Documents Accepted by Finland: Finland is a Schengen-member state. All Schengen member states have jointly agreed about the rules concerning the movement of third-country nationals in their territories and decided which countries' citizens are required to present a visa. Furthermore, each Schengen state has decided which travel documents citizens of different third countries have to present upon entering the country. Further questions concerning visas or travel documents accepted by Finland can be addressed to the Finnish diplomatic consular missions or the Passport and Visa Unit of the Ministry for Foreign Affairs.

Customs: When bringing goods into Finland there are limits set on certain commodities. If a certain amount is exceeded, duty must be paid, and the importer is required to inform customs of the amount of the commodity he or she is bringing in to the country.

Airports and Transportation: Attendees arriving at Helsinki-Vantaa international airport can travel to Helsinki city centre/Railway Station by train, bus or taxi. Airport train operates daily between 5 a.m. and midnight. A one-way ticket costs EUR 5.00. The trip takes approximately 30 minutes. Please visit Finnavia website for more information. Finnair City Bus operates daily between 05.45 AM and 01.10 AM. A one-way ticket costs EUR 6.30. The trip takes 30 minutes. Buses depart from platform 1 (T1) and platform 10 (T2). Please visit Finnavia website for more information. Airport bus number 615 (number 620 during the night) operates daily. A one-way ticket costs EUR 5.00. The trip takes 40-50 minutes. Buses depart from platform 2 (T1) and platform 21 (T2). Please visit Finnavia website for more information. A one-way taxi trip costs about EUR 50.00 and will take approximately 30 minutes. Please visit Finnavia website for more information. For public transport within Helsinki City it is possible to buy a Helsinki travel card that can be used for bus, tram, train and Suomenlinna ferry. 1-hour or 1-day tickets can be purchased on buses and trams. A 1-hour ticket costs EUR 3 and a 1 day ticket costs EUR 8. For more information, please visit the Helsinki Regional Transportation website.

http://formin.finland.fi/public/default.aspx?nodeid=15720&contentlan=2&culture=en-US

http://www.finavia.fi/en/helsinki-airport/to-and-from/train-buses-and-taxis/




http://www.reittiopas.fi/en/index.php

http://www.reittiopas.fi/en/index.php

General Information

11

Location of recommended hotels

General Information

12

Floor plan of main conference site

General Information

13

Floor plan of main conference site

General Information

14

Location of Welcome Reception site

The Welcome Reception will take place on Monday 25th July between 17:30 – 21:00

in Unioninkadun Juhlahuoneistot (Unioninkatu 33), which is located ca. 300 m from

the main conference site.

General Information

15

Location of Lunch and Conference dinner site

All lunches are included in the registration fee and are served in the Restaurant Bank

located on Unioninkatu 20, which is ca. 450 m from the main conference site. The

conference badge received during registration has to be shown when entering the

restaurant.

The conference dinner on Thursday 28th July will take place in the same restaurant

between 19:00 – 01:00. A separate ticket for participating in the conference dinner

is required. If you have signed up for the conference dinner, then the dinner ticket

and additional drink coupons can be found in the envelope provided in your

conference delegate pack.

General Information

16

Location of Helsinki City Reception site

The Helsinki city reception on Tuesday 26th July will take place in the Helsinki City

Hall located on Pohjoisesplanadi 11, which is ca. 350 m from the main conference

site. If you have signed up for the Helsinki city reception event, then the conference

badge received during registration is your ticket for entering the event.

General Information

17

Location of transport for guided tour at

Suomenlinna fortress

The boat transport for the guided tour at Suomenlinna fortress on Wednesday 27th

July leaves from a pier on the Market square (Kauppatori) at 18:20. The distance to

the pier from the conference site is ca. 600 m.

If you have signed up for the guided tour at Suomenlinna fortress, then you will find

a ticket from HSL (Helsinki Region Transport, HRT) for the boat transport in the

envelope provided in your conference delegate pack.

General Information

18

Conference proceedings

Preparation of manuscripts for ICOMF16-LB16 Proceedings (published in "MATEC Web of Conferences", EDP Sciences publisher)

Any conference participant is welcome to submit a manuscript on the topic that he/she presented at ICOMF16-LB16 (oral or poster). Authors are asked to prepare manuscripts using the template available on ICOMF16 website:

Word_Manuscript template_A4_2_columns.docx

Word_Manuscript template_A4_2_columns.doc

Manuscripts should not exceed 4 pages and will include the following sections:

Introduction Materials and Methods Results and Discussion Conclusion Acknowledgements References

The corresponding author will be identified by an asterisk in the author list and his/her email address will be specified.

Manuscripts should be addressed to the conference organizing committee by sending it to the e-mail address [email protected] by September 30th, 2016 for peer review process and publication.

http://www.helsinki.fi/icomf16/files/Word_Manuscript%20template_A4_2_columns.docx

http://www.helsinki.fi/icomf16/files/Word_Manuscript%20template_A4_2_columns.docx

mailto:[email protected]

Scientific program

19

ICOMF16 - Program

Author instructions

The length of the plenary lectures is 60 min (including 10 min for

questions),

The length of the invited lectures is 40 min (including 5-7 min for

questions)

The length of the oral presentations is 20 min (including 3-5 min for

questions).

The poster presenters are encouraged to be present at their posters

during the whole poster sessions.

Posters with odd numbers are presented during the poster

session on Wednesday 27th July 2016.

Posters with even numbers are presented during the poster

session on Thursday 28th July 2016.

Note! The 3 best posters will be rewarded with a poster

price sponsored by the Langmuir journal.

Scientific program

20

Scientific program

21

ICOMF16 - Program at a glance

Scientific program

22

Scientific program

23

ICOMF16 - Scientific program Monday 25th July 2016

8:00 - 17:00 Registration open

17:30 - 21:00 Welcome reception (Unioninkatu 33)

Tuesday 26th July 2016 8:45 - 9:00 Opening session: Professor Helge Lemmetyinen

9:00 - 10:00 Lecture hall 1, Plenary lecture 1 (Chair: J. Peltonen)

Avi Ulman (PL1)

From chemistry to interfaces and back 10:00 - 10:30 Coffee break: Floor 2

Session 1 Session 4 Session 7

Chair: A. Girard-Egrot Chair: M. Goldmann Chair: X. Zhang Lecture hall 1 Lecture hall 5 Lecture hall 13

Langmuir and Langmuir-Blodgett films

Membranes and polymer films, Multilayers

Self-assembled monolayers

10:30 - 11:10

Luciano Caseli Patrick Guenoun Wenke Chang

(IL1) (IL5) (IL9) Why immobilize

biomolecules in Langmuir and Langmuir-Blodgett

films

Ordered block copolymer films at interfaces: from thin films to thick ones

Molecular interactions in supramolecular

assemblies-a single molecule study

11:10 - 11:30

Olivier Dellea (OP1)

Enhanced Langmuir-Blodgett technique

oriented to very large planar or non-planar

substrates (>> dm²) and targeted applications

Michael Zharnikov (OP27)

Nanometer thick poly(ethylene glycol) films

and membranes as a flexible platform for

humidity sensors and bioengineering

Jakub Ossowski (OP52)

Oscillations in stability of consecutive

chemical bonds at the molecule-metal interface in self-

assembled monolayers revealed by static SIMS

11:30 - 11:50

Jiaxing Huang (OP2)

Langmuir−Blodgett colloidal assembly: An electrospray

update

Hodaya Keisar (OP28)

Coordination-based molecular assemblies used as a platform for Integrated

molecular logic

Toru Utsunomiya (OP53)

Rectification properties at the

Si(111)/monolayer/liquid metal junction

11:50 - 13:20 Lunch: Restaurant Bank (Unioninkatu 20)

Scientific program

24

Tuesday 26th July 2016 (cont.) Session 2 Session 5 Session 8

Chair: H.-K. Shin Chair: F. Winnik Chair: P. Cyganik Lecture hall 1 Lecture hall 5 Lecture hall 13


Membranes and polymer films, Multilayers


13:20 - 13:40

Atsuhiro Fujimori (OP3)

The role of modifying molecular chains in the formation of organized

molecular films of organo-modified

inorganic particles

Richard Campbell (OP29) Efficient

polyelectrolyte/surfactant films spread from neutral

aggregates

Tomasz Zaba (OP54)

Structure and stability of highly ordered self-assembled monolayers of alkynes on Au(111)

13:40 - 14:00

Ilya Gorbachev (OP4)

Influence of acidity and temperature on the

quantum dots Langmuir monolayer formation

Maria Sammalkorpi (OP30)

Thermal transition in polyelectrolyte films via dehydration mechanism

Dongsheng Liu (OP55)

The frame-guided assembly

14:00 - 14:20

Cathy McNamee (OP5)

Properties of a Langmuir monolayer of polymer

particles at an air/aqueous interface

after the collision by an external particle

Xi Zhang (OP31)

Layer-by-layer assembly driven by host-enhanced

- Interaction

Chengyou Han (OP56)

Supramolecular polymers with multi-responsiveness based

on the host‒guest chemistry of pillararenes

14:20 - 14:40

Sophie Lecomte (OP6)

Rubber particle proteins, HbREF and HbSRPP,

interact differently with lipids extracted from

RRIM600 H. brasiliensis latex

Vladimir Agabekov (OP32)

Langmuir-Blodgett films of tyrosine containing

oligopeptide

Philippe Fontaine (OP57)

Formation of metal organic nano-object by surface x-ray radiolysis

14:40 - 15:10 Coffee break: Floor 2

Scientific program

25

Tuesday 26th July 2016 (cont.) Session 3 Session 6 Session 9

Chair: M. Iwamoto Chair: A.Girard-Egrot Chair: P. Cyganik Lecture hall 1 Lecture hall 5 Lecture hall 13


Biological and bioinspired systems


15:10 - 15:30

Marian Rosaly Davolos (OP7)

In situ luminescence measurements of Eu3+-

containing polyoxo-metalate Langmuir and Langmuir-Blodgett films

Hyojin Ko (OP33)

Fabrication of carbon fibers by self-rolling

protein films

Ornella Cavalleri (OP58)

Specific and non-specific binding of proteins and

DNA-oligonucleotides on self-assembled

monolayers on gold studied by spectroscopic

ellipsometry

15:30 - 15:50

Emilia Piosik (OP8)

Optical molecular switches based on newly synthetized azobenzene

derivatives

Michael Zharnikov (OP34)

Preparation and characterization of

surface-bound ssDNA films, brushes, and

nanostructures

Hideyuki Mitomo (OP59)

An active plasmonic application using self-

assembled gold nanoparticle film on the

hydrogel

15:50 - 16:10

Sylvie Spagnoli (OP9)

Polymerization and colour transition of

polydiacetylene alcohols layers

Andreas Terfort (OP35)

SAM-based Models of cell surfaces to study the interactions with lectins and bacterial fimbriae

Rosanna Pagano (OP60)

SERS active substrates based on ZnO

nanostructures for cupric and mercuric ions

detection in aqueous matrices

16:10 - 16:30

Tomasz Martynski (OP10)

Spectral properties of chlorinated perylene-

3,4,9,10-tetracarboxylic acid derivatives in

Langmuir-Blodgett films

Orlando Rojas (OP36)

Cellulose nanocrystals and chitosan towards

tunable film development and

wrinkling

Niko Granqvist (OP61)

Characterization of solid-supported ultrathin

films and molecular interactions using MP-

SPR

16:30 - 16:50

Yasuhiro Miura (OP11)

Effects of pressure on resistance in Au(dmit)2

LB films

Kuniharu Ijiro (OP37)

Vesicular assembly of gold nanoparticles and

that plasmonic behavior

Tuesday 26th July 2016 (cont.)

18:00 - 19:00 Helsinki City Reception (Pohjoisesplanadi 11)

Scientific program

26

Wednesday 27th July 2016

9:00 - 10:00

Lecture hall 1, Plenary lecture 2 (Chair: H. Lemmetyinen)

Hiroshi Imahori (PL2) Charge separation and transport in donor-acceptor nanostructures

and interfaces

10:00 - 10:30 Coffee break: Floor 2


Chair: C. de Wolf Chair: H.-K. Shin Chair: J. Peltonen Lecture hall 1 Lecture hall 5 Lecture hall 13



Graphene and carbon materials

10:30 - 11:10

Daniel Mandler Tetsuya Yamamoto Luisa Torsi

(IL2) (IL6) (IL10) Nanoparticles imprinted matrices by LB and self-

assembly

Transcription drives phase separation in chromatin

brush

Electronic probing of biotic-abiotic interfaces

11:10 - 11:30

Alexander Buzin (OP12)

Structural characterization of self-

organized mono- and multilayers of partly

fluorinated polydialkoxy-phosphazenes at the air/water Interface

Riku Paananen (OP38)

Evaporation retarding wax ester monolayers –

insight through molecular dynamics simulations

Nathalie Bonatout (OP68)

Graphene oxide at the air-water interface

11:30 - 11:50

Matthew Paige (OP13)

Phase-separation in mixed hydrogenated-

perfluorinated fatty acid monolayers: Structure –

composition relationships

L Andrew Nelson (OP39)

Substituents modulate biphenyl insertion into

lipid membranes

Hiroyuki Sugimura (OP69)

Covalently attached graphene oxide on

hydrogen terminated silicon for passivation

against surface oxidation and low frictional coating


Scientific program

27

Wednesday 27th July 2016 (cont.) Session 11 Session 13 Session 15

Chair: E. Vuorimaa Chair: A. Bunker Chair: H. Lemmetyinen

Lecture hall 1 Lecture hall 5 Lecture hall 13 Langmuir and Langmuir-

Blodgett films Biological and bioinspired

systems Graphene and carbon

materials

13:20 - 13:40

Osamu Shibata (OP14)

Surface behaviour of gemini type

perfluorinated surfactants with DPPC at the air-water interface -

spacer length effect

Jacek Korchowiec (OP40)

Benzo[a]pyrene in membrane environment -

molecular dynamics studies

Alexey Nabok (OP70)

Graphene-based LbL deposited films: further study of

electrical properties and gas sensing

applications

13:40 - 14:00

Philippe Fontaine (OP15)

Semifluorinated alkanes monolayer at the air

water interface

Aniket Magarkar (OP41)

Effect of liposome size on passive drug release rate: in silico hypothesis and in

vitro validation

Gabriella Caminati (OP71)

Functionalization of graphene oxide/silver nanoparticles hybrid

layers for the detection of amyloid proteins

14:00 - 14:20

George R. Ivanov (OP16)

First observation of 3D aggregates in a single-

component Langmuir film below the ESP.

Nanothermodynamics explanation. Possible sensor applications.

14:20 - 15:00 Sponsors’ pitch: Lecture hall 1

15:00 - 17:00 Poster session: Floor 2

18:00 - 19:00 Transfer to Suomenlinna 19:00 - 21:00 Guided tour at Suomenlinna

Scientific program

28

Thursday 28th July 2016

9:00 - 10:00

Lecture hall 1, Plenary lecture 3 (Chair: M. Yliperttula )

Chunhai Fan (PL3) DNA nanotechnology-based engineering at the interfaces of

cytoplasmic membranes and biosensors 10:00 - 10:30 Coffee break: Floor 2


Chair: M. Yliperttula Chair: E. Vuorimaa Chair: A. Terfort Lecture hall 1 Lecture hall 5 Lecture hall 13




10:30 - 11:10

Renata Bilewicz Takaaki Manaka Andrey Turchanin

(IL3) (IL7) (IL11) Lipid liquid crystalline nanoparticles as drug

carriers and their interactions with

Langmuir-Blodgett monolayers

Visualization and analysis of carrier transport in

organic semiconductor films

Self-assembled monolayers as a

platform for generation of novel 2D

materials

11:10 - 11:30

Takuya Matsumoto (OP17)

Cytochrome c/DNA co-assembling at air-water

interface

Alaric Taylor (OP42)

Biomimetic glass nanostructures for

efficient anti-reflection and self-cleaning

Moonhor Ree (OP62)

Complex morphologies and structural details in

nanoscale thin films and solutions of

functional polymers in various topologies

11:30 - 11:50

Dorota Matyszewska (OP18)

Interactions of anticancer drugs with biomimetic

phospholipid layers

Atsushi Hozumi (OP43)

Bio-inspired organogel exhibiting anti-X surface

properties

Monica Österberg (OP63)

Correlation between thin films

supramolecular structure and surface

interactions


Scientific program

29

Thursday 28th July 2016 (cont.) Session 17 Session 19 Session 21

Chair: C. de Wolf Chair: T. Viitala Chair: A. Terfort Lecture hall 1 Lecture hall 5 Lecture hall 13




13:20 - 13:40

Didem Sanver (OP19)

Modelling of biomembrane-flavonoid

interactions

Maria Raffaella Martina (OP44)

Protein misfolding and aggregation triggered by

adsorption at liquid-condensed boundaries in

Langmuir monolayer

Piotr Cyganik (OP64)

Thiolate versus selenolate: Structure, stability and charge transfer properties

13:40 - 14:00

Joanna Juhaniewicz (OP20)

Membrane activity of ultra-short linear

lipopeptides

Simona Bettini (OP45)

Design and realisation of iron oxide nanoparticles

conjugated by folic acid as targeted hyperthermia

systems

Satoshi Nishijima (OP65)

Conductance enhancement at metal / molecule interface of

double junctioned molecular device

14:00 - 14:20

Burkhard Schulz (OP21)

Morphologies and degradation behaviour of biodegradable polymers at the air-water interface

Marta Orczyk (OP46)

Adsorption of steroidal saponin – digitonin – onto phospholipid monolayers

Yoichi Otsuka (OP66)

Nonlinear electric properties of biological molecular networks in

nanoscale

14:20 - 14:40

Lorand Romanszki (OP22)

Systematic study of Langmuir films of

different amino acid derivatives on several

subphases

Christine Grauby-Heywang (OP47) Influence of oxidized

lipids in the membrane organization, contribution of Langmuir monolayers and Langmuir-Blodgett

films

Jukka Määttä (OP67)

Lipids and PEGylated lipids as tunable

coatings for aqueous dispersion of carbon

nanotubes

14:40 - 15:00

Joana Oliveira (OP23)

Main differences of the Stratum Corneum non-esterified constitutional ceramides - a ternary 2D

model system study

Yuri Gerelli (OP48)

Molecular transport in lipid membranes: lipid

exchange and translocation processes investigated by neutron

scattering

15:00 - 17:00 Poster session: Floor 2 17:00 - 19:00 International advisory committee meeting (members only)

19:00 - 01:00 Conference dinner: Restaurant Bank (Unioninkatu 20)

Scientific program

30

Friday 29th July 2016

9:00 - 10:00

Lecture hall 1, Plenary lecture 4 (Chair: L. Murtomäki)

Maarit Karppinen (PL4) Atomic/molecular layer deposited inorganic-organic hybrid thin

films: from fundamentals to energy applications 10:00 - 10:30 Coffee break: Floor 2

Session 22 Session 23 Session 24 Chair: L. Murtomäki Chair: T. Viitala Chair:

H. Lemmetyinen Lecture hall 1 Lecture hall 5 Lecture hall 13



Inorganic thin films and multilayers

10:30 - 11:10

Antonella Badia Edward Hæggström Manfred Buck

(IL4) (IL8) (IL12) Using surface-confined redox and ion-pairing

reactions at electroactive self-assembled

monolayers to detect the micellization of surfactants

Label-free 3D imaging Balancing interactions: the design of molecular

systems at the liquid/solid interface

11:10 - 11:30

Christine DeWolf (OP24)

Controlling lateral spacing in phenolic surfactant

monolayers

Meriem Chadli (OP49)

New tethered phospholipid bilayers integrating

membrane proteins for the development of membrane

biochips dedicated to ligand binding studies

Takeshi Kawai (OP72)

Transparent conductive thin films with high

flexibility prepared by UV light irradiation on

Langmuir monolayer of metal NPs

11:30 - 11:50

Michel Goldmann (OP25)

Alkyl imidazolium ionic liquids Langmuir layering at the air-water interface

Jan-Henrik Smått (OP50)

Nanocast metal oxide microspheres for

enrichment of phosphopeptides

Olivier Dellea (OP73)

2D array of high aspect ratio TiO2 nano-pillars

using direct photo-patternable TiO2 sol-gel

process and colloidal photolithography

11:50 - 12:10

Evgeny Glughovskoy (OP26)

Simulation of an electric field effect on surfactant

molecules

Oona Freudenthal (OP51)

Nanoscale investigation of colistin interactions with

model phospholipid membranes by combined

infrared and force spectroscopies

12:10 - 13:00 Closing session: Lecture hall 1

Plenary lecture abstracts

31



32


33

From chemistry to interfaces and back

Abraham (Avi) Ulman

Department of Biomolecular and Chemical Engineering, NYU Tandon School of Engineering, Brooklyn, NY, USA

E-mail address: [email protected]

Interfaces are ubiquitous in nature, and solution to almost all technological and medical problems requires understanding and controlling interfacial structure and interactions. The field of interfacial science and engineering is highly interdisciplinary and encompasses diverse areas of activities from studies of the fundamental properties of interfaces, to the development of new medical procedures and of new materials with unique properties for myriad applications. In this talk we review some of the milestones of our studied. From the design and synthesis of new

-assemble multilayers, to surface engineering, to metallic nanoparticles, and to diblock copolymer nanoparticles for the treatment of Osteoarthritis.

PL1


34

Charge separation and transport in donor-acceptor nanostructures and interfaces

Hiroshi Imahori1,2

1 Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan

2 Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan

E-Mail address: [email protected]

Charge separation and transport are one of the most basic processes in physics, chemistry, and biology. For instance, the nanostructured reaction center of natural photosynthesis, photoinduced ET generates a long-lived charge separation (CS) state with ~100% efficiency, leading to light-to-chemical energy conversion. In contrast, photoinduced CS at the interfaces of organic photovoltaic cells and dye-sensitized solar cells generates an electron-hole pair, followed by charge transport, eventually achieving light-to-electricity conversion. However, the interfaces of semiconductor/dye and donor/acceptor (D/A) in artificial photosynthesis and organic photovoltaic cells often suffer from the partial or even large loss of the CS state, which has still been controversial and not been fully understood owing to inevitable inhomogeneous spatial distribution of D-A components.

In this context D-bridge (B)-A linked systems have generated remarkable interest for the last few decades. The covalent linkage between D and A with a suitable bridge can eliminate complex factors and assess the photoinduced CS precisely with the help of homogenous spatial distribution of the D-B-A components. So far these systems have provided basic information on photoinduced CS. Impact of various ET parameters,

i.e., driving force (G0ET), electronic coupling (V), reorganization energy (), and temperature (T), on ET rate

has been evaluated by using elaborated D-B-A linked molecules. In particular, a well-defined D-B-A linked molecule with a rigid bridge has allowed us to shed light on photoinduced CS more accurately. In this talk I will give an overview of our initiatives on the basis of D-S-A nanostructures and interfaces. In particular, I highlight the following three main topics : i) porphyrin-fullerene, phthalocyanine-fullerene, and pyrene-carbon nanotube linked molecules, ii) porphyrin-sensitized TiO2 solar cells and solar fuels, conjugated polymer-fullerene derivative bulk heterojunction solar cells, and organic-inorganic hybrid solar cells, and iii) donor-acceptor linked molecules in biological cell membranes.

References [1] T. Umeyama, H. Imahori, J. Phys. Chem. C (Feature Article) 117, 3195 (2013). [2] T. Umeyama, H. Imahori, J. Mater. Chem. A (Feature Article) 2, 11545 (2014). [3] T. Higashino, H. Imahori, Dalton Trans. (Perspectives) 44, 448 (2015). [4] H. Hayashi, W. Nihashi, T. Umeyama, Y. Matano, S. Seki, Y. Shimizu, H. Imahori, J. Am. Chem. Soc. 133, 10736 (2011). [5] T. Numata, T. Murakami, F. Kawashima, N. Morone, J. E. Heuser, Y. Takano, K. Ohkubo, S. Fukuzumi, Y. Mori, H. Imahori, J. Am. Chem. Soc., 134, 6092 (2012). [6] T. Umeyama, J. Baek, Y. Sato, K. Suenaga, F. Abou-Chahine, N. V. Tkachenko, H. Lemmetyinen, H. Imahori, Nat. Commun. 6, 7732 (2015). [7] T. Higashino, T. Yamada, M. Yamamoto, A. Furube, N. V. Tkachenko, T. Miura, Y. Kobori, R. Jono, K. Yamashita, H. Imahori, Angew. Chem. Int. Ed. 128, 639 (2016). [8] M. Yamamoto, L. Wang, F. Li, T. Fukushima, K. Tanaka, L. Sun, H. Imahori, Chem. Sci. 7, 1430 (2016). [9] S. Zhou, M. Yamamoto, G. Briggs, H. Imahori, K. Porfyrakis, J. Am. Chem. Soc. 138, (2016), in press.

PL2


35

DNA nanotechnology-based engineering at the interfaces of cytoplasmic membranes and biosensors

Chunhai Fan

Division of Physical Biology, and Bioimaging Center, Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China.


Proteins and nucleic acids are dynamically organized in cells to realize their physiological functions with spatial and temporal orderliness. This type of elegant supermolecular assembly has inspired researchers to create molecular/biomolecular structures with dynamic organization outside of the cells. In particular, DNA nanotechnology has proven to possess extraordinary flexibility and convenience for “bottom-up” construction of exquisite nanostructures with high controllability and precision, which holds great promise in a wide range of applications, e.g., nanofabrication and molecular electronics, in-vivo and in-vitro sensing and drug delivery. In this talk, I will present several examples of using tetrahedral DNA nanostructures (TDNs) for engineering the interfaces of cytoplasmic membranes and biosensors. TDNs are three-dimensional (3D) DNA architecture with high mechanical rigidity and structural stability, which are suitable for organization of higher-ordered nanocomplexes and nanodevices. In one example, we employed single-particle tracking to visualize the internalization of TDNs, and dissect the cell entry pathways of these virus-like nanoparticles. In the second example, we dynamically organized biomolecular receptors at the biosensing interface using TDNs, and performed in-vitro diagnostics for various diseases. References

[1] H. Pei, X. L. Zuo, D. Zhu, Q. Huang and C. Fan, Acc. Chem. Res. 47, 550 (2014).

[2] L. Liang, J. Li, Q. Li, Q. Huang, J. Y. Shi, H. Yan and C. Fan, Angew. Chem. Int. Ed. 53, 7745 (2014).

[3] H. Liu, J. Wang, S. Song, C. Fan and K. V. Gothelf, Nat. Commun. 6, 10089 (2015).

[4] M. Lin, J. Wang, G. Zhou, J. Wang, N. Wu, J. Lu, J. Gao, X. Chen, J. Shi, X. Zuo and C. Fan, Angew. Chem. Int. Ed. 54,

2151 (2015).

[5] M. Lin, P. Song, G. Zhou, X. Zuo, A. Aldalbahi, J. Shi and C. Fan, Nature Protocols 11, 1244 (2016).

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36

Atomic/molecular layer deposited inorganic-organic hybrid thin films: from fundamentals to energy applications

Maarit Karppinen

Department of Chemistry, Aalto University, FINLAND E-mail address: [email protected]

Layer-engineered inorganic-organic hybrid materials have the capacity – once carefully designed and fabricated – to exhibit tailored combinations of properties traditionally seen for inorganics or organics separately. An elegant, yet industrially feasible way to realize achieve this is to combine the state-of-the-art gas-phase thin-film deposition technique of inorganics, i.e. ALD (Atomic Layer Deposition), with the emerging MLD (Molecular Layer Deposition) technique for organics. The combined ALD/MLD technique enables the atomic/molecular layer-by-layer fabrication of inorganic-organic hybrid thin films through sequential self-limiting gas-surface reactions with high precision for the film thickness and composition.1 In this talk I will discuss our recent efforts towards synthesizing such fundamentally new types of inorganic-organic hybrid materials. In particular, we have employed the ALD/MLD technique to fabricate oxide-organic thin-film superlattices in which the periodically introduced single/thin organic layers between oxide layers are shown to hinder phonon transport and enhance the thermoelectric properties of (Zn,Al)O and (Ti,Nb)O2 films.2-5 Also discussed are the new directions foreseen for the ALD/MLD technique related to hybrid luminescence materials,6 Li-ion microbattery materials7 and metal organic framework (MOF) materials.8

References

1. P. Sundberg & M. Karppinen, Organic and inorganic-organic thin film structures by molecular layer deposition: A

review, Beilstein J. Nanotechnol. 5, 1104 (2014).

2. T. Tynell, A. Giri, J. Gaskins, P.E. Hopkins, P. Mele, K. Miyazaki & M. Karppinen, Efficiently suppressed thermal

conductivity in ZnO thin films via periodic introduction of organic layers, J. Mater. Chem. A 2, 12150 (2014).

3. J.-P. Niemelä, A, Giri, P.E. Hopkins & M. Karppinen, Ultra-low thermal conductivity in TiO2:C superlattices, J. Mater.

Chem. A 3, 11527 (2015).

4. J.-P. Niemelä, A.J. Karttunen & M. Karppinen, Inorganic-organic superlattice thin films for thermoelectrics, J. Mater.

Chem. C 3, 10349 (2015).

5. A.J. Karttunen, T. Tynell & M. Karppinen, Layer-by-layer design of nanostructured thermoelectrics: first-principles

study of ZnO:organic superlattices fabricated by ALD/MLD, Nano Energy 22, 338 (2016).

6. Z. Giedraityte, P. Sundberg & M. Karppinen, Flexible inorganic-organic thin-film phosphors by ALD/MLD, J. Mater.

Chem. C 3, 12316 (2015).

7. M. Nisula & M. Karppinen, Atomic/molecular layer deposition of lithium terephthalate thin films as high rate

capability Li-ion battery anodes, Nano Lett. 16, 1276 (2016).

8. E. Ahvenniemi & M. Karppinen, Atomic/molecular layer deposition: a direct gas-phase route to crystalline metal-

organic framework thin films, Chem. Commun. 52, 1139 (2016).

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Invited lecture abstracts

37



38


39

Why immobilize biomolecules in Langmuir and Langmuir-Blodgett films

Luciano Caseli

Federal University of São Paulo, Diadema, SP, Brazil


Langmuir and Langmuir-Blodgett films may be constituted of materials that provide excellent matrices for the immobilization of molecules of biological interest. These molecules can be drugs, proteins in general, enzymes, polysaccharides, and even nucleic acids. In general, Langmuir films composed of lipids and proteins are accepted as models for cell membranes and other biointerfaces, and the interaction of these compounds with such interfaces is easily studied using tensiometry. Nowadays modern techniques regarding characterization of Langmuir monolayer have provided a deeper understanding on molecular interactions. These techniques include spectroscopic, structural and morphological ones. Also, the possibility to transfer the floating monolayers to solid supports as Langmuir-Blodgett (LB) films opens the possibility to fabricate devices in a nanoscale arrange, and nanotechnology applied to sensors and optoelectronic devices can be employed for LB films. Some examples of papers from our group about these issues are regarded to drugs with potential action against bacteria and protozoa. The first example is about a peptide with potential action against the protozoa that cause African Sleep Sickness. A region with negative compressibility is found for this peptide in surface pressure-area isotherms, and it is related to the formation of irreversible aggregates during molecular accommodation. This kind of molecular arrangement can be associated to the antiparasitic properties of this peptide since it is also observed for mixed drug-lipid films. In the second example, thymol, a natural product extracted from thyme, had its antimicrobial action studied with lipid Langmuir monolayers, for which a penetration of the compound among the apolar tails of the lipid was proposed. Molecular simulation was applied complementary to these studies and showed that the most stable thermodynamic position of thymol along the monolayer is in the alkyl tails-air interface. Also, our group has been working with models that simulate tumorigenic and non-tumorigenic cells. Working with specific lipids more common in each kind of cell membrane, and also with the cell extract proper can show the selectivity of certain drugs for each kind of interface. Naphtoquinone and quantum dots as a cell marker interact with selected Langmuir monolayers in such a way that the molecular interaction with specific chemical groups can be inferred. Finally, enzymes and other proteins can adsorbed on lipid Langmuir monolayers. For instance, beta lactoglobulin is proved to selectively remove chitosan from negative charged lipids, whose consequences is important in the removing of this protein from cow milk. Also enzymes adsorbed on lipid Langmuir monolayers are transferred to solid supports as Langmuir-Blodgett films. Examples with uricase, horseradish peroxidase, catalase, and urease show not only enzyme activity values that can be controlled at the molecular level, but also architectures that can be modified with carbon nanotubes or polysaccharides in order to improve the conservation of the catalytic properties.

IL1


40

Nanoparticles imprinted matrices (NAIM) by LB and self-assembly

Shlomit Kraus, Netta Bruchiel-Spanier, Yamit Pisman, Maria Hitrik and Daniel Mandler

Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel


The formation of matrices, which can selectively interact with nanoparticles, and are based on the LB and self-assembly approaches, will be the essence of our presentation. Nanotoxicity is a new discipline, which requires the development of appropriate tools for determination of nanoobjects such as nanoparticles (NPs). These tools are also crucial for monitoring the interactions between nanoobjects and organisms. These interactions are affected by the core, size, shape, and stabilizing shell of the objects. Hence, speciation of NPs, is becoming of utmost importance. We will present a new concept for selective recognition of NPs by a polymeric matrix imprinted with the same NPs. This approach can be classified as nanoparticle imprinted polymer (NAIM) in analogy to the well-known concept of molecularly imprinted polymers (MIP) in which the molecular analyte is imprinted in a polymer by polymerization of proper monomers with which it chemically associates. The removal of the template forms complementary cavities capable of selective recognition of the analyte. We have shown that the NIP concept works in three different systems. The first1 is based on forming a polyaniline matrix that extracted Au NPs stabilized by citrate to form NIPs, which showed high selectivity based on the size of the NPs. The second system2 was assembled using cellulose acetate in which hydrophobic Au NPs were incorporated and showed selectivity based on the thickness of the NPs shell. In the third system3 a different strategy was used. NP were first attached to the surface and then the free area was filled with molecular species. The latter wrapped the Au NPs, which were further removed.

Figure 1. One of the concepts of assembling nanoparticles imprinted matrices

References [1] S. Kraus-Ophir, J. Witt, G. Wittstock; D. Mandler; Angew. Chem. Int. Ed. 2014, 53, 294-298 [2] N. Bruchiel-Spanier and D. Mandler, ChemElectroChem, 2015, 2, 795–802 [3] M. Hitrik, Y. Pisman, G. Wittstock and D. Mandler, Nanoscale 2016, in press.

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41

Lipid liquid crystalline nanoparticles as drug carriers and their interactions with

Langmuir-Blodgett monolayers

Renata Bilewicz, Ewa Nazaruk, Monika Szlezak, Elzbieta Jablonowska, Dorota Matyszewska

Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland


Bicontinuous lipidic cubic phases (LCPs) are non-toxic, biodegradable, optically transparent, thermodynamically stable in excess water, and can incorporate active molecules of any polarity. An interesting property of cubic phase is also its ability to disperse into nanoparticles called cubosomes. Cubosome formulations are less viscous which facilitates their transport in the body. Cubosomes are also more resistant to mechanical or osmotic rupture and possess larger ratio of internal surface to volume than liposomes or micelles. Cubic phase is employed as the biomimetic environment for enzymes [1, 2] and the carrier to protect healthy body cells from harmful effects of drugs or stabilize the drug when it is unstable. The cubic phase delivery system can be also used to improve the oral bioavailability of poorly water-soluble drugs. We focus here on the lipid-liquid crystalline monoolein (GMO) phases and cubosomes as effective and safe drug delivery systems [3,4] Cubosomes are shown to disintegrate in contact with a DPPC monolayer treated as one leaflet of a biological membrane. The penetration of GMO molecules from the disintegrated cubosomes into the lipid layer depends on the availability of free adsorption sites in the layer, and hence on the molecular packing of the monolayer. For more porous lipid layers, e.g. corresponding to cancer cell environment, the action of cubosomes disintegration will be more intensive and delivery of the drug can be more efficient. These results are significant, as they enhance our understanding of the molecular interactions between membranes and cubosomes as alternative, biocompatible drug delivery systems. Doxorubicin (DOX), a model anticancer drug is loaded into the cubic phase and cubosomes. The release behavior of DOX to solutions of different pH has been evaluated. The investigation of the release profiles in vitro indicated that DOX was released from nanoparticles faster at pH 5.5 than at pH 7.4. Such pH sensitive release is important for releasing the drugs at the target tumor cells and not at the healthy ones. We show that the monoolein cubic phase can be also doped with hydrophobic or hydrophilic magnetic nanoparticles to move the carrier by means of magnetic field.

References

[1] E. Nazaruk, E. Górecka, R. Bilewicz, J. Colloids Interface Sci., 2012, 385, 130. [2] E. Nazaruk, E. Landau, R. Bilewicz Electrochim Acta, 2014, 140, 96 [3] E. Nazaruk, M. Szlęzak, E. Górecka, R. Bilewicz, Y. M. Osornio, P. Uebelhart, E. M. Landau, Langmuir, 2014, 30, 1383–1390, [4] E. Nazaruk, P. Miszta, S. Filipek, E. M. Landau, R. Bilewicz Langmuir. 2015, 31, 12753-12761.

IL3


42

Using surface-confined redox and ion-pairing reactions at electroactive self-

assembled monolayers to detect the micellization of surfactants

Eric R. Dionne1, Antonella Badia1

1 Département de chimie, Université de Montréal, C.P. 6128 succursale Centre-ville, Montréal, QC H3C 3J7, Canada


Self-assembled monolayers (SAMs) of ferrocenylalkanethiolates chemisorbed to gold surfaces were originally designed for fundamental studies of interfacial electron transfer between an electronic conductor and a molecular redox couple [1]. Oxidation of the SAM-bound ferrocene to ferrocenium proceeds via coupled electron-transfer and ion-pairing reactions. The nature of the electrolyte anion strongly affects the electrochemistry and stability of the ferrocene-terminated SAM in aqueous solution. “Hydrophobic” anions (e.g., PF6

- and ClO4-) pair more effectively with the poorly solvated ferrocenium cation than “hydrophilic”

ones (e.g., Cl- and F-). We have investigated the electrochemical oxidation of ferrocenyldodecanethiolate SAMs in the presence of surface-active organic anions consisting of a hydrophobic hydrocarbon tail and hydrophilic anionic head group [2]. The idea is to combine the tendency of surfactants to aggregate at solid/liquid interfaces with the preference of SAM-bound ferroceniums to pair with liphophilic anions. We show that the redox response in cyclic voltammetry (i.e., formal redox potential, formal width at half-maximum of the anodic peak, and anodic-to-cathodic peak separation) is exquisitely sensitive to the surfactant aggregation state in solution. The surfactant adsorbs to the SAM surface by specific ion-pairing interactions between the anionic head groups and the oxidized ferroceniums. A longer alkyl chain length results in a larger ion-pair formation constant, resulting in ferrocene oxidation at lower potential. Finally, we demonstrate that the interfacial electrochemistry of ferrocene-terminated SAMs can be used to detect the micellization of anionic surfactants in aqueous solution. References [1] C.E.D. Chidsey, Science 251, 919-922 (1991). [2] E. R. Dionne, T. Sultana, L. L. Norman, V. Toader, and A. Badia, J. Am. Chem. Soc. 135, 17457-17468 (2013).

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43

Ordered block copolymer films at interfaces: from thin films to thick ones

Patrick Guenoun

Laboratoire Interdisciplinaire sur l’Organisation Nanométrique et Supramoléculaire (LIONS), UMR 3685

CEA-CNRS, NIMBE, C.E.A. Saclay, Bât. 125, pièce 138A, F91191 Gif sur Yvette Cedex, France


Block copolymers are widely used for making nanostructures at interfaces. Indeed phase separation induces a nanoscale ordering but mastering the order of the structure deposited on a substrate requires different methods adapted to the expected goal. In this lecture I will present three different aspects of these attempts. The first one will review how long-range in-plane ordering can be obtained for thin films. The second one will address a new method for making thick films thanks to multilayers which are characterized by microscopy or GISAXS techniques. At last a third part will briefly address the case of composite films including nanoparticles.

IL5


44

Transcription drives phase separation in chromatin brush

Tetsuya Yamamoto

National Composite Center, Nagoya University, Japan


In a eukaryotic cell, relatively long DNA chains (in the order of meters) are packed in a relatively small nucleus (in the order of micro-meters) by stabilizing a complex (which is called chromatin) with histone proteins [1]. Recent experiments have shown that chromatin in embryonic stem (ES) cells show fluctuations of the local concentrations of nucleosomes (which are repeating units of chromatin) in a relatively long length and time scales, analogous to critical fluctuations [2]. In contrast, chromatin in differentiated cells shows regions of relatively small nucleosome concentrations that coexist with regions of relatively large nucleosome concentrations, analogous to phase separation [2]. Because the rate of transcription depends on the local concentrations of nucleosomes, the critical fluctuations may play an important role in maintaining pluripotency of stem cells and the dynamics of phase separation during differentiation may determine the cell linage. It is thus of interest to theoretically predict the physical mechanism involved in the phase separation of chromatin. In many cases, critical fluctuations and phase separation are driven by the attractive interactions (that tend to stabilize a condensed phase) and random forces (that tend to destabilize the condensed phase). Indeed, nucleosomes (that have net negative charges) show attractive interactions via histone tails (that have net positive charges) in the physiological salt concentration [3]. However, nucleosomes are relatively stable structures, which rarely dissociate from DNA or diffuse along DNA by thermal fluctuations. Which physical process plays a role in the random forces that destabilize the condensation of nucleosomes? Experiments have shown that nucleosomes are disassembled when they collide with RNA polymerase during transcription [4]. The rate of transcription is regulated by the local concentrations of nucleosomes, and the local concentrations of nucleosomes are, in turn, regulated by the rate of transcription dynamics; phase separation may thus be driven by transcription. This concept is best demonstrated by a simple synthetic system, such as DNA brushes [5,6]. In the present study, we theoretically predict that DNA brushes in the solution of RNA polymerase and histone proteins (and other molecules that are necessary for transcription and the assembly of nucleosomes) show phase separation due to the instability arising from the inter-correlation between the transcription dynamics and the local concentrations of nucleosomes [7]. Our theory predicts that phase separation is sensitive to the binding constant that accounts for transcription, the magnitudes of the attractive interactions between nucleosomes, applied pressure to the chromatin, and the stiffness of grafting surfaces, which may also be important physical quantities to drive the differentiation of stem cells. References [1] H. Schiessel, J. Phys. Condens. Matter, 15, R699 (2003). [2] S. Talwar, A. Kumar, M. Rao, G. I. Menon, G. V. Shivashankar, Biophys. J., 104, 533 (2013). [3] F. Muhlbacher, C. Holm, and H. Schiessel, Europhys. Letts., 73, 135 (2006). [4] L. Bintu, M. Kopaczynska, C. Hodges, L. Lubkowska, M. Kashlev, C. Bustamante, Nat. Struct. Mol. Biol., 18, 1394 (2011). [5] A. Buxboim, S. S. Daube, R. Bar-Ziv, Mol. Sys. Biol., 4, 181 (2008). [6] T. Yamamoto and S. A. Safran, Soft Matter, 11, 3017 (2015). [7] T. Yamamoto and H. Schiessel, Langmuir, 32(12), 3036 (2016).

IL6


45

Visualization and analysis of carrier transport in organic semiconductor films

Takaaki Manaka1, Mitsumasa Iwamoto1

1 Tokyo Institute of Technology, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8552, Japan


Organic semiconductors have attracted considerable attention due to their simple and low-cost processing. Various devices consisting of organic semiconductors, such as solar cell, light-emitting diode, and field effect transistor (FET) are widely studied. As we all know, the important parameter to characterize organic semiconductor thin-film is carrier mobility that represents the carrier transport property. However, transport phenomena in organic semiconductors is not fully understandable. Carrier transport is still a fundamental and significant issue in organic electronics, and is a key factor for practical application of organic semiconductors. Recent development of the fabrication process for single crystalline organic devices [1] has motivated us to revalue the advantage of single crystalline materials with high mobility. Depending on the crystal structure, organic single crystal possibly shows large anisotropic carrier transport properties. Single crystalline materials also provide us proper subjects of fundamental research for carrier transport. In this presentation, we introduce a novel method to study the carrier transport in anisotropic organic thin films by using the time-resolved microscopic second harmonic generation (TRM-SHG) imaging [2,3]. We used the FET electrode arrangement with a round-shaped source electrode. Since the round-shaped electrode can inject carriers uniformly in all directions, angular dependence of the carrier velocity (carrier mobility) is directly visualized at once [4]. According to the TRM-SHG measurement, carriers spread from the electrode, and the shape of the SHG distribution was not a perfect circle, indicating that the carrier velocity strongly depended on the flowing direction (see Fig. 1). In other words, the elliptic-shaped SHG image directly represents the anisotropic carrier velocity. Analyzing the SHG image, mobility anisotropy was estimated accordingly. Microscopic transport mechanism is also discussed on the basis of the temperature dependence of the mobility [5]. Mobility decreases with increase of the temperature, indicating the band-like hole transport and the phonon scattering in the TIPS pentacene single crystalline grains. Thus, the TRM-SHG measurement becomes a powerful tool to investigate the anisotropic nature of transient carrier transport in the practical devices. In the presentation, we also introduce a recently developed technique for visualizing carrier transport in photoluminescent polymer thin film on the basis of the transient photoluminescent decay imaging. This method is simple, but enables us a real-time observation of carrier transport phenomena on the scale of several millimeters in photoluminescent thin film.

References [1] H. Minemawari, et al., Nature 475, 364 (2011). [2] T. Manaka, E. Lim, R. Tamura, M. Iwamoto, Nature Photon. 1, 581 (2007). [3] T. Manaka, M. Iwamoto, Light Sci. Appl. 5, e16040 (2016). [4] K. Matsubara, T. Manaka, M. Iwamoto, Appl. Phys. Express 8, 041601 (2015). [5] T. Manaka, K. Matsubara, K. Abe, M. Iwamoto, Appl. Phys. Express 6, 101601 (2013).

IL7

Figure 1.TRM-SHG images from

TIPS pentacene single crystalline

grain with the round-shaped

electrode.


46

Label-free 3D imaging

Edward Hæggström1, Tapani Viitala1, Anton Nolvi1,2, Alejandro García Pérez1, Niklas Sandler2, Kim Grundström3 and Ivan Kassamakov1

1 University of Helsinki, Helsinki, Finland 2 Åbo Akademi, Turku, Finland

3 Kimmy Photonics, Espoo, Finland E-mail address: [email protected]

Scanning White Light Interferometry (SWLI) is an established 3D imaging method that allows Å (Angstrom) sensitivity in the vertical direction (z-direction). The method allows imaging static and oscillating samples with frequencies up to 5 MHz. Furthermore sub-surface imaging in visible and infrared range is possible. Stitching together sub-aperture images allows 3D characterization of large samples while maintaining the nanometer vertical precision. Label free 3D imaging of biological samples is possible by SWLI. To avoid confounded images due to optical phase changes, a biological transfer standard was developed. The standard consists of an 8-step tall stair formed with Langmuir-Blodgett deposited stearic acid films. The step height in the stair is 4 nm. SWLI is laterally diffraction limited and cannot resolve lateral features smaller than 200 nm. To overcome this limitation we developed a 3D super resolution SWLI setup. Figure 1 shows a super resolution SWLI image of a recordable BluRay-disc (BD-R) where features less than 100 nm wide and ca 20 nm are resolved [1].

Figure 1. Super resolution SWLI image of BD-R disc.

References [1] I. Kassamakov, A. Nolvi, and E. Hæggström, "3D Super-resolution Label-free Imaging," CLEO: Applications and Technology 2016, AM4O.2 (2016)

1 2 3

IL8


47

Molecular interactions in supramolecular assemblies---a single molecule study

Wenke Zhang

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R.China


The study of molecular interactions in supramolecular assemblies at single molecule level is of crucial importance for a better understanding of the formation mechanism of those elegant naturally occurring systems (such as virus particle) as well as for the building of novel functional assembly systems. However, due to the complexity of the system, it is quite challenging to study such interactions at single molecule level using AFM-based single-molecule force spectroscopy (SMFS). This presentation will discuss how to extend the usefulness of AFM-SMFS to the study of polymer interactions in polymer single crystals and intact virus particles---two model systems of macromolecule assemblies [1-4], as shown in Fig. 1. By proper sample preparation, we were able to immobilize polymer single crystal and TMV in more controlled fashion, which facilitate the pulling experiment. In addition, we demonstrate that proper labeling of the sample and the combination of AFM-imaging with SMFS are very crucial for the investigation of polymer interactions in complicated systems [2,3,5].

Figure 1. Schematic drawing of the trend for SMFS study of polymer interactions

References [1] N. N. Liu, B. Peng, Y. Lin, Z. H. Su, Z. W. Niu, Q. Wang, W. K. Zhang, H. B. Li, J. C. Shen, J. Am. Chem. Soc., 132, 11036-11038 (2010). [2] K. Liu, Y. Song, W. Feng, N. N. Liu, W. K. Zhang, X. Zhang, J. Am. Chem. Soc., 133, 3226-3229 (2011). [3] Y. Song, W. Feng, K. Liu, P. Yang, W. K. Zhang, X. Zhang, Langmuir, 29, 3853-3857 (2013). [4] N. N. Liu, Y. Chen, B. Peng, Y. Lin, Q. Wang, Z. H. Su, W. K. Zhang, H. B. Li, J. C. Shen, Biophys. J., 105, 2790-2800 (2013). [5] Y. R. Xue, X. Li, H. B. Li, J. C. Shen, Nat. Commun., 5:4348 (2014).

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48

Electronic probing of biotic-abiotic interfaces

Luisa Torsi

Dipartimento di Chimica Università degli Studi di Bari (Italy) E-mail address: [email protected]

Printable and organic bioelectronic is a highly interdisciplinary research field that aims at the development of key-technologies to investigate biointerfaces as well as to face novel challenges in life-science and medicine [1]. It currently encompasses, besides biosensors, many other different applications, including neural interfaces, tissue engineering and drug delivery. It is a powerful tool that exploits the direct interfacing of a field-effect transistor (FET) with functioning or even living bio-systems. These systems can be used to investigate fundamental aspects of bio-chemical interactions and exploit this knowledge to realize ultra-sensitive biological and chemical sensor. These systems can be used to investigate fundamental aspects of bio-chemical interactions and exploit this knowledge to realize ultra-sensitive biological and chemical sensors. Bioelectronic FET micro-devices are based on solution processed organic semiconductors but also on printable metal oxides, carbon nanotubes as well as graphenes. Novel devices structures that integrate a layer of functional biological recognition elements that is directly coupled with an electronic interface, have been lately proposed. The study of such interfaces allowed to get insights into the understanding of conformational changes occurring in the bio-systems upon interaction with external stimuli and to obtain label-free, ultra-sensitive and selective biosensing [2-5]. In particular, the ultra-sensitive, quantitative measurement of the weak interactions associated with neutral enantiomers differentially binding to odorant binding proteins immobilized to the gate of an organic bio-electronic transistor [3], will be presented. It will be shown that the transduction is remarkably sensitive as the transistor output current is governed by the small capacitance of the protein layer undergoing minute changes as the ligand-protein complex is formed. Accurate determination of the free-energy balances and of the capacitance changes associated with the binding process allows derivation of the free-energy components as well as of the occurrence of conformational events associated with ligand binding. Capacitance modulated transistors open a new pathway for the study of ultra-weak molecular interactions in surface bound protein-ligand complexes through an approach that combines bio-chemical and electronic thermodynamic parameters. References

[1] J. Rivnay et al. Chem. Of. Mat. 26, 679, 2014 [2] K. Manoli, Angewandte Chemie International Edition, 2015, 54, 12562–12576. [3] Y. Mulla et al. Nat. Comm. 6:6010 2015 [4] G. Palazzo et. al. Adv. Mater. 27:911 2015 [5] E. Macchia et al. Scientific reports 6:28085 2016

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49

Self-assembled monolayers as a platform for generation of novel 2D materials

Andrey Turchanin

Institute of Physical Chemistry, Friedrich Schiller University Jena, Jena Center for Soft Matter (JCSM) 07743 Jena, Germany


Electron irradiation of aromatic self-assembled monolayers results in their conversion into a novel 2D

carbon material Carbon Nanomembranes (CNMs) molecular nanosheets with a thickness of ~ 1 nm [1]. Similar to graphene or other atomically thin 2D materials (hBN, MoS2, etc.) they possess mechanical integrity and therefore can be transferred from their original substrates onto new substrates, fabricated as suspended sheets or stacked into van der Waals heterostructures with the precise control over their thickness. Their physical and chemical properties can be tuned via an appropriate choice of molecular precursors or their post modification, providing a flexible platform for engineering of functional 2D materials. In this talk, some examples of these materials and their device applications will be presented. These examples include: (i) biofunctional and photoactive CNMs [2]; (ii) growth of graphene with adjusted electronic and structural properties [3-4]; (iii) chemical functionalization of graphene and MoS2 field-effect devices [5]; (iv) nanolithography of free-standing atomically thin sheets [6]; (v) novel hybrid 0D/2D layered materials [7]. References [1] A. Turchanin and A. Gölzhäuser, Adv. Mater. (2016) DOI: 10.1002/adma.201506058. [2] Z. Zheng et al., Angew. Chem. Int. Ed. 49 (2010) 8493-8497 [3] D. G. Matei et al., Adv. Mater. 25 (2013) 4146-4151. [4] N.-E. Weber, S. Wundrack, R. Stosch and A. Turchanin, Small 12 (2016) 1440-1445. [5] M. Woszczyna et al., Adv. Mater. 28 (2014) 4831-4837. [6] C. Brand et. al, Nat. Nanotech. 10 (2015) 845-848. [7] Z. Zheng et al., Nanoscale 7 (2015) 13393-13397

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50

Balancing interactions: the design of molecular systems at the liquid/solid interface

Manfred Buck

EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews, KY16 9ST, United Kingdom


Directional and non-directional intermolecular interactions, molecule-substrate interactions and molecular shape are some of the parameters spanning a complex space for the design of twodimensional molecular layers. With options ranging from supramolecular patterns to densely packed layers of upright standing molecules as illustrated in Figure 1, numerous opportunities arise for surface functionalisation, templating and patterning with utmost precision. However, the prospects for such systems will depend on the extent to which we can control the energy landscape associated with this parameter space. In addition, crucial aspects of molecular selfassembly such as error correction, tolerance to intrinsic defects and molecular dynamics have to be taken into account. Presenting examples of hierarchical stepwise assembly of sub-5 nm structures on Au(111) [1, 2] and self-assembled monolayers of aromatic carboxylic acids on different metal surfaces [3,4] opportunities and challenges for molecular systems to access the bottom end of the nanoscale are addressed.

Figure 1. STM images and molecular models of two different types of molecular layers. (a) Supramolecular structure hierarchically assembled on a Au surface using a hydrogen-bonded network of melamine and perylene-3,4:9,10-tetracarboxylic diimide which act as a template for the adsorption of a phenyleneethynylene star molecule. (b) Monolayer of biphenyl-3,4’,5-tricarboxylic acid on Cu whose assembly is driven by the coordination bonding of carboxylic acid moieties to the substrate.

References [1] B. Karamzadeh, T. Eaton, I. Cebula, D. M. Torres, M. Neuburger, M. Mayor, M. Buck, Chem. Commun. 50, 14175 (2014) [2] M. T. Räisänen, A. G. Slater, N. R. Champness, M. Buck, Chem. Sci. 3, 84 (2012) [3] H. Aitchison, H. Lu, M. Zharnikov, M. Buck, J. Phys. Chem. C 119, 14114 (2015) [4] I. Cebula, H. Lu, M. Zharnikov, M. Buck, Chem. Sci. 4, 4455 (2013)

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Oral presentation abstracts

51



52


53

Enhanced Langmuir-Blodgett technique oriented to very large planar or non-

planar substrates (>> dm²) and targeted applications

O. Dellea1, O. Shavdina1, L. Berthod2, C. Ducros1, H. Marie1, G. Marchand1, S. Vignoud1, P. Fugier1, Y. Jourlin2

1CEA/LITEN, Laboratory for Innovation in New Energy Technologies and Nanomaterials, F-38054 Grenoble,

France 2Laboratory Hubert Curien, University Jean Monnet, Bâtiment F, 18 Rue du Professeur Benoît, F-42000

Saint-Étienne, France E-mail address: [email protected]

The printing of nanostructures on large rigid or flexible surfaces becomes an increasing demand from different industrial fields to enhance yields and obtain innovative properties derived from structures in the nanometer range. In this context, we develop at CEA an enhanced Langmuir-Blodgett technique able to meet industrial constraints [1] [2]. This process uses a moving liquid on which colloids are dispensed and then organized as a film, thanks to hydrodynamic forces. One of the main advantages of this process is its capability to deposit compact film of colloidal particles as monolayer of microspheres on large area (>> dm²) and non-planar substrates as well (Figure 1). Many experimental and computational works have been done at CEA with this technology for several years. The authors will present the process developed to obtain compact films of particles on very large surfaces and on non-conventionnal substrates, enabling to open the route to new fields of applications. The authors will focus and illustrate their presentation from two applicationsbased examples achieved at CEA: i) In the field of thin film solar cells, we introduce a simple method for preparing textured reflectors using hexagonal close packed (HCP) silica microspheres films which lead to 10% of enhancement of the solar cell efficiency, ii) In the field of sensors, opals were manufactured with the enhanced Langmuir-Blodgett technique and were used to mold molecularly imprinted polymers (MIP) as inverse opals. These inverse opals, which exhibit a shift of the Bragg peak upon recognition of a specific analyte by the MIP, were successfully tested as photonic sensors.

Figure 1. 2D array of SiO2 microspheres on metallic film (length 1 m, width 30 cm) (left) and on glass cylinder (centre), example of textured reflector (right) References [1] O. Delléa, O. Shavdina, P. Fugier, P. Coronel, E. Ollier, S.F. Désage, IPAS 2014, 435, 107─117 (2014). [2] O. Shavdina, L. Berthod, T. Kämpfe, S. Reynaud, C. Vei

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54

Langmuir−Blodgett colloidal assembly: An electrospray update

Huali Nie1,2 and Jiaxing Huang1

1 Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208,

United States 2 College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620,

China


LB assembly has been routinely used in research labs for nearly a century for preparing molecular and colloidal monolayers. Volatile, water-immiscible solvents are convenient for spreading, but they have also been a “pain” in terms of colloidal stability, processability and chemical safety, making scaled up applications difficult. The use of water-miscible spreading solvents would avoid all of these problems, but it tends to lose most materials to water subphase due to intermixing, making such LB colloidal assembly ineffective and hard to standardize or reproducible. This dilemma can be solved by electrospray spreading, in which the small volume of the microdroplets is readily depleted during initial spreading, leaving no extra solvent for mixing. As is demonstrated with several prototypical colloidal systems, electrospray allows high-yield, high-throughput spreading of colloidal materials on water surface using environmentally benign, water-miscible solvents (even water itself), which liberates this century-old technique from many constrains related to material processing and significantly expands its scope.[1] Electrospray apparatus can be readily automated and fully integrated with existing LB systems, which should help to standardize this technique and scale it up from LB assembly to LB manufacturing.

Figure 1. Electrospray enables high-yield spreading of ethanol on water surface, which is visualized using Au/PVP nanoparticles (c, d). This is in contrast to conventional spreading that results in complete intermixing (a-b).

References [1] Nie, H.L.; Dou X; Tang Z.H.; Jang, H.D.; Huang J.X. J. Am. Chem. Soc. 137, 10683−10688 (2015).

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55

The role of modifying molecular chains in the formation of organized molecular

films of organo-modified inorganic particles

Atsuhiro Fujimori

Graduate School of Science and Engineering, Saitama University 255, Shimo-okubo, Sakura-ku, Saitama, Japan 338-8570


The role of organo-modifying molecular chains in the formation of molecular films of organo-modified nanodiamond [1, 2] is discussed herein based on interfacial chemicalparticle-integration of organo-modified nanodiamond having a particle size of 5 nm. The surface of nanodiamond is known to be covered with a nano-layer of adsorbed water. This water nano-layer was exploited for organo-modification of nanodiamond with long-chain fatty acids viaadsorption, leading to nano-dispersion of nanodiamond in general organic solvents as a mimic of solvency. The organo-modified nanodiamond dispersed "solution" was used as a spreading solution for depositing a mono-"particle" layer on the water surface, and a Langmuir particle layer was integrated at the air/water interface[3-6]. Multi-"particle" layers were then formed viathe Langmuir-Blodgett technique, and were subjected to fine structural analysis. The effect of organo-modification enabled integration and multilayer formation of inorganic nano-particles due to enhancement of the van der Waals interactions between the chains (Fig. 1). That is to say, the "encounter" between the organo-modifying chain and the inorganic particles led to solubilization of the inorganic particles and enhanced interactions between the particles, which can be regarded as imparting new function to the organic molecules. The morphology of the single-particle layer was maintained after removal of the organic region of the composite viathe baking process, whereas the regularity of the layered period was disordered. Thus, the organic chains are essential as modifiers for maintenance of the layered structure. References [1] A. Fujimori, Y. Kasahara, N. Honda, S. Akasaka, Langmuir, 31, 2895-2904, (2015). [2] M. A. A. Mamun, Y. Soutome, Y. Kasahara, Q. Meng, S. Akasaka, A. Fujimori, ACS Appl. Mater. Interf., 7, 17792-17801, (2015). [3] A. Fujimori, N. Honda, H. Iwashia, Y. Kaneko, S. Arai, M. Sumita, S. Akasaka, Colloids Surf. A, 446, 109-117, (2014). [4] A. Fujimori, Y. Kaneko, T. Kikkawa, S. Chiba, Y. Shibasaki, J. Colloid Interf. Sci., 418, 338-349, (2014). [5] A. Fujimori, K. Ohmura, N. Honda, K. Kakizaki, Langmuir, 31, 3254-3261, (2015). [6] Q. Meng, N. Honda, S. Uchida, K. Hashimoto, H. Shibata, A. Fujimori, J. Colloid Interf. Sci., 453, 90-99, (2015)

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Figure 1. Schematic illustration of formation of organo-

modified inorganic nanoparticle and their application.


56

Influence of acidity and temperature on the quantum dots Langmuir monolayer

formation

Gorbachev I.A.1, Shtykov S.N.2, Brezesinski G.3, Glukhovskoy E.G.1

1 National Research Saratov State University named after N.G. Chernyshevsky, Education and Research Institute of Nanostructures and Biosystems, Saratov, Astrahanskaya 83, 410012 Russia

2 National Research Saratov State University named after N.G. Chernyshevsky, Institute of chemistry, Saratov, Astrahanskaya 83, 410012, Russia

3 Max Planck Institute of colloids and interfaces, Germany, Max Planck Institute of Colloids and Interfaces Potsdam-Golm Science Park Am Mühlenberg 1 OT Golm 14476 Potsdam


One of the simplest creation way of quantum dots thin film is a Langmuir-Blodgett technology [1]. There are many external parameters has an influence on the monolayer formation process for instance acidity and temperature. Generally, the influence of subphase temperature and acidity on monolayer stability was not studied in detail. Therefore, main task of this work is the studies of the influence of these subphase parameters on the stability of hydrophobic CdSe/CdS/ZnS QD monolayers stabilized by oleic acid. Compression isotherms of Langmuir monolayers formed on subphase with temperature alternate in range of 4 to 34 and acidity of 2 to 12,6 were showed in images below. So increasing of the subphase temperature leads to decreasing of the maximal surface pressure and changing in the monolayer phase condition from liquid condensed to liquid expanded. The increasing of the pH value in the range of 7 to 12,6 leads to ionization of oleic acid headgroup and as a result to extremely decreasing of the monolayer gas phase area. The same decreasing of monolayer gas phase area could be observed at the low pH value (<7) but in this case it connected with impossibility of oleic acid molecules headgroup ionization [2]. The research supported by grant of the Russian Science Foundation (project №14-12-00275) and the National Research Saratov State University

Figure 1. Compression isotherms of monolayer formed at the different conditions.

References [1] Lambert K., Wittebrood L., Moreels I., Deresmes D, Grandidier B, Hens Z., Langmuir-Blodgett monolayers of InP

quantum dots with short chain ligands J Colloid Interface Sci. 300, 597 (2006). [2] Kanicky J.R. and Shah D.O., Effect of degree, type, and position of unsaturation on the pKa of long-chain fatty acids J Colloid Interface Sci. 256, 201 (2002)

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57

Properties of a Langmuir monolayer of polymer particles at an air/aqueous

interface after the collision by an external particle

Cathy E. McNamee1, Hans-Juergen Butt2, Michael Kappl2

1 Shinshu University, Tokida 3-15-1, Ueda 386-8567, Japan 2 Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.


Dispersions of liquids or bubbles in liquids can be stabilized by adsorbing particles at the air/liquid or liquid/liquid interface. The effectiveness of the stabilization is affected by the size, number, and type of particles and by the packing density and structures formed by those particles at the interface. A successful stabilization can be better realized, if we understand the mechanism and forces responsible for the adsorption of particles to deformable interfaces, and the factors affecting the physical properties of the interface once particles have adsorbed. We modelled a particle stabilized bubble that was dispersed in a liquid by creating Langmuir monolayers of polystyrene particles loaded with poly(N,N-dimethylaminoethylmethacrylate) (“PDMA-PS”) at air/aqueous interfaces. We determined the effect of the particle charge and packing density on the forces and physical properties of the monolayers at air/aqueous interfaces. We subsequently studied ways to vary the strength of the particle monolayers. The physical properties of the monolayers were investigated using the Monolayer Particle Interaction Apparatus, which measured the surface pressure-area isotherms of the monolayers and the forces between a particle (probe) in the water subphase and the Langmuir monolayer at the air/water interface. The particles in the monolayer at an air/aqueous interface were found to move laterally for loose packing densities, giving monolayers with a low stiffness. This lateral movement of the particles decreased as the packing density increased. The particles at high packing densities, however, were also seen to move, when a particle (probe) from the aqueous subphase collided with the particles in the monolayer. This resulting particle movement reduced the stiffness of the Langmuir monolayer [1]. We next tried to reduce the movement of the PDMA-PS particles caused by colliding particles. This was achieved by introducing links between the PDMA-PS particles in the Langmuir monolayer by adding poly(2-hydroxyethyl methacrylate) (“PHEMA”) to the monolayer. Strings of PDMA-PS particles were observed for the 27% particle-73% PHEMA system. The occurrence of these strings decreased as the ratio of PHEMA in the mixed monolayer decreased, indicating that PHEMA could link the PDMA-PS particles. The stiffness of the mixed monolayer was seen to increase as the ratio of PHEMA in the mixed monolayer increased, even after a particle from the aqueous subphase collided with the monolayer. It was concluded that the stiffness of the particle monolayer could be changed by adding a polymer to the Langmuir monolayer of particles. References [1] C.E. McNamee, S. Fujii, S. Yusa, Y. Azakami, H.-J. Butt and M. Kappl, Colloid Surf. A-Physicochem. Eng. Asp., 470,

322-332 (2015).

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58

Rubber particle proteins, HbREF and HbSRPP, interact differently with lipids

extracted from RRIM600 H. brasiliensis latex

K. Wadeesirisak1, S. Castano2, K. Berthelot2,3, F. Peruch3, L. Vaysse4, F. Bonfils5, K.Ratanaporn1, S. Liengprayoon5, C.Bottier4and S. Lecomte2

1Faculty of Agro-Industry, Kasetsart University, 10900 Bangkok, Thailand

2CNRS, CBMN, UMR 5248, Univ. Bordeaux, Bordeaux INP, 33600 Pessac, France 3CNRS, LCPO, UMR 5629, Univ. Bordeaux, Bordeaux INP, 33600 Pessac, France

4 CIRAD UMR IATE- HRPP -Kasetsart University, 10900 Bangkok, Thailand

5CIRAD-INRA-SupAgro-Univ. Montpellier 2, UMR 1208 IATE, 34060 Montpellier, France

6Kasetsart Agricultural and Agro-Industrial Product Improvement Institute, Kasetsart University, 10900 Bangkok, Thailand


Latex tapped from Hevea brasiliensis (rubber tree) contains rubber particles dispersed in C-serum.The spherical Hevea rubber particle can be described as a core of polymer surrounded by a biological membrane made of lipids and proteins. While it is agreed that the particle is made of an hydrophobic core of poly(cis-1,4-isoprene), the structure and composition of its lipid-protein surface membrane is still controversial [1-3]. Two major proteins are abundant at the surface of Hevea rubber particles namely, the rubber elongation factor (HbREF) and the small rubber particle protein (HbSRPP), which are mainly located at the surface of large rubber particles and small rubber particles, respectively [4]. Lipids extracted from rubber particles include phospholipids (PL), glycolipids (GL) and neutral lipids (NL) [5]. Recently, an approach in Langmuir films was applied to study the interactions of recombinant REF and SRPP with synthetic lipids (DMPC and asolectin) [6]. In the present study, we used surface pressure kinetics, ellipsometry, Brewster angle microscopy and polarization-modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS) to investigate the interactions between recombinant REF and SRPP with native lipids extracted and purified from Hevea RRIM600 latex collected in the Chanthaburi province, Thailand. Monolayers of native phospholipids, glycolipids and neutral lipids were successfully formed at the air-water interface. Pure lipid (PL, GL or NL) and mixed lipid-protein Langmuir monolayers were studied. The interactions between REF and SRPP with lipids are completely different. SRPP interacts mostly in surface with all types of lipids (PL, GL or NL), without modification of its secondary structure. In contrast REF inserts deeply in the lipid monolayer with all lipid classes. When it interacts with NL, REF is able to switch from a

conformation in -helices to -sheet structures, as in its aggregated form (amyloid form) [7]. Interactions between REF and NL may have specific role in the plugging of rubber particles. References [1] Cornish K., Wood D. F., Windle J. J., Planta,210, 85-96 (1999). [2] Nawamawat K., Sakdapipanich J. T., Ho C. C., Ma Y., Song J., Vancso J. G., Colloid Surface A, 390, 157-166 (2011). [3] Rochette C. N., Crassous J. J., Drechsler M., Gaboriaud F., Eloy M., de Gaudemaris B., Duval J. F. Langmuir,29, 14655-65 (2013). [4] Berthelot K., Lecomte S.,Estevez Y., Peruch F., Biochimie,106, 1-9 (2014). [5] Siler, D. J., Goddrich-Tanrikulu M., Cornish, K., Stafford, A. E., McKeon, T. A. (1997). Plant Physiology and Biochemistry, 35, 881-889 (1997). [6] Berthelot K., Lecomte S., Estevez Y., Zhendre V., Henry S., Thévenot J., Dufourc E.J., Alves I. D., Peruch F., BBA Biomembranes, 1838, 287-299 (2014). [7] Berthelot K., Lecomte S., Estevez Y., Coulary-Salin B., Peruch F., BBA - Proteins and Proteomics, 1844, 473-485 (2014).

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59

In situ luminescence measurements of Eu3+-containing polyoxometalate Langmuir

and Langmuir-Blodgett films

H.H.S. Oliveira1,2, M.A. Cebim1, M.R. Davolos1 1 Instituto de Química, UNESP - Univ Estadual Paulista, Campus de Araraquara, SP, Brazil

2 Instituto Federal de Educação, Ciência e Tecnologia de São Paulo - IFSP, Campus Matão, SP, Brazil


Two-dimensional systems, as nanostructured thin films on the solid surfaces have potential application in nanotechnology and self-assembly processes of these systems have been increasingly studied and employed [1-2]. The evaluation of the interfaces dynamics in two-dimensional systems are important for the determination of strategies to construction, manipulation and control of these nanoarchitectures. Luminescent Langmuir-Blodgett films (LB) constitute two-dimensional systems with potential application in optoelectronics. In this work, luminescent Langmuir and Langmuir-Blodgett films of DODA(dimethyldioctadecylammonium)/[Eu(W5O18)2]9- systems were successfully prepared. To understand the luminescent properties of the films, in situ photoluminescence spectroscopy (PLS) measurements were performed during the molecules organization using the new instrumentation developed by the research group of the Luminescent Materials Laboratory (UNESP, Brazil) and the results were correlated to different aggregation states in the Langmuir films. Fig. 1(a) shows that the emission intensity increases in smaller molecular area, however, the increase becomes less pronounced at liquid (L) and solid (S) aggregation states. At smaller molecular areas, the molecules concentration at surface is higher, increasing the emission intensity. Nevertheless, the arrangement of the molecules makes the quenching luminescence processes more important. In the Fig. 1(b), the R21 parameter increases in smaller molecular area, probably because the changes in the aggregation states decreases the local symmetry around Eu3+ ions, evidencing different structural arrangement of the monolayer in gas (G), liquid (L) and solid (S) analogous states. Multilayered LB films were prepared by deposition of 11, 21, 31, 41 and 51 monolayers on glass substrate. In situ luminescence spectra of the LB films were recorded on the Langmuir-Blodgett through every 10 depositions. Emission intensities of the LB films present linear increase with the depositions number and the spectral profile is different from that observed to the monolayer, indicating that structural changes occur during the transfer process of the monolayer to the solid substrate.

Figure 1. (a) Luminescence intensity and (b) R21 parameter of the DODA/[Eu(W5O18)2]9- monolayer correlated to the surface pressure area isotherm.

References [1] ZHUANG, X. D. et al. Advanced Materials 27, 403-427 (2015). [2] SAKAKIBARA, K.; HILL, J. P.; ARIGA, K. Small Journal 7, 1288-1308 (2011).

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Optical molecular switches based on newly synthetized azobenzene derivatives

E. Piosik1, A. Modlinska1, J. Makowiecki1, Z. Galewski2, T. Martynski1

1 Institute of Material Research and Quantum Engineering, Poznan University of Technology, Piotrowo 3, 60-965, Poznan, Poland

2 Faculty of Chemistry, University of Wroclaw, J. Curie 14, 50-383 Wroclaw, Poland


The concept of “programmable” and “reconfigurable” soft matter has emerged in science and technology in the last decades due to the possibility of switching between two well-defined states with different chemical, physical and functional properties by external stimulation such as light irradiation or heat treatment. The azobenzene derivatives are an example of organic compounds exhibiting reversible trans-cis photoisomerization. The electronic absorption spectrum of the compounds containing azobenzene chromophores is characterized by two separated spectral bands. The high-intensity band in the ultraviolet region (≈360 nm) refers to the π-π* transition, while the band with the much lower intensity in the visible range (≈450 nm) is related to the n-π* transition. The energy of ultraviolet light corresponds to the energy gap of the π-π* transition and can cause the conversion from the trans to the cis isomer. The back-transition is possible by visible light irradiation or thermal treatment. The photoisomerization process involves changes in the molecular conformation and cross-sectional area of the molecule due to difference in the shape of trans and cis isomers. In the result the macroscopic properties of material such as refractive index, dielectric constant and dichroic ratio may change. From this reason azobenzene derivatives have a great application potential in optical storage devices, molecular junctions of electronic devices, command layers of liquid crystal displays or holographic gratings. The research on low-dimensional systems of functional materials like 2D layer architectures are of particular interest due to a strong interface at interfaces and enhanced interactions between the stimulus and molecules in the layer compared to the bulk material. Here, we demonstrate the reversible photoisomerization of four newly synthetized azobenzene derivatives in chloroform solutions as well as in the molecular layers at air/water and air/solid state interfaces (Langmuir and Langmuir-Blodgett films). All investigated compounds form stable and compressible Langmuir films. The course of surface pressure-mean molecular area isotherms is strongly influenced by the fraction of trans and cis isomers in monolayer. The mean molecular area for azobenzene derivative in the cis form is significantly higher than for the all trans isomers. Monolayers were transferred in both forms at particular surface pressure onto quartz substrates with the transfer ratio near one for spectroscopic characterization. On the basis of recorded isotherms and absorption spectra conclusions about molecular organization and aggregation of different isomer molecules in Langmuir-Blodgett films were drawn. Textures of the LB films were characterized in nanoscale by atomic force microscopy AFM.

Acknowledgments Presented work has been financed by the Ministry of Science & Higher Education in Poland in 2016 year under Project No 06/65/DSMK/0003.

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61

Polymerization and colour transition of polydiacetylene alcohols layers.

S. Spagnoli1, M.-C. Fauré2,3, M. Goldmann2,3,5, M. Schott2, C. Allain4

1 LIPhy : 140 avenue de la physique, BP87, 38402 Saint Martin d’Hères France. 2 INSP : 4 place Jussieu 75252 Paris Cedex 05 France.

3 Faculté des Sciences Fondamentales et Biomédicales, 45 rue des Saints-Pères 75006 Paris France 4 PPSM : 61 avenue du président Wilson 94235 Cachan France

5 Synchrotron SOLEIL L’Orme des Merisiers Saint-Aubin-BP48 91192 Gif/Yvette Cedex France E-mail address: [email protected]

Polydiacetylenes (PDA): =(CR-C- -CR’)n= are conjugated polymers, generally obtained by UV irradiation, that undergo a colour transition, blue to red, when they are stimulated (Fig. 1). This transition corresponds to a conformational and electronic structure change of the polymerized chain. If an appropriate group is attached at the end of R’, the colour transition can be selectively triggered by reaction of this group with a suitable target (molecule, protein, ion etc.). These compounds present therefore suitable properties to be used as sensors [1,2] whose efficiency is related to the surface/bulk ratio. We use the versatility of the molecules forming a Langmuir film to study and control the basic mechanism of this transition which is still not understood.

We have studied the newly synthesized alcohol DAs 13-nOH: CH3(CH2)12-C-CC-C-(CH2)n-1-CH2OH with n=4, 6, 8, 9. These molecules have been chosen for their insensitivity to pH (a pH change triggers the color transition). They have been studied by surface pressure-molecular area isotherms. One observes a liquid expanded (LE) phase followed by a (LC) phase before the collapse to the trilayer structure. However, the monolayer-trilayer transition appears as totally reversible in this case. The polymerization and the color transition of the film under UV irradiation have been followed in-situ by UV-Visible spectroscopy (Fig. 1). These two characteristics depend on the molecular architecture of the monomer. The film structure has been studied by GIXD on water subphase in: non-irradiated monolayer and trilayer states (monomer case) and in-situ irradiated monolayer (polymerized case). Among the various results, one underlines the disappearance of the structure of the non-irradiated monolayer under compression indicating an unusual transition of the LC phase. Results of this first series of experiments will be discussed.

Figure 1. 13-4OH (left) in-situ absorption spectra during UV polymerization at 0.07nm2/molecule, (right) reversibility of the monolayer-trilayer transition evidenced by compression-expansion cycle.

References [1] M.A. Reppy and B.A. Pindzola, Chem. Comm. 42, 4317 (2007) [2] X. Chen, G. Zhou, X. Peng and J. Yoon, Chem. Soc. Rev. 41, 4610 (2012)

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62

Spectral properties of chlorinated perylene-3,4,9,10-tetracarboxylic acid

derivatives in Langmuir-Blodgett films

(empty line)

E. Piosik1, A. Synak2, R. Hertmanowski1, J. Makowiecki1, T. Martynski1

1 Institute of Material Research and Quantum Engineering, Poznan University of Technology, Piotrowo 3,

60-965, Poznan, Poland 2 Institute of Experimental Physics, University of Gdansk, Wita Stwosza 57, 80-952 Gdansk, Poland


In the last decades organic semiconductors have attracted attention due to their potential application in optoelectronic devices such as solar cells, light emitting diodes, field effect transistors, dye lasers, sensors of different types, and other flexible and large area devices. They can be easy and low cost chemically tuned to obtain desired spectroscopic, electronic, and processing properties. Organic semiconducting materials are classified as hole transporting (p-type) and electron transporting (n-type) depending on carrier type, which is the most effectively transported through semiconductor. Chemically stable p-type semiconducting materials possess properties, which meet application requirements. In contrast, there is a lack of electron transporting organic semiconductors due to low chemical stability under ambient conditions, low carrier mobility, and difficulties in the synthesis. The n-type organic semiconductors can be synthetized by attaching strong electron-withdrawing atoms such as F, Cl, CN, or alkanoyl and perfluorobenzene to the core of molecules. Here, we present a spectroscopic investigation of p-type (Pn) and n-type (PCln) derivatives of perylene-3,4,9,10-tetracarboxylic acid with four lateral alkyl chains composed of n number of carbon atoms (n = 2 – 13) in monomolecular films created by using the Langmuir technique. To the main perylene skeleton of PCln dyes molecules have been attached additionally chlorine atoms in bay positions. The perylene derivatives exhibit high molar absorption coefficients and near 100 % luminescence quantum yields in nonpolar organic solvents. In the densely packed, well-ordered structures, such as Langmuir-Blodgett films, they create aggregates in the consequence of π-π interactions between perylene cores of the molecules. The aggregation process reduces the luminescence quantum yield, that can restrain applications of these dyes in optoelectronic devices. The substitution of halogen atoms results in a strong twist of the perylene core. This effect can limit the interactions between molecules in films and therefore can improve their spectral properties. The aggregation process of Pn and PCln dyes was investigated by steady-state and pulse spectroscopy techniques (TCSPC and TRES). The luminescence quantum yields (QY) of Langmuir-Blodgett films were determined using the integrating sphere method. QY of the PCn dyes in organic solvents is lower than for Pn ones. Langmuir-Blodgett films of PCn dyes show two-exponential decay of fluorescence with short lifetime comparable to the monomeric form in solution and longer emission lifetime an attribute of aggregates. Acknowledgments Presented work has been financed by the Ministry of Science & Higher Education of Poland, Project No

06/65/DSPB/0516

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63

Effects of Pressure on Resistance in Au(dmit)2 LB Films

Yasuhiro F. Miura1, Hiroyuki Hasegawa2, Kiyoshi Torizuka3, Yoshiya Uwatoko3

1Toin University of Yokohama, 1614 Kurogane-cho, Aoba-ku, Yokohama, 225-8503 JAPAN 2Graduate School of Science, Hokkaido University, Kita-10 Nishi-8 Kita-ku, Sapporo, 060-0810 Japan 3Institute for Solid State Physics, University of Tokyo, Kashiwanoha 5-1-5, Kashiwa, 277-8581 Japan


Since lipid bilayer membranes have a highest sensitivity to high pressure among biomolecules, the pressure effect on “artificially-fabricated lipidic nanostructures” is also an interesting research subject [1]. In this paper, we focus on pressure effects on resistance of the LB film based on ditetradecyldimethylammonium-Au(dmit)2 salt [2C14N+Me2-Au(dmit)2, Fig. 1]. The LB film exhibits a high room-temperature conductivity of 40 S/cm after electro-oxidation showing a metallic behaviour down to 56 K under vacuum [2]. It also shows a magnetic anomaly, which suggests superconductivity below 3.9 K [3]. We postulate that the resistance is sensitive to pressure considering that the ammonium with two hydrocarbon chains should have various pressure-dependent ordered states as in lamella structures of phospholipids. The 2C14N+Me2-Au(dmit)2 salt was spread on pure water and was transferred onto a 0.1-mm thick polyester substrate by the horizontal lifting technique. The resistance was measured along the film plane under pressure in a hydrocarbon medium. Figure 2 shows the room-temperature resistance of the 20-layered LB film plotted against pressure. With increasing pressure, the resistance gradusally decreases, and at 0.74 GPa, it is 58 % smaller compared to the ambient value. Since our atomic force microscopy observation has revealed that the LB film consists of 2D crystalline domains with lateral sizes of 5.20±1.52 μm [4], the resistance behaviour may vary depending on the gap distance of the electrodes. We will present resistance behaviours measured using various electrode gaps (5 μm to 500 μm) in a wide temperature range of 0.7 K – 298 K. References [1] H. Isotalo, J. Paloheimo, Y. F. Miura, R. Azumi, M. Matsumoto, T. Nakamura, Phys. Rev. B 51, 1809 (1995) [2] Y. F. Miura, M. Kitao, H. Matsui, M. Sugi, M. Hedo, K. Matsubayashi, Y. Uwatoko, Jpn. J. Appl. Phys. 47, 8884 (2008). [3] Y. F. Miura, M. Horikiri, S.-H. Saito, M. Sugi, Solid State Commun. 113, 603 (2000). [4] Y. F. Miura, H. Matsui, K. Inoue, J. Hoshino, K. Ikegami, Synth. Met. 207, 54 (2015).

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Figure 1. 2C14N+Me2-Au(dmit)2 salt.

Figure 2. The resistance of a 2C14N+Me2-Au(dmit)2 LB film plotted against pressure; the measurement was performed as schematically shown by the inset.


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Structural characterization of self-organized mono- and multilayers of partly

fluorinated polydialkoxyphosphazenes at the air/water Interface

A.I. Buzin1, G. Brezesinski2, V.S. Papkov3, S.N. Chvalun1,4

1Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, Profsoyuznaya 70, 117393 Moscow, Russia

2Max Planck Institute of Colloids and Interfaces, Am Muhlenberg 1 OT Golm, 14476 Potsdam 3Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences, Vavilova 28, 119991

Moscow, Russia 4National Research Centre “Kurchatov Institute”,Ak. Kurchatova 1, 123182 Moscow, Russia

E-mail address : [email protected]

The layering transitions of mesomorphic poly[bis-(2,2,3,3-tetrafluoropropoxy)phosphazene], poly[bis-(2,2,3,3,4,4,5,5-octafluoropentoxy)phosphazene] and poly[bis-(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-heptoxy)phosphazene] induced by compression were found to result in the formation of stable multilayers directly at the air/water interface. This phenomenon is discussed with particular emphasis on its in situ structural characterization by Brewster angle microscopy, infra-red spectroscopy, synchrotron grazing incidence X-ray diffraction and X-ray reflectivity data [1]. In the uncompressed state Brewster angle microscopy images demonstrate a partial coverage of the surface by solid-like islands. Further compression results in the formation of an uniform monolayer followed by layer-by-layer growth manifested by pronounced steps in the pressure/area isotherm. Grazing incidence X-ray diffraction reveals only one diffraction peak for the monolayer as well as for multilayers, which corresponds to an interchain spacing d = 12.3, 15.3 and ~17.5 Å for the three samples studied, correspondingly. The in-plane correlation length ξxy reaches 350 Å for the uncompressed monolayer and up to 470 Å for the tetralayer. In poly[bis-(2,2,3,3-tetrafluoropropoxy)phosphazene] after formation of the 4-layer thick film the transition into a 3D crystalline triclinic phase with a = 13.19 Å, b = 11.42 Å, c = 4.83 Å, α = 90o, β = 102o, and γ = 116o is observed. Such 3D phase is not observed in the other two polyphosphazenes studied. The topography of mono- and multilayers transferred onto solid substrates was analyzed by scanning probe microscopy. The thickness values of the floating polymer layers estimated from the Bragg rod’s width, X-ray reflectivity measurements and scanning probe microscopy are in good agreement. On this basis we conclude that partly fluorinated polydialkoxyphosphazene films possess high degree of stable structural order. Acknowledgements This work was supported by Russian Science Foundation (project 14-13-01402).

References [1] Buzin A.I., Brezesinski G., Tur D.R., Papkov V.S., Bakirov A.V., Chvalun S.N. Macromolecules 48 3327-3336 (2015).

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Phase-separation in mixed hydrogenated-perfluorinated fatty acid monolayers: Structure – composition relationships

Matthew F. Paige1, Jeveria Rehman1, David Sowah-Kumah1, Hessamaddin Younesi Araghi1

1University of Saskatchewan, Department of Chemistry, 110 Science Place, Saskatoon, SK., Canada.


Phase-separation of immiscible surfactants provides a useful approach for manipulating the composition, morphology and mechanical properties of thin films at air-water and solid-air interfaces. Our research group has been investigating phase-separation in a variety of mixed fluorocarbon-hydrocarbon monolayer films with an ultimate goal of developing a detailed understanding of how film properties correlate with the molecular structure of film constituents (see [1-2], for example). In this paper, we describe a series of simple mixed film systems, consisting of mixtures of perfluorinated fatty acids and hydrogenated fatty acids, which exhibit unique and controllable film morphologies (Fig. 1). We describes recent efforts at chemical mapping in these systems, using a combination of atomic force microscopy, Brewster angle microscopy and TOF-SIMS imaging, complemented by thermodynamic miscibility measurements on the Langmuir trough. Attempts to develop a simple model that describes the diverse film morphologies and mixing thermodynamics in terms of the underlying molecular structures of the film constituents are described as well as future research directions in extracting molecular level (crystallographic) information on film structure.

Figure 1. A) Atomic force microscope image (10 m x 10 m)of a phase-separated Langmuir Blodgett monolayer prepared from a mixture of arachidic acid and perfluorotetradecanoic acid; B) Brewster angle microscope image of the same monolayer film at the air-water interface.

References [1]S. E. Qaqish and M. F. Paige, Langmuir 23, 10088-10094 (2007) [2] A. Eftaiha and M.F. Paige, J. Colloid Interface Sci. 380, 105-112 (2012)

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Surface behaviour of Gemini type perfluorinated surfactants with DPPC at the air-water interface - spacer length effect

Riku Kato, Hiromichi Nakahara, Osamu Shibata

Department of Biophysical Chemistry, Faculty of Pharmaceutical Sciences, Nagasaki International University, 2825-7 Huis Ten Bosch, Sasebo 859-3298, Japan


A fluorocarbon chain has lower cohesiveness and higher rigidity than hydrocarbon chains. In addition, a fluorocarbon has simultaneous hydrophobicity and lipophobicity. Hence, fluorinated surfactants show some special properties such as high surface activity, and chemical and biological inertness. In terms of surface activity, fluorinated surfactants are more efficient than hydrogenated surfactants because the surface tension can be reduced by small amounts of fluorinated surfactants. Moreover, the feature of hydrophobicity and lipophobicity provides phase separation and self-assembly. These properties are useful for applications in various fields such as biomedical and industry fields [1]. Perfluorinated double long-chain salts with divalent counterions with various hydrocarbon spacer lengths have been synthesized in recent years. The solution properties and the interfacial behaviour of fluorinated compounds have been investigated previously [2, 3]. It is found that the solution properties and the interfacial behaviour depend on the spacer length. Herein, the binary monolayer properties of the fluorinated compounds and dipalmitoylphosphatidylcholine (DPPC) were investigated to understand the spacer length effect and an aspect of biomembrane interaction on their interfacial behaviour.

Experimental:

The fluorinated compounds, 1,1’-(1,ω-alkanediyl)-bispyridinium perfluorotetradecane carboxy-late (abbreviation: CnBP(FC14)2; n = 2, 6, 10), were synthesized. DPPC was obtained from Avanti Polar Lipids

(Alabaster, AL). Surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms were measured on 0.15 M NaCl at 298.2 K. Brewster angle microscopy (BAM), fluorescence microscopy (FM) and atomic force microscopy (AFM) were also employed.

Discussion: We have investigated the behaviour of binary Langmuir monolayers of DPPC and CnBP(FC14)2. Two-dimensional phase diagrams were constructed on the basis of the disordered/ordered phase transition pressure and the monolayer collapse pressure versus the molar fraction of CnBP(FC14)2 (XCnBP(FC14)2). The transition pressures and collapse pressures changed against XCnBP(FC14)2. In the morphology (BAM and FM), the dispersion degree of two regions (ordered and disordered) were depending on the spacer length of Gemini type perfluorinated surfactants. The miscibility is also confirmed by AFM at nanometer scales. References [1]M. P. Krafft, Soft Matter. 2015 (30):5982-5994. [2] Y. Matsumoto, H. Nakahara, Y. Moroi, O. Shibata, Langmuir 23 (2007) 9629-9640. [3] J. Masuda, H. Nakahara, S. Karasawa, Y. Moroi, O. Shibata, Langmuir 23 (2007) 8778-8783.

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Semifluorinated alkanes monolayer at the air water interface

P. Fontaine1, L. Bardin1,2, M.-C. Fauré2,3, E. Filipe4, M. Goldmann2, 3, 1

1 SIRIUS Beamline, Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin, BP48, 91192 Gif sur Yvette Cedex, France

2 Institut des NanoSciences de Paris, Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05,France

3 Faculté des Sciences Fondamentales et Biomédicales, Université Paris Descartes, 45 rue des Sts-Pères, 75006 Paris, France

4 Centro de Quimica Estrutural, Instituto Superior Tecnico (IST), Av. Rovisco Pais, 1049-001 Lisboa, Portugal.


Despite the lack of polar head group semifluorinated alkanes (CnF2n+1CmH2m+1, FnHm for short) form Langmuir monolayers ie. mono-molecular thick layer at the air-water interface. Grazing Incidence Small Angle X-ray Scattering (GISAXS) demonstrated that these molecules on liquid surface self assemble in a hexagonal array of nano-domains with a very large parameter (typ. 30 nm) [1] (Fig 1-A). This network is observed on water for different hydrocarbon chain length [2]. This structure is in agreement with the domain size observed by Atomic Force Microscopy (AFM) on silicon substrate [3]. However, the stability even after collapse [4] of such domains remains puzzling. On high-resolution AFM images, the domains shape appears as separated by a hump (Fig. 1-B). Macroscopic measurement combined with GISAXS and wide-angle x-ray scattering (GIXD) suggest that some molecules do not belong to the domains made of upright molecules. Indeed, Qxy-Qz GISAXS spectrum can be simulated by considering a corona representing lying molecules around the domains (Fig. 1-C). The presence of such lying molecules could explain the stability of the structure against coalescence of the domains upon compression of the monolayer in relationship with the polar nature of the substrate and the dipole of the SFA molecules.

A B C

Figure 1. A: Qz-integrated GISAXS spectrum of a F8H16 monolayer. All diffraction peaks can be indexed on a hexagonal lattice of parameter 33.6nm. B: AFM image of a spin-coated F8H18 layer on silicon substrate. C: Simulated GISAXS spectra of FnHm domains surrounded by a corona of lying molecules, lines are the position of the maximum of intensity along Qz for simulation and experiment.

References [1] P. Fontaine, M. Goldmann, P. Muller, M.C. Fauré, O. Konovalov, M.P. Krafft, J. Am. Chem. Soc. 127, 512-513 (2005). [2] L. Bardin, M.-C. Fauré, D. Limagne, C. Chevallard, O. Konovalov, E. J. M. Filipe, G. Waton, M.-P. Krafft, M.

Goldmann, P. Fontaine, Langmuir, 27, 13497-13505 (2011). [3] L. Bardin, M.-C. Fauré, E. J. M. Filipe, P. Fontaine, M. Goldmann, Thin Solid Films, 519, 414–416 (2010). [4] P. Fontaine, M.-C. Fauré, L. Bardin, E. J. M. Filipe, and M. Goldmann, Langmuir , 30 , 15193-15199 (2014).

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First observation of 3D aggregates in a single-component Langmuir film below the

ESP. Nanothermodynamics explanation. Possible sensor applications.

George R. Ivanov

Laboratory for Nanoscience and Nanotechnology, University of Architecture, Civil Engineering and Geodesy, 1 blvd. Hr. Smirnenski, 1046 Sofia, Bulgaria


Single component monolayers from Diplamitoyl Phosphatidyl Ethanolamine head labelled with the fluorescent chromophore NitroBenzoxaDiazole (DP-NBD-PE) were investigated at the air-water interface as Langmuir films and deposited on silicon wafers or glass plates as Langmuir-Blodgett (LB) films. 3D aggregates - cylinders with 50 – 300 nm diameter and bilayer height were observed with Atomic Force Microscopy (AFM) when deposition was carried at 7 mN/m, just above the main phase transition from liquid-expanded to liquid-condensed film. This pressure is significantly lower than the equilibrium spreading pressure of 19.6 mN/m for this molecule. When LB film deposition is carried just below the main phase transition a uniform height layer of film in liquid phase is observed with AFM. Both compression and deposition were carried at very low speeds with large time to relax in ordered to avoid kinetic effects. At least the picture at micrometer scale is preserved comparing fluorescence microscopy at the air-water interface and on the solid substrate using the fluorescence self-quenching new effect discovered by us for this molecule for high contrast observations. If the bilayer aggregates are regarded as a new phase then this contradicts the Gibbs’ phase coexistence rule valid in thermodynamic systems as we have a coexistence of a liquid phase, solid phase and 3D phase for a single component isotherms. Explanation in the framework of nanothermodynamics is suggested. Fluorescence Lifetime Imaging Microscopy (FLIM) of the LB film monolayers compared with integral fluorescence lifetime measurements suggest that molecules in these 3D aggregates are in the liquid phase. This fact together with the highly developed area and combined with fluorescence self-quenching effect for DP-NBD-PE yields these structures as ideal matrices for sensors with enhanced sensitivity, selectivity and fast reaction times. For better understanding of this new phenomenon a combination of a range of experimental techniques including 5 scanning probe microscopy methods, polarized grazing incidence and ATR FTIR spectroscopy, X-ray diffraction, polarised UV-VIS and Stark spectroscopy is combined with detailed molecular conformational analysis at simulated air-water interface.

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Cytochrome c/DNA co-assembling at air-water interface

Pabitra Kumar Paul1,2, Dock-Chil Che1, Kishimoto Hiroyuki1, Kento Araki1,

Takuya Matsumoto1

1Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama-Cho, Toyonaka, Osaka, Japan

2Department of Physics, Jadavpur University, Jadavpur, Kolkata-700 032, India


Interactions of DNA with proteins have attracted great attention in recent years for fundamental and biotechnological importance, namely molecular recognition, enzyme immobilization and also in many other bioelectronics. For the study of DNA-protein interactions, Langmuir-Blodgett (LB) method provides a reaction field for DNA-proteins self-assembling with supramolecular interactions because it is already known that protein molecules have high tendency to accumulate at their phase boundary at the surfaces [1] and DNA can also associate at the air-water interface [2]. In the present work, we have addressed the formations of molecular layer at the air-water interface of two water soluble biomaterials namely Cytochrome c (Cyt c) and λ-DNA. Time dependent adsorption of these materials and the formation of Cyt c/λ-DNA complex interfacial layer in the Langmuir trough were studied by recording the surface pressure versus trough area isotherms after allowing various incubation times. In case of water-soluble biomolecules, a number of molecules participating at air-water interface is determined by the equilibrium between the bulk and interface. We demonstrated that surface-area normalized isotherms are useful to extract the information of phase transition of interface layer excluding the effect of the number of molecules on surface pressure. The interfacial films were also transferred onto mica substrate under various surface pressures and after various incubation times allowed to sub-phase surface. The film morphology was analyzed by means of atomic force microscopy and surface potential images were obtained by electrostatic force microscopy. The results show that cyt c and DNA form network complex rapidly at air-water interface and then change to rod-like large aggregates with long time incubation.

Figure 1. (a) Surface pressure vs. surface area isotherms of cytochrome c and DNA mixed solution. (b) Schematic illustration of the barrier compression of Cytochrome c/DNA complexes networks.

References [1] Lev Razumovsky and Srinivasan Damodaran, Langmuir, 15, 1392 (1999). [2] Xuan Dai, Chuanwan Wei, Zhengyuan Li, Zhifang Sun, Rujuan Shenand Yi Zhang; RSC Advances, 3 16116 (2013).

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Interactions of anticancer drugs with biomimetic phospholipid layers

Dorota Matyszewska1, Renata Bilewicz2

1 Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Żwirki i Wigury 101, 02089 Warsaw, Poland

2 Faculty of Chemistry, University of Warsaw, ul. Pasteura 1, 02093 Warsaw, Poland


Langmuir method proved to be very useful in the studies of the interactions of drugs, toxins and other biologically important species with phospholipid monolayers formed at the air-water interface and treated as simple models of one leaflet of cell membranes [1,2]. The main advantage of such approach is the fact that the composition of a biomimetic layer may be adjusted to mimic different types of cellular membranes. We studied the influence of selected model anticancer drug, doxorubicin, on the properties of phospholipid mono- and bilayers treated as simple models of healthy and cancer cell membranes. Doxorubicin (DOx) is anthracycline antitumor drug, which finds application in the treatment of various types of cancer including leukemia, breast cancer, ovarian cancer, lung carcinoma, as well as several sarcomas [3]. Results of Langmuir studies show the drug incorporates into the 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) monolayers at the air-water interface, which leads to the changes in such properties of model membranes as area per molecule. The changes in the morphology of the layer due to the presence of the drug were also confirmed by Brewster angle microscopy studies. Interestingly, the effect of anthracyclines on the model membranes composed of 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS), a phospholipid occurring in an elevated level in cancer cell membranes [4], is much more pronounced. It may be explained by the presence of electrostatic interactions between negatively charged polar heads of DMPS and positively charged anthracyclines, which are not that significant in case of neutral polar headgroups of DMPC. The differences in the interactions of anticancer drugs with model membranes with the composition typical for healthy cells (phosphocholines and phosphoethanoloamines) and cancer cells (phosphocholines and phosphoserines) were also shown for other potential anticancer drugs such as inorganic complexes of ruthenium [5]. More detailed information on the interaction of DOx with model membranes were obtained from electrochemical and spectroscopic studies of supported phospholipid bilayers prepared by the combination of Langmuir-Blodgett and Langmuir-Schaefer techniques. PMIRRAS experiments confirmed the interactions of DOx with DMPC bilayers, which resulted in a significant decrease in the tilt angle of DMPC molecules in the bilayer. Low value of tilt angle (approximately 10o) may imply that the drug interacts strongly with polar heads of phospholipids. Additionally, electrochemical experiments allowed us to confirm the incorporation of anthracyclines into both DMPC and DMPS supported bilayers and allowed for the comparison of the drug interactions with these two model membranes.

References [1] C. Stefaniu, G. Brezesinski, H. Möhwald, Adv. Colloid Interf. Sci. 208, 197–213 (2014). [2] D. Matyszewska, R. Bilewicz, Electrochim. Acta 162, 45–52 (2015). [3] H. Cortes-Funes, C. Coronado, Cardiovasc Toxicol. 7, 56–60 (2007). [4] R. F. A. Zwaal, P. Comfurius, E. M. Bevers, Cell. Mol. Life Sci. 62, 971–988 (2005). [5] M. Frik, A. Martínez, B. T. Elie, O. Gonzalo, D. Ramírez de Mingo, M. Sanau, R. Sanchez-Delgado, T. Sadhukha, S. Prabha, J. W. Ramos, I. Marzo, M. Contel, J. Med. Chem. 57, 9995−10012 (2014).

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Modelling of biomembrane-flavonoid interactions

D. Sanver1, A. Sadeghpour1, M. Rappolt1, B. S. Murray1, A. Nelson2

1School of Food Science and Nutrition, the University of Leeds, UK 2School of Chemistry, the University of Leeds, UK


Flavonoids are emerging as potential drug candidates for oxidative stress-related diseases including cancer and diabetes [1]. This introduces a significant question whether the molecular mechanism of action is due to specific interactions involving protein-flavonoid binding or whether it is due to changes in the organisation in the membranes themselves. The current work addresses this problem using a comprehensive approach. A structure-dependent membrane interaction of a variety of naturally occurring flavonoids with phospholipid monolayers on microfabricated Pt/Hg electrodes was established by recording current peak changes as rapid cyclic voltammograms (RCV) [2]. Based on RCV; quercetin, rutin and tiliroside, were selected for follow-up experiments with Langmuir monolayers, Brewster Angle Microscope (BAM) and X-ray scattering. Relaxation phenomena in DOPC monolayers and visualization of the surface with BAM by compressing the monolayer up to and beyond the collapse pressure revealed a pronounced stabilization effect with quercetin and tiliroside. However, introduction of rutin demonstrated a different mode of action involving a complete disruption of the monolayer structure by rendering the surface entirely smooth and devoid of lipid islands. Thermal and structural alterations of the bilayer membrane with different flavonoid content ranging from 0 to 12 mole% were also studied via SAXS. The measurements showed a monotonous membrane thinning for all studied compounds associated with an increase of the root mean square fluctuations of the membrane in a dose-and temperature-dependent manner. Rutin, quercetin and tiliroside thin DOPC by ~0.45 Å, 0.8 Å, 1.1 Å at 6 mol %, respectively. All studied flavonoids were found to localize in the lipid/water interface region. The localization of the compounds and the membrane perturbations in the mode of interaction is implicated in the therapeutic activities of flavonoids.

Figure 1. Electron density profiles and corresponding real space models: DOPC bilayers in the presence of 6 mol. % of quercetin

References [1] Rice-Evans, C.; Packer, L., Flavonoids in health and disease. 2nd. Ed.; Marcel Dekker: New York, (2003) [2] Coldrick, Z.; Penezić, A.; Gašparović, B.; Stevenson, P.; Merrifield, J.; Nelson, A. , Journal of Applied

electrochemistry, 41 (8), 939-949 (2011)

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Membrane activity of ultra-short linear lipopeptides

Joanna Juhaniewicz1, Joanna Wenda2, Slawomir Sek1

1 Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Zwirki i Wigury 101, 02-089, Warsaw, Poland

2 Université de Genève, Département de biologie moleculaire, Sciences II 30 quai Ernest-Ansermet, CH-1211 Genève 4, Switzerland


The discovery of antibiotics was a milestone in the human fight against infectious diseases and has led to the substantial increase in quality of human's life [1]. However, the overuse of antibiotics has caused the increase in resistance of many bacteria and pathogens. Clinical infection due to drug-resistant bacteria is a serious challenge to people safety and highlights the need for new classes of antimicrobial drugs [2]. As a source of new antibiotics, microorganisms have drawn increasing attention [3]. The active compounds produced by various bacteria strains are peptide antibiotics, such as lantibiotics and lipopetides. Unfortunately, until now only two natural lipopeptides are used as drugs [4]. Therefore, we need to find new short and structurally simple peptides with broad spectrum of activity and low-cost production. Here we present the results of our studies on interactions of two synthetic ultra-short lipopeptides composed of four amino acid residues (Lys-Leu-Lys-Trp) and 16-carbon chain with model lipid membranes. The only difference in these two peptides is that leucine employed in peptide synthesis had different optical activity. The biomimetic lipid films were composed of a) phosphatidylcholine and cholesterol and b) phosphatidylethanolamine and phosphatidylglycerol, reflecting the eukaryotic and bacterial cell membrane, respectively. The influence of lipopeptides on the behaviour of lipid membranes was examined by means of surface pressure and Brewster Angle Microscopy. The experiments performed using Langmuir through allowed us to determine the affinity of peptides to particular lipid components of the cell membranes. To better mimic the natural membrane, we prepared lipid bilayers by transferring the lipids on solid support using the combination of Langmuir-Blodgett and Langmuir-Schaefer techniques. The action of lipopeptides was imaged by means of Atomic Force Microscopy. Our results clearly show that the presence of a D-amino acid residue(s) is crucial for antibacterial activity of lipopeptides. Moreover, different optical activity of lipopeptide molecule results in different mode of action on model lipid membranes. References [1] Y. Huang, J. Huang, Y. Chen, Protein and Cell 1, 143-152 (2010).

[2] J. Juhaniewicz, S. Sek, Electrochimica Acta 162, 53-61 (2015). [3] Z. Huang, Y. Hu, L. Shou, M. Song, BMC Microbiology 13, 87-94, (2013). [4] G. Pirri, A. Guiliani, S. Nicoletto, A. Rinaldi, Central European Journal of Biology 4, 258-273 (2009).

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Morphologies and degradation behaviour of biodegradable polymers at the air-

water interface

Burkhard Schulz1,2, Anne-Christin Schöne1,2, Andreas Lendlein1,2

1Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam, Germany

2 Institute of Biomaterial Science and Berlin-Brandenburg Center for Regenerative Therapies, Helmholtz-Zentrum Geesthacht, Kantstraße 55, 14513 Teltow, Germany


Aliphatic (co)polyesters or polyanhydrides are established in clinical applications but, for more sophisticated uses a comprehensive understanding of their degradation behaviour is needed. The biodegradation rates of the polymers can be varied whereby largely depending on the type of repetitive units, composition, sequence structure, molecular architecture, molecular weight, or morphology. The complex interplay of so many parameters makes predictions of short- and long-term degradation as well as of systemic effects of degradation products extreme difficult. There are two main pathways for the hydrolytic and enzymatic material degradation: the bulk and the surface erosion mechanism. Because, corresponding biological-system/material interactions occur at the interface the elucidation of chemical and physical processes at the surfaces is of fundamental importance. Polymer monolayers prepared by Langmuir techniques serve as 2D models to mimic the chemical and physical behaviour of polymer surfaces. The precise formation of monomolecular thin films at the air-water interface from multi-component materials with defined molecular architectures allows a detailed investigation of 2D morphologies. Moreover, the specific interactions of polymer surfaces with biomolecules or even cells is possible by combination of Langmuir experiments with optical and spectroscopic techniques. The presentation addresses the morphological control of polyester based films [1,2] and the in vitro Langmuir monolayer degradation (LMD) technique which allows a direct in situ monitoring of chain cleavages without consideration of water/enzyme diffusion processes [3,4]. It will be discussed in detail how the rates of hydrolytic and enzymatic degradation are largely dependent upon the type of polymer composition, sequence structures in multi-block copolymers, and molecular architectures [5]. The effect of enzymes, non-defined and defined degradation products on polyester film morphologies and their degradation behaviour [6] will also be presented. The given results elucidate the Langmuir techniques as powerful tool to investigate both the degradation behaviour and the morphologies of polymer films at the air-water interface mimicking biomaterials surfaces in aqueous environments. References [1] A.-C. Schöne, B. Schulz, K. Richau, K. Kratz, A. Lendlein, Macromol. Chem. Phys. 215, 2437-2445 (2014).

[2] A.-C. Schöne, K. Kratz, B. Schulz, J. Reiche, S. Santer, A. Lendlein, Polym. Adv. Technol. 26, 1411-1420 (2015) [3] A. Kulkarni, J. Reiche, A. Lendlein, Surf. Interface Anal. 39, 740–746 (2007). [4] J. Reiche, K. Kratz, D. Hofmann, A. Lendlein, Int. J. Artif. Organs 34, 225-230 (2011). [5] A.-C. Schöne, K. Richau, K. Kratz, B. Schulz, A. Lendlein, Macromol. Rapid Commun. 36, 1910−1915 (2015)

[6] A.-C. Schöne, O. Travkova, S. Falkenhagen, K. Kratz, B. Schulz, A. Lendlein, Polym. Adv. Technol. 26, 1402-1410 (2015).

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Systematic study of Langmuir films of different amino acid derivatives on several

subphases

L. Románszki1, J. Telegdi2, Zs. Keresztes1

1 Research Centre for Natural Sciences, Hungarian Academy of Sciences, Institute of Materials and Environmental Chemistry, 1117 Budapest, Magyar tudósok körútja 2., Hungary

2 Institute of Media Technology and Light Industry, Faculty of Light Industry and Environmental Engineering, Óbuda University, 1034 Budapest, Doberdó u. 6., Hungary

E‐mail address: [email protected]

Langmuir films and Langmuir–Blodgett layers of long sidechain amino acid derivatives are interesting for the investigation of (bio)sensing mechanisms, drug delivery processes, 2D chiral organization etc., and the development of sensor, corrosion inhibitor, anti‐biofouling etc. layers. In a Langmuir trough equipped with a Brewster angle microscope (BAM), we studied the formation and the behaviour upon compression of Langmuir films of 1) two α‐alkyl derivatives (hexadecyl, respectively octadecyl) of tert‐butoxycarbonylated glycine, respectively glycine methyl ester (BOC‐GlyMe‐C16 and BOC‐Gly‐C18) on L‐ and D‐amino acid subphases with/without Cu2+ ions, and 2) N‐palmitoyl derivatives of four L‐amino acids (Ala, Ser, Glu, and

Phe) on pure water subphase. The films were characterized by their Ac and A0 molecular areas, c collapse pressure, C-1 compression moduli, and the 𝐶𝑚𝑎𝑥

−1 surface pressure at maximum compression modulus (Fig.

1 and 2). In this contribution, the found peculiarities of the different amphiphile–subphase pairs and the drawn conclusions about the structure of the films and the interactions of the amphiphiles with the subphases will be presented.

Figure 1. c collapse pressure and Ac molecular area values (A), respectively 𝐶𝑚𝑎𝑥

−1 maximum compression moduli and the corresponding 𝐶𝑚𝑎𝑥

−1 surface pressure values (B) determined from the Langmuir film isotherms of BOCGlyMe‐C16

(empty symbols), respectively BOC‐Gly‐C18 (filled symbols), recorded on different subphases: water (■); CuAc2 (●); D‐

Ala (▲); L‐Ala (▼); D‐Asn ( ); D‐Asn + CuAc2 ( ); L‐Asn ( ); L‐Asn + CuAc2 ( ).

Figure 2. Langmuir film isotherms (A), compression moduli graphs (B), and mean collapse coordinates with standard errors of means (C) of N‐palmitoyl‐L‐amino acids (1: Ala; 2: Ser; 3: Glu; 4: Phe) on pure water subphase.

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Main differences of the Stratum Corneum non-esterified constitutional ceramides -

a ternary 2D model system study

Joana S.L. Oliveira1, Gerald Brezesinski1

1 Max-Planck-Institut für Kolloid- und Grenzflächenforschung, Wissenschaftspark Potsdam-Golm, Am Mühlenberg 1, 14476 Potsdam, Germany


The Stratum Corneum (SC), the outermost layer of the skin, is responsible for the barrier function of the human skin, while keeping the skin in optimal hydration levels. When considering dermal/transdermal drug delivery systems, the SC is the main responsible for the low penetration ability of drugs and strategies have been investigated to transpose this barrier effectively. The SC is known to be composed by corneocytes (dead cells) embedded in a lipid matrix, which main components are ceramides (40% of the SC lipids), free fatty acids and cholesterol. Ceramides are composed of a sphingoid base slightly hydrophilic and a fatty acid. The length of the two chains might vary. To date, 16 ceramides subclasses were found in the human SC [1], but little is known about their individual behavior. Our aim is to shed light on the properties and function of 4 constitutional ceramides with different head group structures – ceramide NP, NS, AP and AS. By keeping the chain length fixed (C18:18 alkyl chains), structural differences induced by chain variation or mismatches are eliminated. Furthermore, the influence of stearic acid and/or cholesterol in the structure and behavior of ceramides is also of interest. To do so, we used Langmuir Monolayers (pressure-area isotherms) coupled to other surface sensitive techniques like Infrared Reflection Absorption Spectroscopy (IRRAS), Brewster Angle Microscopy (BAM) and Grazing Incidence X-Ray Diffraction (GIXD). Ceramide [AP] presents the larger area per molecule of the four ceramides in isotherms measurements, which is in agreement with its bulkier head group. Sphingosines show a less complex packing structure than phytosphingosines. While phytosphingosines show a complex GIXD pattern, ceramide [AS] showed a rectangular in plane lattice, which adjust into a hexagonal packing upon compression. As a SC lipid matrix model a ternary mixture with ceramide, stearic acid and cholesterol in a molar ratio of 1:1:0.7, respectively, was used. Using binary mixtures of cholesterol and/or stearic acid the stiffness of the ceramide monolayer decreases significantly. Cholesterol was shown to effectively lose the tight packing found for pure ceramide layer in a dependent way of its concentration, while binary mixtures with stearic acid kept the rigid packing. GIXD measurements proved the complete miscibility of the ternary mixture if a molar ratio of 1:1:0.7 is used. The characterization of such systems was performed as a first step to validate the SC model used, to afterwards study the influence of penetration enhancers in the packing properties of these systems. References [1] t’Kindt, R., Jorge, L., Dumont, E., Couturon, P. David, F., Sandra, P. and Sandra, K. Analitical Chemistry 84, 403-411

(2012).

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Controlling lateral spacing in phenolic surfactant monolayers

R. Miclette Lamarche, C. DeWolf

Concordia University, 7141 Sherbrooke St. W., Montreal, Quebec, Canada H4B1R6


Phenolic compounds such as tannins exhibit antioxidant, metal chelating and protein-binding abilities [1]; surfactants with this functionality may confer these properties to self-assembled structures and surfaces. We have previously shown the phenolic headgroup to be extremely self-adhesive yielding strong lateral rigidity to Langmuir monolayers at liquid surfaces [2]. This in turn yielded high aggrega-tion at zero surface pressure and confered a high resistance to changes in molecular orientation and conformation (i.e. relatively invariant structure and tilt angles). The extent to which the phase behav-iour can be tuned by modifying the intermolecular interactions via changes in subphase composition (such as pH, salt concentration and temperature) will be presented for lauryl gallate (C12) and octa-decylgallate (C18) surfactants which exhibit liquid expanded and condensed phases, respectively, at the air water interface. The film organizational changes are determined by grazing incidence x-ray diffraction (GIXD) while morphology is assessed using Brewster angle microscopy at the air-water interface and atomic force microscopy for films deposited on mica. The competition of hydrogen-bonding and π-stacking interactions between headgroups can be manipulated to yield highly direc-tional domain growth and control over the inter-surfactant distance. GIXD measurements show that the gallate headgroups are arranged in a crystalline packing state with limited free rotation, attribut-ed to strong hydrogen bonding and π-stacking interactions of the gallate headgroup. The parameters required to modify this preferred headgroup arrangement will be discussed in terms of their impact on film organization and the design of functional surface coatings.

Figure 1. AFM image of octadecylgallate monolayer deposited by Langmuir-Blodgettry onto mica.

References [1] N. J. Baxter , et al., Biochemistry, 36, 5566-5577 (1997) [2] R. Schmidt, C., E., DeWolf, Langmuir, 20, 3284-3288 (2004)

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Alkyl imidazolium ionic liquids Langmuir layering at the air-water interface

Nathalie Bonatout1, 2, Philippe Fontaine3, Eduardo Filipe3, François Muller1 and Michel Goldmann2, 4

1 Laboratoire des Interfaces Complexes et de l’Organisation Nanométrique (LICORNE), ECE-Paris, Paris,

France 2 Institut des Nanosciences de Paris, UMR, Paris, France

3 Centre for Structural Chemistry, Instituto Superior Tecnico, Av Rovisco Pais Universidade Tecnica de Lisboa 1049-001, Lisboa Portugal

4 Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin BP48, 91192 Gif-Sur-Yvette, France

E-mail address: [email protected], [email protected]

ILs are organic salts with the outstanding property to be liquid around ambient temperature. This results from a competition between electrostatic, Van der Waals and hydrogen-bond interactions. Such balance is known to impose mesoscopic organization in the bulk [1,2]. However, very few studies on the meso-structuration of IL films have been performed [3]. We study Langmuir films formed by the alky-alkyl imidazolium cation family and focused on the C18mimNTf2 (Figure 1). The isotherms indicate a single condensed phase with a compressibility of about 50 m/N before a plateau associated to the collapse of the monolayer. Brewster Angle Microscopy (BAM) confirm the fluid nature of this phase (Figure 2). It also shows the growth of a layered structure after the collapse. These results are in agreement with the simulations [4]. One also observes the melting of the layered structure under the film expansion. We performed Grazing Incidence X-Ray Diffraction (GIXD) on the C18mimNtF2 Langmuir film on a salted (NaCl) water subphase (for film stabilzation). At low surface pressures, no diffraction peak was observed, in agreement with a fluid phase of the monolayer. After the plateau (about 37mN/m), one observes diffraction peaks indicating the ionic liquid organization in the layered structure. We performed similar experiments (under treatement) on C12C12imNtF2 to probe the alkyl chains influence.

References [1] Sloutskin E et al., Journal of the American Chemical Society, 127, 7796-7804 (2005). [2] Triolo, A. et al., J. Phys. Chem. B, 111, 4641−4644 (2007). [3] Tamam, L.et al., Physical Review Letters, 106, 197801 (2011) [4] Filipe E. et al., Chem. Comm, accepted

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Figure 1. Structural Formula of C18mimNTf2

Figure 3. BAM images of C18mimNTf2

Figure 3. GIXD measurements of C18mimNTf2


78

Simulation of an electric field effect on surfactant molecules

Natalich A.V.1, Chumakov A.S.1,3, Camacho L.2, Giner-Casares J.J.2, Glukhovskoy E.G.3

1 National Research Saratov State University named after N.G. Chernyshevsky, Faculty of Nano- and Biomedical technologies, Astrakhanskaya 83, Saratov 410012, Russia

2 University of Cordoba, Department of Physical Chemistry and Applied Thermodynamics, Campus de Rabanales, Edificio Marie Curie, Cordoba E-14014,Spain

3 National Research Saratov State University named after N.G. Chernyshevsky, Education and Research Institute of Nanostructures and Biosystems, Astrakhanskaya 83, Saratov 410012, Russia


Thin monolayer films obtained by Langmuir-Blodgett method are useful for many different applications. To form these films is simple, cheap and does not require any complicated conditions, such as significant variations of temperature and pressure [1]. Surfactant molecules can be used to form different structures [2]. There are many factors affecting the formation of new structures such as the initial concentration of surfactants, presence of metal ions and electric field. We have investigated the action mechanism of such factors. This knowledge is helpful in understanding the influence of electric field and metal ions on cell membranes, micelles, liposomes, microcapsules and related interfaces [3]. A quantum-chemical simulation was performed in this work to study the influence of external electric field and metal ions on arachidic acid molecules. The value of the applied electric field varied from 5,14*102 V/m to 25,7*105 V/m. Calculations of total energy were performed for pure arachidic acid and in presence of Pb2+, Li+, Ca2+, K+ ions. The total energy as a function of the electric field in the presence of metal ions is shown in fig. 1. The research was supported by grant of the Russian Science Foundation (project №14-12-00275) and the National Research Saratov State University.

Figure 1. Full energy of the Langmuir monolayer of arachidic acid system in presence of ions and electrical field.

References [1] Chumakov A.S., Ermakov A.V., Kim V.P., Gorbachev I.A., Glukhovskoy E.G., Nanotech France 2015 Conference &

Exhibition. Posters session. Nanomaterials characterization, 15 (2015).

[2] Giner-Casares J.J., Brezesinski G., Möhwald H., Curr. Opin. Interf. Sci. 19, 176 (2014).

[3] Gzyl-Malcher B., Filek M., Brezesinski G., Langmuir. 27, 10886 (2011).

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http://www.sgu.ru/en/structure/fnbmt

http://www.sgu.ru/en/structure/fnbmt


79

Nanometer thick poly(ethylene glycol) films and membranes as a flexible platform

for humidity sensors and bioengineering

M. Khan and M. Zharnikov

Applied Physical Chemistry, Heidelberg University, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany


We discuss possible applications of novel poly(ethylene glycol) (PEG) hydrogel films and membranes, abbreviated as PHFs and PHMs, respectively. They were fabricated by thermally activated crosslinking of amine- and epoxy-terminated, star-branched PEG oligomers and characterized by tuneable thicknesses of 4 - 200 nm [1]. These systems possess a variety of useful properties, including biocompatibility, robustness, and extreme elasticity [1,2]. They can also serve as a basis for hybrid materials and nanofabrication [1,3]. Here we demonstrate that PHFs and PHMs can also be used as highly sensitive elements in humidity sensors and moisture-responsive nanoelectronic devices, relying on resistive transduction technique [4]. Their resistance change by ca. 5.5 orders of the magnitude upon relative humidity variation from 0 to 100% (see Fig. 1a), which is unprecedented response for homogeneous materials. The resistive response to humidity can be modified by the introduction of gold and silver nanoparticles into the PHM matrix. As another representative example, we show that PHFs and PHMs are able to host protein-specific receptors, providing, at the same time, protein-repelling and humidity-responsive matrix with a characteristic mesh size up to 8.4 nm. A noticeable grafting density of the test avidin protein, specifically attached to the biotin moieties coupled to the free amine groups in the PHMs, was achieved, whereas the analogous values for non-specifically adsorbed proteins were lower by a factor of 4-5 (see Fig. 1b). The engineering of PHMs with biomolecule-specific receptors and their loading with biomolecules are of potential interest for sensor fabrication and biomedical applications, including tissue engineering and regenerative therapy.

Figure 1. (a) Resistance of pristine PHM as a function of relative humidity; (b) grafting density of specific (avidin) and non-specific (BSA and albumin) proteins for a series of the PHMs functionalized with NHS-biotin.

References [1] N. Meyerbröker, T. Kriesche, and M. Zharnikov, ACS Appl. Mater. Interfaces 5, 2641−2649 (2013). [2] N. Meyerbröker and M. Zharnikov, Adv. Mater. 26, 3328-3332 (2014). [3] N. Meyerbröker and M. Zharnikov, ACS Appl. Mater. Interfaces 6, 14729−14735 (2014). [4] M. Khan, S. Schuster, and M. Zharnikov, J. Phys. Chem. C 119, 14427−14433 (2015).

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80

Coordination-based molecular assemblies used as a platform for Integrated

molecular logic

Hodaya Keisar, Michal Lahav and Milko E. van der Boom

The Weizmann Institute of Science, Department of Organic Chemistry, 76100 Rehovot, Israel


Molecules have been shown to mimic logic functions ranging from basic logic gates such as AND, OR, and NOT to logic circuits including Flip-Flops.[1-3] Logical units are physically integrated into semiconductor-based technologies. However, molecular logic integration remains a large challenge due to the requirement of data transfer between the entities. Functional integration of logic operations eliminates the need for direct data flow between the molecular components. We demonstrate that surface molecular assemblies (MAs) can be used for the functional integration of molecular logic. These MAs consist of networks of redox-active metal complexes immobilized on the surfaces of transparent conductive oxides. The system operates by using electrical inputs (IN) to change the metal oxidation state (M2+/3+). The output (OUT) is the coloration of the MA, which is a function of the oxidation state (Figure 1). We used two physically separated MAs that can be addressed independently and read out simultaneously. Both MAs are placed in parallel in an electrochemical cell equipped with counter and reference electrodes. Their IN-OUT combination determines the logical operation of the system, resulting in the mimicry of decoders.

Figure 1. Schematic illustration of the system

References [1] de Silva, A. P. ; Uchiyama, S, In Luminescence Applied in Sensor Science, Prodi, L., Montalti, M., Zaccheroni, N., Eds, Springer, Berlin Heidelberg (2011) [2] Gupta, T.; van der Boom, M. E. Angew. Chem. Int. Ed. 47, 5322-5326 (2008), [3] de Ruiter, G.; Motiei, L.; Choudhury, J.; Oded, N.; van der Boom, M. E. Angew. Chem. Int. Ed. 49, 4780-4783,

(2010).

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Efficient polyelectrolyte/surfactant films spread from neutral agregates

Richard A. Campbell1, Andrea Tummino1,2, Boris Noskov3, Imre Varga2

1 Institut Laue-Langevin, 71 avenue des Martyrs, CS20156, 38.042 Grenoble Cedex 9, France 2 Institute of Chemistry, Eötvös Loránd University, Budapest 112, P. O. Box 32, H-1518 Hungary

3 Institute of Chemistry, St. Petersburg State University, 198904 St. Petersburg, Russian Federation


Oppositely charged polyelectrolyte/surfactant (P/S) mixtures generate sustained interest as a result of the huge commercial value of formulations we use in our everyday lives [1]. There has been growing awareness in the last decades that non-equilibrium effects can determine the behavior of these systems due to the production of kinetically-trapped aggregates [2]. In recent years we have shown that these particles can either diminish the interfacial properties through depletion of surface-active material from the bulk [3] or enhance them by various direct interactions [4]. In the present work [5], we describe a new methodology to prepare efficient polyelectrolyte/ surfactant films at the air/water interface by exploiting the dynamic dissociation and spreading from charge-neutral aggregates. Our approach results in interfacial confinement of more than one third of the macromolecules in the system even though they are not even surface-active alone. When the films are subject to changes in the surface area, the interfacial coverage can be reset to that of a monolayer and they behave as perfectly insoluble films. The components bind faithfully in a one-to-one charge ratio at the interface independently of the sample history, which is rationalized in terms of the low ionic strength of the solution. To our knowledge, this is the first time in which the dynamic interfacial composition of such a mixed system has been resolved in situ. We discuss how this understanding may open up the potential for the preparation of memory-retaining membranes for encapsulation and in a range of deposition-based technologies including bio-sensing applications.

Figure. (Left) Ellipsometry measurements: A and C are spread films while B and D are adsorbed layers with equivalent compositions, 100 ppm, 17k NaPSS with (A) 6 mM and (C) 0.4 mM DTAB; E is just the pure surfactant; (Centre) Langmuir isotherms of spread films where each cycle is displayed darker in shading; (Right) Interfacial composition resolved using neutron reflectometry where the maxima = compression and minima = expansion.

References [1] J. M. Rodriguez Patino, C. C. Sanchez, Ma. R. Rodriguez Nino, Adv. Colloid Interf. Sci. 140, 95 (2008). [2] A. Naderi, P. M. Claesson, M. Bergstrom & A. Dedinaite, Colloid Surf. A 253, 83 (2005). [3] R. A. Campbell, M. Y. Arteta, A. Angus-Smyth, T. Nylander & I. Varga, J. Phys. Chem. B 115, 15202 (2011). [4] R. A. Campbell, M. Y. Arteta, A. Angus-Smyth, T. Nylander, B. A. Noskov & I. Varga, Langmuir 30, 8664 (2014). [5] R. A. Campbell, A. Tummino, B. A. Noskov & I. Varga, submitted (2016).

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Thermal transition in polyelectrolyte films via dehydration mechanism

Erol Yildirim1, Ran Zhang1,2, Yanpu Zhang3, Hanne S. Antila1, Jodie L. Lutkenhaus3, Maria Sammalkorpi1

1 Department of Chemistry, Aalto University, P.O. Box 16100, 00076 Aalto, Finland

2 State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, P.R. China

3Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, USA


Hydrated polyelectrolyte (PE) complexes and multilayers undergo a well-defined thermal transition that bears resemblance to a glass transition. Even though its origins are not well understood, this transition is widely used in, e.g., thermo-responsive drug delivery and in the emerging field of saloplastics. We have probed via molecular simulations interconnected with differential scanning calorimetry (DSC) experiments the fundamental nature of this thermal transition of molecular thin films. Our findings show the diffusion behavior, hydrogen bond formation, and bridging capacity of water molecules plasticizing the PE assemblies experiences a sudden change at the transition temperature. By combining molecular simulations and DSC, we establish for the first time that dehydration drives the thermally induced change in plasticization of the complex and in the diffusion behavior of its components. DSC experiments show that the thermal transition appears when the assemblies are hydrated in water but not in the presence of alcohols, which supports that water is required for this transition. We quantify the behavior and map its chemistry specificity through comparison of strongly and weakly charged PE complexes, as well as, different ionic strengths and species in the system. We conclude the transition is actually via a LCST type mechanism and not a glass transition as previously supposed. These findings connect PE assemblies more generally to thermoresponsive polymers and liquid crystal phases, which bear phase transitions driven by the (de)hydration of functional groups, thus forming a fundamental link toward an integrated understanding of the thermal response of molecular materials in aqueous environments.

References [1] Erol Yildirim, Yanpu Zhang, Jodie L. Lutkenhaus, and Maria Sammalkorpi, ACS Macro Letters 4, 1017-1021 (2015). [2] Ran Zhang, Yanpu Zhang, Hanne S. Antila, Jodie L. Lutkenhaus, and Maria Sammalkorpi, under preparation.

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83

Layer-by-layer assembly driven by host-enhanced - Interaction

X. Zhang, B. Yuan, H. Yang

Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China


Although the method of Layer-by-Layer (LbL) deposition has been well-established, we are enriching the

field by introducing host-enhanced – interaction as a new kind of driving force for fabricating multilayer thin films [1-3]. To this end, multi-armed building blocks bearing naphthalene groups were designed and synthesized, which could form supramolecular complexes with cucurbit[8]uril (CB[8]) in aqueous solution

via host-enhanced – interaction. To transfer supramolecular complexation from solution to the interface, multilayer thin films with controlled structure and composition can be fabricated by LbL assembly, as shown in Fig. 1 [4]. Moreover, by introducing functional groups such as porphyrin into the building blocks, functional surfaces with photocatalysis properties can be fabricated [5]. Upon irradiation of visible light, the as-prepared films exhibit good catalytic activity towards the oxidation of various phenols. This kind of LbL assembly may be regarded as a sort of supramolecular polymerization at the interface and its degree of supramolecular polymerization is controlled efficiently by adjusting layer pairs. Considering that the diversity of building blocks with different functional groups, it is anticipated that this strategy provides a new method to fabricate stimuli-responsive functional surfaces by transferring supramolecular polymerization from solution to the liquid–solid interface, which may have potential applications in fields such as bio-interface, sewage disposal, and biocatalysis.

Figure 1. Layer-by-layer assembly by alternative deposition of naphthalene bearing molecules and CB[8] driven by

host-enhenced - interaction

References [1] G. Decher, J. B. Schlenoff, Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, Wiley-VCH: Weinheim, Germany, 2003. [2] Y.L. Liu, Y. Yu, J. Gao, Z.Q. Wang, and X. Zhang, Angew. Chem. Int. Ed., 49, 6576-6579 (2010). [3] L.L. Yang, X.X. Tan, Z.Q. Wang and X. Zhang, Chem. Rev. , 115, 7196-7239 (2015). [4] H. Yang, Z. Ma, B. Yuan, Z.Q. Wang, and X. Zhang, Chem. Commun., 50, 11173-11176 (2014). [5] B. Yuan, H. Yang, Z.Q. Wang, and X. Zhang, Langmuir, 30, 15462-15467 (2014).

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84

Langmuir-Blodgett films of tyrosine containing oligopeptide

I.V. Paribok1, V.E. Agabekov1, Y.-S. Lee2

1 Institute of Chemistry of New Materials, NAS of Belarus, 36 Fr. Skaryna Street, Minsk BY-220141, Republic of Belarus

2 School of Chemical and Biological Engineering , Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul, Korea 151-742


Recently, a number of tyrosine containing oligopeptides with a tendency to spontaneous facet formation has been developed [1]. The planar facets of H-Tyr-Tyr-Ala-Cys-Ala-Tyr-Tyr-OH (YYACAYY) are supposed to be useful in many applications e.g. as catalytic scaffolds or ion-selective membranes. We assumed the alternative way to form thin organized films of YYACAYY. Our goal was to test YYACAYY as a surfactant and to find appropriate conditions for deposition of oligopeptide Langmuir-Blodgett (LB) films on solid substrates. A molecule of a surfactant-like peptide usually consists of a hydrophobic tail (5-6 amino acids) and a hydrophilic head (1-2 amino acids) [2-4]. YYACAYY has extremely different structure. Nevertheless, it shows the properties of a typical surfactant that is proved by appropriate “Surface pressure – Area per molecule” isotherms. We formed Langmuir monolayers by spreading a1 mg/ml YYACAYY solution in dimethyl sulfoxide on the surface of distillated water or 10-2 M CuCl2 solution. Despite on the partial loss of peptide molecules in the subphase volume, high-quality Langmuir films were successfully formed and deposited on precleaned Si wafers by traditional LB method [5]. We used two alternative ways to analyze the film thickness by atomic force microscopy (AFM): to produce an artificial defect in the coating by multiple scanning of a small area at a force ~10 nN or to form patterned film by microcontact printing (µCP) [6]. Formation of YYACAYY patterned films was easily performed if the Langmuir-Schaeffer method was used for stamp modification (Figure 1). Thus, by combining different techniques we were able to successfully form YYACAYY LB films with controllable design and thickness.

Figure 1. Patterned LB films of YYACAYY: (a) 1 layer; (b) 3 layers

Acknowledgments The work is partially supported by BRFFR project X15Kor-002.

References [1] H.-S. Jang et al., Nature Communications 5, Article number: 3665 (2014). [2] C. Tang et al., Journal of Nanomaterials 2013, Article ID 469261, (2013). [3] G. Maltzahn et al., Langmuir 19, 4332–4337 (2003). [4] S. Santoso et al., Nano Letters 2, 687–691 (2002). [5] V.E. Agabekov et al., Acta Physica Polonica A. 93, 383-386 (1998). [6] I.V. Paribok et al. Russian Journal of General Chemistry 80, 1060-1063 (2010).

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Fabrication of carbon fibers by self-rolling protein films

H. Ko1, L. F. Deravi2, S. J. Park3, J. Jang4, T. Lee4, C. Kang5, J. Lee5, K. K. Parker3, K. Shin1

1 Department of Chemistry and Institute of Biological Interfaces, Sogang University, Seoul 04107, Korea 2 Department of Chemistry, University of New Hampshire, Durham, NH 03824, USA

3 Disease Biophysics Group, Wyss Institute of Biologically Inspired Engineering, School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA

4 Department of Physics and Astronomy, and Institute of Applied Physics, Seoul National University, Seoul 08826, Korea

5 Department of Chemistry, Sookmyung Women’s University, Seoul 04373, Korea


Inspired by active motions in nature (e.g., coiling, twisting or bending), strain-driven self-rolling techniques have been developed. The strain induced from mismatch between different layers gives rise to internal stress at an interface. When this stress is released it leads to the rolling motions. By this method, we fabricated conductive carbon fibers. (Fig.1) Fibronectin, one of the extracellular matrix proteins was prepared by microcontact printing as a stretched state. Carbon nanotube (CNT) and graphene oxide (GO) were deposited on top of the pre-strained fibronectin pattern. When this layer is released from a substrate by dissolving the sacrificial layer, the pre-strained protein layer contracts instantly while forming the carbon materials fiber inside of the protein tube. Before the self-rolling, the deposited CNT or GO particles on the protein layer were physically separated and non-conductive, but the contraction of the pre-strained protein layer leads to form homogeneous and conductive fibrous structures. The selective removal of the protein layer was further performed, and their morphologies and the electric properties of the self-rolled CNT or reduced GO fibers were characterized. This novel method provides a general fabrication method for highly aligned fibrous structures of various nanomaterials.

Figure 1. Formation process of CNT fiber via self-rolling protein layer

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86

Preparation and characterization of surface-bound ssDNA films, brushes, and

nanostructures

M. Zharnikov



DNA holds great promise as the basis for new biotechnologies due to its unique recognition and coupling properties. In particular, surface-bound DNA has been exploited in such diverse applications as DNA computing, nanoparticle assembly, and the directing of cell settlement, in addition to the more standard microarray applications that have proven valuable for high throughput genetic screening. However, the efficient functioning of these systems is highly dependent on their design and on a variety of parameters, above all on packing density and molecular orientation. In this context, different strategies to couple single stranded DNA (ssDNA) to solid substrates and to optimize the resulting films will be discussed. The structural properties and hybridization ability of these films were thoroughly analyzed using a number of complementary characterization techniques [1,2]. New approaches to control the density of the surface-bound ssDNA are discussed. The most promising strategy, relying on irradiation-promoted exchange reaction, allows to prepare mixed monolayers of thiolate-bound ssDNA and oligo(ethylene glycol) substituted alkanethiols (OEG-AT) in a broad range of compositions as well as ssDNA/OEG-AT patterns of desired shape embedded into a biorepulsive background [3]. The composition of the mixed films or ssDNA/OEG-AT spots (lithography) can be precisely adjusted by electron or UV dose in almost entire composition range. The above procedure relies on commercially available compounds and is applicable to both thiol-terminated and symmetric and asymmetric disulfide-terminated ssDNA. The fabricated OEG-AT/ssDNA templates and patterns (see Figure 1a) can be extended into the z-dimension by surface-initiated enzymatic polymerization of ssDNA, which results in the formation of highly ordered ssDNA brushes and allows topographically complex ssDNA brush patterns to be sculpted on the surface (see Figure 1b and 1c).

Figure 1. Atomic force microscopy images of an ssDNA pattern in a biorepulsive OEG-AT matrix (a) as well as representative ssDNA brush nanostructures grown on the engineered ssDNA/OEG-AT templates (b,c).

References [1] S. Schreiner, A. Hatch, D. Shudy, C. Howell, J. Zhao, P. Koelsch, M. Zharnikov, D. Petrovykh, and A. Opdahl, Anal. Chem. 83, 4288-4295 (2011). [2] C. Howell, H. Hamoudi, S. Heissler, P. Koelsch, and M. Zharnikov, Chem. Phys. Lett. 513, 267-270 (2011). [3] M. N. Khan, V. Tjong, A. Chilkoti, and M. Zharnikov, Angew. Chem. Int. Ed. 51, 10303-10306 (2012).

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SAM-based models of cell surfaces to study the interactions with lectins and

bacterial fimbriae

A. Terfort1, T.K. Lindhorst2

1 University of Frankfurt, Max-von-Laus-Str. 7, D-60438 Frankfurt, Germany 2 University of Kiel, Otto-Hahn-Platz 3, D-24118 Kiel, Germany


Biologically important events such as cell-cell adhesion or infection typically start by directed and selective interactions with the highly glycosylated layer surrounding most eukaryotic cells. This layer, called the glycocalyx, consists of intricate glycopolymers, which – although in apparent disorder – clearly identify the cells. It is therefore of paramount interest to understand, which structural elements are important for the cell identification. Self-assembled monolayers (SAM) can be used to simulate the chemical and sterical environment within such a glycocalyx. For this, glycosides are attached to oligoethyleneglycol (OEG) chains, which simulate the hydrogel matrix for the respective receptor. In this talk, we will focus on mannose-derivatives, which can be selectively recognized either by a lectin, concanvalin A, or by the adhesive fimbriae (tiny protein extrusions) of E. coli cells. We would like to present different strategies for the construction of such SAMs [1,2] and discuss the advantages and disadvantages of these approaches. In extension of the mostly static systems, we will also present an approach to dynamically reorient the glycoside at the interface to determine the influence of steric factors on surface recognition [3].

References [1] Kleinert, M.; Winkler, T.; Terfort, A.; Lindhorst, T.K. Org. Biomol. Chem. 6, 2118-2132 (2008) [2] Grabosch, C.; Kind, M.; Gies, Y.; Schweighöfer, F.; Terfort, A.; Lindhorst, T. K. Org. Biomol. Chem. 11, 4006-4015 (2013). [3] Weber, T.; Chandrasekaran, V.; Stamer, I.; Thygesen, M.B.; Terfort, A.; Lindhorst, T.K. Angew. Chemie Int. Ed. 53, 14583–14586 (2014).

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Cellulose nanocrystals and chitosan towards tunable film development and

wrinkling

H. Izawa1, O.J. Rojas2

1 Graduate School of Engineering, Tottori University, 4-101 Koyama-Minami, Tottori 680-8550, Japan 2 Department of Forests Products Technology, Aalto University, Vuorimiehentie 1, FI-00076 Aalto, Finland


We report on our efforts to assemble nanocellulose as ultrathin films, including the main techniques used for the deposition of coating layers of cellulose nanocrystals (CNC). The Langmuir–Schaeffer (surface lifting) method is introduced as a suitable way to produce thin films with tunable surface packing density. Advances are presented to align CNCs under convective and shear-assisted assembly. The orientation of the component nanoparticles have been shown to be sensitive to external electric fields, which allow additional control of film structure and morphology. Some physical and electromechanical properties of the produced CNC films are briefly introduced. Continuous films obtained by phase-separation of bicomponent solutions of cellulose derivatives are also discussed. As an extension of this work, novel surface wrinkling systems are presented, inspired by wood. Microscopic wrinkles were fabricated on the surface of chitosan films and fibres by a facile procedure that involved immersion, surface reaction, and drying. We revealed that the immersion process induces/controls surface wrinkling by the formation of covalent bonds between the substrate (chitosan, CS) and phenolic acid molecules (PH). PH-bound moieties acted as precursors or reaction sites for crosslinking through horseradish peroxidase (HRP)-catalyzed polymerization and to yield a skin layer with different elastic modulus compared to the CS support. Further, surface wrinkling was induced by water evaporation during drying. Wrinkling morphology can be controlled by the choice of PH molecular structure, immersion temperature, as well as the drying stress applied. The proposed versatile wet processing for wrinkling formation provides the base for designing 3D materials for given functions. It is noteworthy that this is a totally bio-based system involving green materials and processes. Overall, our biomimetic approaches exemplifies bio-based films and wrinkled surfaces that not only informs about surface interactions but can be useful in a number of applications.

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Vesicular assembly of gold nanoparticles and that plasmonic behavior

K. Ijiro1, J. Wei2, N. Iyo2, Matsuo1, H. Mitomo1, K. Niikura1

1 Research Institute for Electronic Science, Hokkaido University, N21W10, Sapporo 001-0021, Japan 2 Graduate School of Chemical Sciences and Engineering, Hokkaido University, N13W8, Sapporo 060-8628,

Japan


In living cells, there are various lipid capsules, e.g. endoplasmic reticulum, for the vesicular transport. Some of the viruses have protein capsules called capsid enclosing genetic materials. Both are constructed by the self-assembly of their components (lipids or proteins). Self-assembled nano-capsules like lipid capsules (liposome) or protein capsules (virus capsid) can be good drug carriers. A simple approach to the creation of colloidal assemblies from heterogenous nanoparticles is in high demand for the development of functional devices. The interparticle plasmonic coupling in the assemblies can produce collective properties different from those of dispersed particles, therefore metal and semiconductor nanoparticle assemblies are of considerable interest in many fields, such as material, analytical and medical sciences. Particularly, vesicular assembly of nanoparticles (nanoparticle vesicles) will propose new applications of nanoparticles facilitating the inner space, such as drug delivery, catalyst carrier, surface-enhanced Raman scattering (SERS) sensing platforms. Herein we demonstrate that the surface modification with single molecule; semi-fluorinated ligand can efficiently produce sub-100 nm (ca. 60 nm in a diameter) nanoparticle vesicles in THF solution [1, 3]. This approach is based on simple one-pot ligand modification and applicable to gold nanoparticles with a diameter from 5 to 20 nm. The newly synthesized semi-fluorinated ligands (SFL) were composed of three parts; oligoethyleneglycol (OEG), fluorinated triethyleneglycol (FG) and alkyl chain (C11) having thiol terminus. We applied these nanoparticle vesicles for sensing system based on SERS, which give largely increased Raman signals compared with general Raman signals. Application for light-responsive drug carrier [2] of the nanoparticle vesicles will be discussed.

Figure 1. Schematic illustration of nanoparticle vesicle (left) and STEM image (right)

References [1] K. Niikura, N. Iyo, T. Higuchi, T. Nishio, H. Jinnai, N. Fujitani and K. Ijiro, J. Am. Chem. Soc., 134, 7632 (2012). [2] K. Niikura, N. Iyo, Y. Matsuo, H. Mitomo, and K. Ijiro, ACS Appl. Mater. Interfaces, 5, 3900 (2013). [3] J. Wei, K. Niikura, T. Higuchi, T. Kimura, H. Mitomo, H. Jinnai, Y. Joti, Y. Bessho, Y. Nishino, Y. Matsuo,

and K. Ijiro, J. Am. Chem. Soc., 138, 3274 (2016).

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Evaporation retarding wax ester monolayers – insight through molecular dynamics simulations

Riku O. Paananen1, Matti Javanainen2, Ilpo Vattulainen2, Juha M. Holopainen1

1 Helsinki Eye Lab, Ophthalmology, University of Helsinki and Helsinki University Hospital, P.O. Box 220, 00290 Helsinki, Finland

2 Department of Physics, University of Helsinki, P.O. Box 64, 00014 University of Helsinki, Finland


Wax esters (WE) are nonpolar lipids that consist of two hydrocarbon chains connected by an ester moiety. They are of specific interest due to their high abundance in the secretions of Meibomian glands, which are located in the inner eyelids of mammals. This secretion forms a thin layer, which covers the surface of the eye, called the tear film lipid layer (TFLL). Tear film lipid layer is thought to reduce evaporation of aqueous tears from the surface of the eye and prevent the eye from drying. However, the molecular level organization of the TFLL is not known and conflicting results have been obtained concerning the evaporation resistance of TFLL-like films [1]. Recent studies have found that Langmuir monolayers of pure WEs have strong evaporation resistance [2], and it is based on a solid, bulk-like organization of the molecules at the air-water interface [3]. In the current work we have developed an all-atom molecular dynamics model based on the OPLS force field [4] with the L-OPLS re-parameterization of long chain hydrocarbons [5] for three WEs (palmityl laurate, palmityl palmitate and behenyl oleate). The model was evaluated by comparing the bulk properties of WEs to experimental melting point and X-ray diffraction data from the literature. The model was also used to simulate WE monolayers at the air water-interface in combination with the recently developed OPC water model [6] and the results were compared with experimental Langmuir monolayer surface potential and Brewster angle microscopy measurements. Good agreement was found between the simulation model and experimentally determined bulk melting points and crystal structures. Simulations at the air-water interface produced qualitatively similar surface potential as measured in Langmuir monolayer experiments. Both bulk-like extended conformation and hairpin-like conformation were found to be stable at the air-water interface, depending on the temperature and mean molecular area, similar to experimental results. Water permeation was found to be faster through disordered WE films compared to solid films. The developed model is found to be suitable for simulating wax esters at the air-water interface. Importantly, it satisfies two criteria required for a good model of the TFLL: First, it reproduces crystalline ordering of WEs, since TFLL has been found to have significant crystalline order at physiological temperatures [7]. Second, it reproduces both the bulk and monolayer properties of WEs, since TFLL likely contains regions of bulk lipid in addition to a monolayer.

References [1] Millar TJ, Schuett BS, Exp Eye Res. 137, 125-138 (2015). [2] Rantamäki AH, Wiedmer SK, Holopainen JM, Invest Ophthalmol Vis Sci. 54(8), 5211-5217 (2013). [3] Paananen RO, Rantamäki AH, Holopainen JM, Langmuir 30(20), 5897-5902 (2014). [4] Jorgensen WL, Maxwell DS, Tirado-Rives J, J. Am. Chem. Soc. 118, 11225-11236 (1996). [5] Siu SWI, Pluhackova K, Böckmann RA, J. Chem. Theory Comput. 8(4), 1459-1470 (2012). [6] Izadi S, Anandakrishnan R, Onufriev AV, J. Phys. Chem. Lett. 5(21), 3863-3871 (2014). [7] Leiske DL, et al. Langmuir 28(32), 11858-11865 (2012).

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Substituents modulate biphenyl insertion into lipid membranes

L. A. Nelson1, A. Rashid1, A. Vakurov1, S. Mohamadi1, Didem Sanver2

1School of Chemistry, University of Leeds, Woodhouse lane LS2 9JT, Leeds, UK 2School of Food Science and Nutrition, University of Leeds, LS2 9JT, Leeds, UK


Biphenyl (BP) and its derivatives are well known for their thermal stability, electrical insulation and resistance to redox processes and have been widely used in the past in transformers and capacitors as dielectric fluids. Moreover, these substance have also been employed in the preparation of pesticides, optical brighteners, and as fungicides in waxing many fruits. However substituted BPs are established environmental toxins. Chlorobiphenyls (Cl-BPs) have been a significant issue for their toxicity, bioaccumulation and environmental persistence because of their stability. Fluorescence spectroscopic and electrochemical impedance techniques and quantum mechanical binding energy calculations have been applied to the study of the interaction of ortho (o)-, meta (m)-and para (p)-Cl-, o-, m-and p-HO-, p-H3CO-, p-H3C-, p-NC-and p-O3-S-substituted biphenyls (BPs) with dioleoyl phosphatidylcholine (DOPC) vesicles and Hg supported DOPC monolayers in order to understand their biological activity. Non-planar o-substituted BPs exhibit the weakest interactions whereas planar p-substituted BPs interact to the greatest extent with the DOPC layers. The substitutedBP/DOPC bilayer and monolayer interaction depends on the effect of the substituent on the aromatic electron density, which is related to the substituents' mesomeric Hammett’s constants. Substituted BPs with increased ring electron density penetrate the DOPC vesicle membranes and do not increase the DOPC monolayer thickness on Hg. Substituted BPs with lower ring electron density remain in the interfacial and superficial layer of the free standing DOPC membranes and can cause an increase in the monolayer’s thickness on Hg depending on their location. Quantum mechanical calculations show a higher binding energy of electron-withdrawing substituted BP rings with methyl acetate as a model for the –CH2-(CO)O-CH2-fragment of a DOPC molecule. This explains theaccumulation of these BPs within the interfacial and superficial regions of the DOPC monolayer as shown in Figure 1 below.

Figure 1. Schematic presentation of (A) p-OH-BP, (B) p-Cl-BP and (C) p-NC-BP interaction with DOPC

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Benzo[a]pyrene in membrane environment - molecular dynamics studies

J. Korchowiec1, S. Trojan1, A. Stachowicz-Kuśnierz1, B. Korchowiec2

1 Department of Theoretical Chemistry, Faculty Of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Cracow, Poland

2 Department of Physical Chemistry and Electrochemistry, Faculty Of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Cracow, Poland


The influence of benzo[a]pyrene, a common air pollutant, on model pulmonary surfactant monolayers was investigated using molecular dynamics simulations. The simulations were carried out in NVT- and NpnAT-ensembles, where N, V, T, pn, and A are number of particles, volume, temperature, normal pressure, and surface area, respectively. The simulation setup included a water slab bounded by two vacuum slabs. Two symmetric monolayers, each composed of 100 phospholipid molecules, were placed at the vacuum/water interfaces [1,2]. Two monolayer models of pulmonary surfactants, namely DPPG/DPPC and DPPC/POPC, were taken into account. MD calculations were carried out using NAMD2 [3] package and CHARMM [4] force field. The obtained results, i.e., surface tension and atomic level information were compared with the experimental findings (surface pressure-surface area isotherms and Brewster angle microscopy) [5]. The perform calculations confirmed the experimentally observed condensing effect of benzo[a]pyrene molecules on model monolayers. Acknowledgement This work was supported by the Polish National Science Centre, Project No. 2014/13/B/ST4/04995.

References [1] B. Korchowiec, J. Korchowiec, M. Gorczyca, J-B Regnouf de Vains, E. Rogalska, J. Phys. Chem. B, 119, 2990-3000

(2015). [2] B. Korchowiec, M. Gorczyca, E. Rogalska, J.-B. Regnouf de Vains, M. Mourer, and J. Korchowiec, Soft Matter, 12,

181-190 (2015). [3] L. Kale, R. Skeel, M. Bhandarkar, R. Brunner, A. Gursoy, N. Krawetz, J. Phillips, A. Shinozaki, K. Varadarajan and K.

Schulten, J. Comput. Phys., 151, 283-312 (1999). [4] B. R. Brooks, R. E. Bruccoleri, B. D. Olafson, D. J. States, S. Swaminathan and M. Karplus, J. Comput. Chem., 4, 187-

217 (1983). [5] B. Korchowiec, Y. Corvis, T. Viitala, C. Feidt, Y. Guiavarch, C. Corbier, J. Phys. Chem. B, 112, 13518-13531 (2008).

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Effect of liposome size on passive drug release rate: in silico hypothesis and in vitro

validation

Aniket Magarkar1,2, Tatu Lajunen2, Pavel Jungwirth1,3, Arto Urtti2, Tapani Viitala2 and Alex Bunker2

1 Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Prague,

Czech Republic 2 Division of Pharmaceutical Biosciences, Faculty of Pharmacy, University of Helsinki, Helsinki, Finland

3 Department of Physics, Tampere University of Technology, Tampere, Finland


We have developed novel protocol in order to simulate the surface of the liposomes less than 100nanometers in size; this has allowed us to look into liposome sizes and their biophysical properties and if they are altered/modified due to geometry of liposome alone such as effect surface charge and interaction with drug molecules. We looked into structure of one of the FDA approved liposome based drug delivery formulation, doxil®, that is doxorubicin molecule encapsulated in liposome of different sizes. Our molecular dynamics simulation results showed that there is degree of dependence on the liposome size with respect to partitioning of doxorubicin molecule within lipid bilayer and interactions of doxorubicin molecule with lipids. This also reflects in the rate of passive drug release; which is smaller the liposomes, faster is the drug release rate. These in silico results were validated by the in vitro UPLC experiments.

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Biomimetic glass nanostructures for efficient anti-reflection and self-cleaning

Alaric Taylor1, Ioannis Papakonstantinou2, Ivan P. Parkin1

1Department of Chemistry, University College London, Gordon Street, London WC1H OAJ, United Kingdom.

2Department of Electronic and Electrical Engineering, University College London, Torrington Place, London WC1E 7JE, United Kingdom.


Tapered, high aspect-ratio nanostructures, with a sub-wavelength periodicity, act as highly-efficient anti-reflection interfaces. These type of surfaces mimic the corneal nanostructures found on the eyeballs of moths which enable them to evade detection from predators. “Motheye” antireflection interfaces are broadband, polarisation-insensitive and omnidirectional and therefore attractive for a variety of optical applications. In addition, these nanostructured interfaces promote enhanced wetting and can be exploited to either self-clean under the action of rain (super-hydrophobic) or prevent fogging (super-hydrophilic). The combination of the above optical and wetting functionalities can be used to enhance a variety of technologies ranging from goggles to smart-windows. However, their creation over large areas can be challenging. We will present a facile and low-cost method for fabricating “motheye” nanostructures using a Langmuir–Blodgett colloidal lithography technique (see Fig. 1) that can be applied to a variety of different substrate materials and topologies.

Figure 1. Self-assembled polystyrene nanosphere monolayer (a) u

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Bio-inspired organogel exhibiting anti-X surface properties

C. Urata, G. J. Dunderdale, T. Sato, M. W. England and A. Hozumi

National Institute of Advanced Industrial Science and Technology (AIST), 2266-98, Anagahora, Shimoshidami, Nagoya 463-8560, Japan


The creation of novel liquid-repellent surfaces for various liquids (aqueous and organic) has recently attracted increased attention, ranging from fundamental surface science to practical coating applications. The pinning of residual droplets to solid surfaces often causes corrosion, contamination by impurities, and can lead to poor visibility for windows and touch screens. Generally, studies related to this field have focused on maximizing the static contact angles, and decreasing the contact area between the liquid drop and surface, by combining textured surfaces with perfluorinated organic compounds. However, once such artificial surfaces are physically or chemically damaged, their surface properties are permanently lost. On the other hand, some living organisms maintain their surface properties through secretion of plant wax and mucus. In this study, we report on novel materials/coatings inspired by such biological systems [1]. To realize long-lasting surface properties, we have particularly focused on the syneresis of organogels, which were prepared by hydrosilylation of 2 types of silicones [2], and several guest organic liquids (Scheme1). As compatibility is decreased to a certain critical point, induced by chemical and/or physical effects, the guest organic liquids gradually leach out onto the organogel surface. Thanks to this unique artificially secreting nature, contact of various liquids/solids and ices can be effectively prevented, resulting in the excellent anti-sticking properties [1]. We first confirmed secretion of liquid phases from the matrices of our organogels and their excellent anti-sticking surface properties. For the purpose of anti-icing applications, we tuned the critical incompatibility point of our organogels, which possess reversible thermo-responsive secretion properties. In this case, the secretion starts when the temperature is cooled below 0 °C, and the secreted liquids are absorbed back into the matrices by leaving them in air, at ambient temperature, for a few hours. Thanks to these smart surface properties, an ice-pillar formed on the organogel at -15 °C easily slid off at a very low tilt angle, without any additional force. Furthermore, we have successfully demonstrated regeneration of superhydrophobicity, artificially mimicking lotus leaves by using a liquid that is chemically reactive to ambient humidity. Our technique, demonstrated here, undoubtedly shows great potential for application in dynamic, multifunctional, and self-recovering coatings. Acknowledgements

This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas (A.H. and C.U.; No.

24120005) of The Ministry of Education, Culture, Sports, Science, and Technology (MEXT).

References

[1] A. Hozumi et al., J. Mater. Chem. A., 3, 12626 (2015).

[2] A. Hozumi et al., JACS, 134, 10191 (2012).

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Scheme 1. Conceptual image of this study.


96

Protein misfolding and aggregation triggered by adsorption at liquid- condensed

boundaries in Langmuir monolayers

M. R. Martina, P. Baglioni, G. Caminati

Department of Chemistry “Ugo Schiff”/CSGI, University of Florence, Via della Lastruccia 3-13, I-50019, Sesto Fiorentino (Firenze), Italy


Severe neurodegenerative disorders including Parkinson’s and Alzheimer’s diseases are currently associated with the deposits of insoluble protein aggregated in amyloid fibrils, at the same time an increasing number of scientific reports evidence that protein misfolding and aggregation can be triggered by interaction with the phospholipid membrane. In particular, the presence of condensed phospholipid domains is considered to play a major role in the onset pathologically relevant aggregation of proteins. In the work, the role of lateral phase separation on the misfolding and aggregation of a water-soluble model protein has been extensively investigated for planar membrane models, i.e. Langmuir monolayers. Lysozyme was selected as model protein since its misfolding and pre-amyloid fibril-like aggregation was previously shown to occur at phospholipid liposomes interface [1]. The results collected for Langmuir monolayers allowed for the direct visualization of phospholipid phase domain formation and lysozyme adsorption from solution flanked by the thermodynamic and spectroscopic investigation. We studied mixed phospholipid monolayers of DSPC/DOPC/Cholesterol at the water-air interface by means of surface-pressure area isotherms and Brewster Angle Microscopy as a function of monolayer composition and temperature. The same techniques were adopted to investigate the interaction of the water-soluble lysozyme adsorbed at the monolayer interface: native as well as preliminary fibrillated lysozyme was injected in the subphase under the phospholipid monolayer at selected lipid composition, temperature and surface pressure. Lysozyme insertion was studied for homogeneous expanded phases of the monolayer as well as in the presence of raft-like condensed domains. For both native and fibrillated lysozyme, we observed that the protein is adsorbed at the monolayer/water interface but with different kinetics. In both cases, the adsorbed lysozyme segregates along the border of the condensed domains eventually forcing a transition from a circular to a polygonal structure of the phospholipid domains. Monolayer/lysozyme systems were transferred onto solid support and the resulting protein structure was characterized by means of circular dichroism and FT-IR/ATR spectroscopy. The results evidenced the presence of the characteristic features of β-sheet units not only for the pre-fibrillated protein but, more importantly, for the globular form after interaction with the raft-domains in the monolayer. Spatially-resolved fluorescent spectra collected by means of Confocal Laser Scanning Microscopy after staining of the monolayer/lysozyme film with Congo Red (CR) clearly evidenced the appearance of β-sheet structures for all systems thus indicating the presence of aggregates enriched in fibril-like structure and confirming the direct the involvement of lipid rafts in amyloidogenic processes.

Acknowledgements We acknowledge the financial support from the Tuscany Region in the framework of PARFAS 2007-2013 (Linea d’Azione 1.1 - Azione 1.1..2 -SUPREMAL ).

References [1] Al-Kayal, T., Russo, E., Pieri, L., Caminati, G., Berti, D., Bucciantini, M., Stefani, M., Baglioni, P. Soft Matter 8, 9115-9126 (2012).

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Design and realisation of iron oxide nanoparticles conjugated by folic acid as

targeted hyperthermia systems

Gabriele Giancane1, Rosanna Pagano2, Valentina Bonfrate, Ludovico Valli3, Simona Bettini2

1Department of Cultural Heritage, University of Salento, Via per Arnesano, Lecce, Italy 2Department of Engineering for Innovation, University of Salento, Via per Arnesano, Lecce, Italy

3Department of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, Lecce, Italy


The possibility to target a drug into a diseased cell is a paramount goal to avoid involvement of healthy tissues in therapies. Most of the cancer therapies are not selective and very invasive. In order to overcome this problem, super paramagnetic magnetite nanoparticles have been synthetized and their hyperthermal properties have been evaluated. If cancer cell temperature increases above 42°C, the cellular death is induced; on the contrary healthy cells appear more robust than the diseased ones. Besides this, paramagnetic nanoparticles were capped by means of a SiO2 shell to protect them even in oxidant environments. The core-shell structure of magnetite-SiO2 has been decorated with folic acid which works as a “Trojan horse” for the cancer cells. In fact, many kinds of tumor cells overexpress folate receptor (FR) and the supramolecular nanoadduct can be easily targeted in the cell [1].

Figure 1. TEM micrographs of a) IO@ SiO2, c) IO@SiO2@FA and schematization of the surface morphology of d) IO NPs, c) IO@SiO2, d) IO@SiO2@FA

The supramolecular adduct was demonstrated to be internalized, as expected, by HeLa cells, that overexpress FR on their membrane. Furthermore, such nanoadducts was demonstrated not cytotoxic even after 72 hours treatment. More in particular, ellipsometric analysis evidences the behavior of folate receptor as accumulating point for micrometric aggregates of the hyperthermic nanoadducts across the cell membrane, permitting the internalization via potocytosis, a caveolin-coated endocytosis pathway.

References

[1] D. G. Archer, J Phys Chem, 27, 915 (1998). [2] S. Bettini, A. Santino, L. Valli, G. Giancane, RSC Adv., 5, 18167-18171 (2015).

a

d

c

b

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98

Adsorption of steroidal saponin – digitonin – onto phospholipid monolayers

Marta Orczyk1, Kamil Wojciechowski1, Gerald Brezesinski2

1Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland 2Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, 14476 Potsam, Germany

E-Mail address: [email protected]

Saponins are a family of glycoside type biosurfactants produced by plants, microorganisms as well as some marine organisms. In spite of numerous potential applications of saponins there is still lack of viable and detailed information confirming the effectiveness and mechanism of their interaction with biological membranes [1]. Digitonin, a steroidal saponin, is an interesting object of research, mostly because of a wide spectrum of its biological properties [2].

Figure 1. Possible application of saponins

In this study, Langmuir monolayers of zwitterionic (DPPC, DMPE, POPC, POPE, DSPC, DSPE, DPPE) and ionic (DPPS, DPPG) phospholipids were used to understand the effect of digitonin on the lipid organization by surface pressure relaxation measurement, infrared reflection absorption spectroscopy (IRRAS) and fluorescence microscopy. The increase of surface pressure (Π) suggests that digitonin adsorbs at the air/water interface and is capable of penetrating all uncompressed phospholipid monolayers (Π0 < 1 mN/m). However, the detailed data obtained from IRRAS show that digitonin interacts with the lipid monolayers in a very selective way. It turns out that the headgroup, the lipid tails and the phase, all affect the interaction of digitonin with the lipid monolayer. Nevertheless, it should be noted that digitonin did not cause any disruptive effects on the monolayers. Even when incorporated into the lipid, it could be easily squeezed out by mechanical compression, e.g. in the case of DPPE and DPPS. The conclusions obtained from the IRRAS measurements are in the line with the micrographs obtained from the fluorescence microscopy. Acknowledgements This work was financially supported by the Polish National Science Centre, grant no. 2014/13/N/ST4/04122.

References [1] J.P. Vincken, L. Heng, A. Groot, H. Gruppen, Phytochemistry 68, 275-297 (2007). [2] M.J.H. Geelen, Analytical Biochemistry 347, 1-9 (2005).

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Influence of oxidized lipids in the membrane organization, contribution of

Langmuir monolayers and Langmuir-Blodgett films

C. Grauby-Heywang1, F. Moroté1, M. Mathelié-Guinlet1,2, I. Gammoudi3, T. Cohen-Bouhacina1

1LOMA, Univ. de Bordeaux, UMR CNRS 5798, 351 cours de la libération, 33405 Talence cedex, France

2ICMCB, UPR CNRS 9048, 87 avenue du Dr Schweitzer, 33608 Pessac cedex, France 3NanoPhyNov, LOMA, Univ. de Bordeaux, 351 cours de la libération, 33405 Talence cedex, France


Oxidation of membrane lipids can occur via different processes, leading to lipid derivatives with truncated and more polar chains. Their presence in membranes induces strong modifications of their biophysical properties (fluidity, thickness, molecular interaction...). In this frame Langmuir monolayers and Langmuir-Blodgett (LB) films are particularly pertinent membrane models, that we couple with atomic force microscopy (AFM). AFM is a non-damaging and high resolution imaging method, based on the measurements of interaction forces between a fine tip and the sample surface, giving information on the sample topography, but also on its visco-elastic properties. In a first step, we studied the oxidation by air oxygen of LB films of POPC, a monounsaturated phospholipid [1]. AFM showed that these films are sensitive to oxidation, even if this process is rather slow, occurring in a few days. It led to the formation of domains regularly distributed on the film surface, suggesting that oxidation occurs locally, likely in areas presenting a local defect. These domains were also higher (around 0.8 nm) than the surrounding intact phase. We assume that this is due to the reversal of the oxidation chain, as previously described in molecular simulations [2]. However, it was not possible to define the chemical composition of oxidized lipids resulting from POPC oxidation in our samples. Therefore, in a second step, we explored the behaviour of two oxidized derivatives of POPC embedded in POPC monolayers at different molar ratios: PoxnoPC and PazePC bearing both a truncated chain ending with an aldehyde and a carboxylic function, respectively [3]. Surface pressure measurements showed that PoxnoPC induces an expansion of mixed monolayers, whereas PazePC-POPC monolayers behave ideally. However the presence of both oxidized lipids increases the monolayer elasticity, as shown by compressibility modulus. The expansion induced by PoxnoPC could be due to an increase of the tilt angle of the partially reversed oxidixed chain in POPC monolayers as compared to pure PoxnoPC ones. PazePC carboxylic function being protonated under our experimental conditions, the oxidized chain would keep on the contrary an usual non reversed orientation, without changing mean molecular areas. At last, AFM images show that mixed monolayers are on the whole homogenous, supporting the hypothesis of a homogenous distribution of PoxnoPC and PazePC in POPC monolayers. However, some protrusions are also observed under specific conditions of surface pressure in PazePC-POPC LB films, due to the local formation of monomolecular layers superimposed locally under the monolayer at the air-water interface. Profile heights show that up to five monolayers could be superimposed.

References [1] N. R. Faye, F. Moroté, C. Grauby-Heywang, T. Cohen-Bouhacina, Int. J. Nanotechnology 10, 390-403 (2013). [2] H. Khandelia, O. G. Mouritsen, Biophys. J. 96, 2734-2743 (2009). [3] C. Grauby-Heywang, F. Moroté, M. Mathelié-Guinlet, I. Gammoudi, N. R. Faye, T. Cohen-Bouhacina, submitted to Chem. Phys. Lipids.

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Molecular transport in lipid membranes: lipid exchange and translocation

processes investigated by neutron scattering

Gerelli Yuri1, Porcar Lionel1, Perez-Salas Ursula2 and Fragneto Giovanna1

1Institut Laue – Langevin, 71 avenue des Martyrs, Grenoble, France

2Department of Physics, University of Illinois, 845 W. Taylor St. M/C 273, Chicago, US

E-mail address:[email protected]

The phospholipid bilayer is the basic structural motif of most biological membranes. As such, many biological processes occur within or in the proximity of the cell membrane, and therefore, interest in the properties and behavior of lipids in membranes is considerable. For example, it is found that in nature the lipid distribution across the inner and outer leaflet of cell membranes is asymmetric [1] and this asymmetry plays a prominent role in processes like cell fusion, activation of the coagulation processes and the recognition and removal of apoptotic cells by macrophages. Therefore there is great interest in studying the factors determining lipid movement across membranes as well as the resulting lipid mapping in the membrane, both of which are far from being understood and characterized. In the literature it is found that there are big discrepancies in the timescale of the occurrence of lipid flip-flop in model bilayer systems, partly due to the fact that these measurements were based on the indirect observation of the process [2,3]. However, with the sub-nanometer spatial resolution of neutron reflectometry, it is possible to directly obtain lipid composition differences in the leaflets of a bilayer, and in particularly resolve them for times scales as short as a few minutes. Starting from these results we extensively studied, by neutron reflectometry, temperature and time dependence of the structure of lipid bilayers looking for traces of structural asymmetry and consequent relaxation towards an equilibrated symmetric bilayer. We discovered that the structure of an asymmetric reconstituted lipid bilayer spontaneously relaxes, on a subsecond time-scale, if the lipids are in the fluid phase i.e. in biological relevant conditions [4]. The same results were confirmed by the monitoring the time- and temperature-dependence of the structure of a solid supported lipid bilayer exposed to a solution of isotopically labeled vesicles [5]. In this case, lipid interbilayer exchange was shown to be the time limiting process, while lipid intra-bilayer movement (flip-flop) was too fast to be visualized within the experimental acquisition time. The exchange process was characterized by an Arrhenius-like behavior and the activation energy of the process was found to be concentration-independent. The combination of the two results offers a novel point of view on the characteristics of inter- and intra-bilayer rearrangement processes.

Figure 1. Pictorial sketch of the exchange process as measured by Neutron

Reflectometry. Time evolution of reflectivity curves is also shown.

References [1] P.F. Devaux, Biochemistry 30, 1163 – 1173 (1991) [2] M. Nakano et al., Phys. Rev. Lett. 98, 238101 (2007) [3] T. Anglin et al., J. Phys. Chem. B 114, 1903 – 1914 (2010) [4] Y. Gerelli et al., Langmuir 28, 15922 – 15928 (2012) [5] Y. Gerelli et al., Langmuir 29, 12762 - 12769 (2013)

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New tethered phospholipid bilayers integrating membrane proteins for the

development of membrane biochips dedicated to ligand binding studies

M. Chadli1,2, S. Rebaud1, O. Maniti1, C. Marquette1, B. Tillier2, S. Cortes2, A. Girard-Egrot1

1Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, ICBMS,

UMR CNRS 5246, 43 Bd du 11 Novembre 1918, F-69622 VILLEURBANNE, France 2Synthelis, Biopolis, 5, avenue du Grand Sablon, 38700 LA TRONCHE, France


Biomimetic membranes are ideally suited to investigate many issues in membrane biology like membrane/protein interactions. They also represent appropriate supports for protein interaction screening biochips. To that end, we developed a new simple and versatile technique for creating tethered Bilayer Lipid Membranes (tBLM), an attractive platform thanks to its quasi-natural assembly adapted for membrane protein reinsertion. In this approach, the lipid bilayers are achieved by vesicles fusion triggered by a synthetic fusogenic peptide to obtain tBLM on peptide spacers grafted on Au surface [1]. Surface Plasmon Resonance imaging (SPRi) and Atomic Force Microscopy (AFM) have been used to characterize and to visualize the formation process. The main original feature of this simple methodology to form tBLM on gold surface is that the lipid composition of the bilayer can be easily tuned. Hence, it is adapted for (trans)membrane protein reinsertion since we have shown that fusion of proteoliposomes on peptide tethers can be efficiently achieved (Figure 1). Another advantage of this system is the possible miniaturization of the process by spotting all the components on a gold biochip adapted to SPRi measurements. In this context, we tested the interaction between CXCR4, an integral membrane protein expressed by cell-free in liposomal membrane, and two ligands: SDF-1α, its natural ligand and T22, a synthetic antagonist. We were able to detect a specific interaction signal between the reconstituted CXCR4 attached on the peptide tethers and these ligands. Hence, we demonstrated this new approach is a versatile tool for investigating membrane protein reincorporation. It represents a promising way of creating membrane biochips adapted for screening agonists or antagonists of transmembrane proteins, by fusion of proteoliposomes or cell-free expression of these proteins on a pre-formed peptide tethered bilayer lipid membrane.

Figure 1. Proteoliposomes formation and fusion on Au-peptides triggered by a synthetic fusogenic peptide

References [1] French patent pending application, FR14 60 349 (October 2014)

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Nanocast metal oxide microspheres for enrichment of phosphopeptides

A. Leitner1, M. Sakeye2, C.E. Zimmerli1, J.H. Smått2

1Department of Biology, Institute of Molecular Systems Biology, ETH Zurich, Auguste-Piccard-Hof 1, 8093

Zurich, Switzerland 2Laboratory of Physical Chemistry and Center of Functional Materials, Åbo Akademi University,

Porthansgatan 3-5, 20500 Turku, Finland


Protein phosphorylation is important in many biochemical processes such as controlling signaling pathways and cell death. Mass spectrometry is the technique of choice for investigating phosphorylation, but due to the low abundance of phosphorylated proteins in biological samples, the sample needs to be enriched prior to analysis. Metal oxide affinity chromatography (MOAC) is a widely used enrichment method, where different metal oxides show diverse affinity to phosphopeptides [1]. However, until now it has been difficult to compare their relative performance as different material synthesis protocols have been used in their preparation. In this study [2], we have utilized the nanocasting approach to prepare a range of previously known (TiO2, ZrO2, SnO2 and Fe2O3) and new (In2O3, Co3O4 and NiO) affinity materials by replicating porous micrometer-sized silica spheres. In the nanocasting process [3], the porous silica beads are infiltrated with a metal oxide precursor followed by heating at elevated temperatures and etching in NaOH solution. The method allows for the precise tuning of the surface area (BET: 45-72 m2/g) independently of the composition and particle morphology, which makes a direct comparison between the materials possible (see Fig. 1). Following an earlier described protocol [4], the materials were evaluated by enrichment of complex biological samples and analyzing them by LC-MS/MS. Furthermore, the acidity of the metal oxides was determined by zeta potential titrations. Initial tests using synthetic peptides revealed clear differences in performance between the metal oxides. Strongest binding of phosphopeptides was observed for the most acidic oxides (TiO2 and ZrO2), while the selectivity for peptides containing two or more phosphorylation sites was higher for the less acidic NiO and Co3O4 materials. Furthermore, over 6700 phosphorylated peptides were confidently identified from a HEK 293 cell lysate sample, but the best performing material (ZrO2) could only detect about 58% of these. The complementary affinity by combining different oxides gives a more complete representation of biological events, including highly phosphorylated peptides.

Figure 1. SEM images of various metal oxide microspheres produced by the nanocasting method

References [1] A. Leitner, Trends Anal. Chem. 29, 177-185 (2010). [2] A. Leitner, M. Sakeye, C.E.Zimmerli, J.H. Smått, ACS Appl. Mater. Interfaces, under review (2016). [3] J.H. Smått, N. Schüwer, M. Järn, W. Lindner, M. Lindén, Microporous Mesoporous Mater. 112, 308-318 (2008). [4] A. Leitner, M. Sturm, O. Hudecz, M. Mazanek, J.H. Smått, M. Lindén, W. Lindner, K. Mechtler, Anal. Chem. 82, 2726-2733 (2010).

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Nanoscale investigation of colistin interactions with model phospholipid

membranes by combined infrared and force spectroscopies

O. Freudenthala,d, F. Quilèsa, G. Franciusa, K. Wojszko,c,d M. Gorczycac, E. Rogalskad

aUniversité de Lorraine, CNRS, Laboratoire de Chimie Physique et Microbiologie pour l’Environnement,

LCPME, UMR 7564, Villers-lès-Nancy, F-54600, France cDepartment of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, ul. R.

Ingardena 3, 30-060 Krakow, Poland

dUniversité de Lorraine, Structure et Réactivité des Systèmes Moléculaires Complexes, SRSMC, UMR7565,

Vandœuvre-lès-Nancy cedex, F-54506, France


The excessive use of antibiotics has led to a growing interest of microbial resistance1. The antimicrobial action of peptides is of interest, as bacteria are less likely to develop resistance against such peptides2. Colistin is an antimicrobial peptide of the polymyxin family acting on the external leaflet of Gram negative bacteria outer membrane, more specifically on the negatively charged phospholipids (PL) and lipopolysaccharides (LPS)3-5. However, the detailed mechanism of action of colistin still remains unclear. We have examined the effect of colistin on different PL monolayers at the air/liquid interface via Langmuir isotherms as well as on PL bilayers in aqueous media via atomic force microscopy (AFM), through imaging and force spectra, and with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The PLs under our scope were those particularly found at the outer membrane of Gram- bacteria; zwitterionic 1,2-Dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC)6. The interactions of PLs with colistin at several concentrations (10 µM, 50 µM and 150 µM) have been studied by observations with the above mentioned techniques. The effects of colistin (50 µM) on chosen PL monolayer isotherms in comparison to equivalent monolayers on pure water subphase have been observed. Insights into the topographical and elastic changes in the PL bilayers after colistin injection are presented via AFM imaging and force spectra. Finally, changes in the PL bilayer’s ATR-FTIR spectra as a function of time within three bilayer compositions and the influence of colistin on their spectral evolution were examined together with the evolution of the Amide II and νC=O band integrated intensity ratios. This work shows how three physico-chemical techniques (Langmuir isotherms, AFM and ATR-FTIR) can be used to clarify the importance of PL membrane composition as well as peptide total concentration on the colistin action on PLs. We show that complementary information can be obtained on peptide action on model PL membranes via both, mono- and bilayers.

References [1] R. Gonzales, et al., Clinical Infectious Diseases, 33 (2001) 757-762 [2] V. Balhara et al., (BBA)-Biomembranes, 1828, (2013), 2193-2203 [3] C. Mestres, et al., Int. J. Pharm., 160 (1998) 99-107 [4] S. Roes, et al., Langmuir, 21 (2005) 6970-6978 [5] H.S. Chung, C.R.H. Raetz, Biochemistry, 49 (2010) 4126-4137 [6] W. Dowhan et al. Annual Review of Biochemistry, 66, (1997) 199-232

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Oscillations in stability of consecutive chemical bonds at the molecule-metal

interface in self-assembled monolayers revealed by static SIMS.

J. Ossowski1, J. Rysz1, M. Krawiec2, D. Maciazek1, Z. Postawa1, A. Terfort3, and P. Cyganik1

1Institute of Physics, Jagiellonian University, 30-059 Kraków, Poland 2Marie Curie Sklodowska University, Institute of Physics, Pl M Curie Sklodowskiej 1, 20-031 Lublin, Poland

3Chemistry Department, Goethe University, 60438 Frankurt, Germany


Despite significant experimental and theoretical efforts the structure of the substrate-molecule interface for chemisorbed species and its stability are still poorly known even for the simplest systems. At the same time this missing information remains of a key importance for most of applications which are based on much more complicated systems leaving them, therefore, particularly difficult to analyze. In this presentation we report extensive static secondary ion mass spectrometry (SIMS) studies[1,2] on homologic series of thiols (BPnS, CH3-C6H4-C6H4-(CH2)n-S-(Au(111)/Ag(111)), n = 2-6) and selenols (BPnSe, CH3-C6H4-C6H4-(CH2)n-Se-(Au(111)/Ag(111)), n = 2-6) where film structure and stability at the molecule-metal interface can be modified systematically as verified by our previous experiments [3-5]. Correlating SIMS data with previous microscopic[2], spectroscopic[3] and very recent neutral mass spectrometry studies [4,5] we show that SIMS can be successfully applied to monitor fine changes in the molecule-substrate interface stability of these model SAMs. More importantly, our data exhibit clear positional oscillations for the stability of consecutive chemical bonds along the adsorbed molecule, with the amplitudes diminishing with increasing distance from the molecule-metal interface. To explain these observations, we have performed molecular dynamics simulations and density functional theory calculations. Our calculations show that the observed oscillations in chemical bond stability have a very general character in chemistry related to breaking the translational symmetry in molecules.

Figure 1. The strength of a chemical bond does not only influence the strength of its immediate neighbours, but the effect penetrates deeper into the molecules. Studying ordered surface monolayers by TOF-SIMS opens the opportunity to look at this influence on all bonds at once.

References [1] Ossowski, J.; Rysz, J.; Krawiec, M.; Maciazek, D.; Postawa, Z.; Terfort, A.; Cyganik, P.; Angew. Chem., Int. Ed., 54, 1336–1340 (2015) [2] Ossowski, J.; Rysz, J.; Terfort, A.; Cyganik, P; in preparation [3] Cyganik, P.; Buck, M.; Azzam, W. ; Wöll, Ch.; J. Phys. Chem. B, 108, 4989–4996 (2004) [4] Cyganik, P.; Szelagowska-Kunstman, K.; Terfort, A.; Zharnikov, M.; J. Phys. Chem. C, 112, 15466–15473 (2008) [5] Szelagowska-Kunstman, K.; Cyganik, P.; Schüpbach, B.; Terfort, A.; Phys. Chem. Chem. Phys., 12, 4400–4406 (2010)

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Rectification properties at the Si(111)/monolayer/liquid metal junction

T. Utsunomiya, A. Cheng, T. Ichii, H. Sugimura

Department of Materials Science and Engineering, Graduate School of Engineering, Kyoto University, Yoshida-hommachi, Sakyo-ku, Kyoto 606-8501, Japan


Self-assembled monolayers (SAMs) formed on noble metals such as Au and Ag have been intensively studied as a component in molecular electronics. In particular, SAMs of ferrocene (Fc) derivatives have been proposed as a molecular rectifier, where liquid metal was used as the damage-less electrode [1]. Our group has reported the fabrication process of Fc-terminated SAM on the hydrogen-terminated Si(111) substrate [2]. In this study, we characterized the rectification properties of alkanethiolate- and ferrocenylalkanethiolate-SAMs formed on Si(111) by using liquid metal as the contact electrode. We prepared three SAM samples: 11-Ferrocenyl-1-undecanethiol (FUT, Figure 1a), 6-Ferrocenyl-1-hexanethiol (FHT, Figure 1a), and Hexadecanethiol (HDT) SAM on Si(111). Photochemical grafting of these molecules was performed on hydrogen-terminated Si(111) substrates (highly doped n-type and p-type, Resistivity: 0.001-0.004 Ω•cm). The eutectic alloy of gallium and indium (EGaIn) was used as a contact electrode and DC electrical properties of EGaIn/ SAM/ Si samples were studied as shown in Figure 1b. Figure 1c shows the current-voltage characteristics of FUT-SAM on n-type Si(111). Asymmetric responses were obtained. In order to eliminate several uncertainty originating from the fluctuation of contact area and contact resistances, we calculated the rectification ratio of the junctions by using defined equation (1).

Figure 1d shows the histogram of the rectification ratio (r) for FUT-, and FHT-SAM on Si(111). The averaged r value is 0.5, and 2.43 for the FUT-SAM, and for the FHT-SAM, respectively. The measured r value of HDT-SAM shows the no rectification in this bias voltage range. These results indicate that the origin of rectification is the terminal ferrocene, and that the rectification direction can be reversed with the molecular length.

Figure 1. (a) Molecular structures of FHT and FUT. (b) Schematic illustration of the I-V measurements. (c) The obtained current-voltage characteristics. (d) The histogram of the rectification ratio.

References [1] W. F. Reus, M. M. Thuo, N. D. Shapiro, C. A. Nijhuis, G. M. Whitesides, ACS Nano, The SAM, Not the Electrodes, Dominates Charge Transfer in Metal-Monolayer//Ga2O3/Gallium–Indium Eutectic Junctions, 6, 4806 (2012). [2] M. U. Herrera, T. Ichii, K. Murase, H. Sugimura, ChemElectroChem, Use of Diode Analogy in Explaining the Voltammetric Characteristics of Immobilized Ferrocenyl Moieties on a Silicon Surface, 2, 68 (2015).

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Structure and stability of highly ordered self-assembled monolayers of alkynes on

Au(111)

Tomasz Zaba1, Anna Krzykawska1, Jakub Ossowski1, Agnieszka Noworolska1, Carleen M. Bowers2, Benjamin Breiten2, George M. Whitesides2, and Piotr Cyganik1

1 Smoluchowski Institute of Physics, Jagiellonian University, Lojasiewicza 11, 30-348 Krakow, Poland 2 Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge,

Massachusetts 02138, United States E-mail address: [email protected]

Nowadays, one of the greatest challenge in the field of the molecular electronics is the connection of organic molecules into inorganic electrodes in order to obtain sustainable and stable electrical con-tact. Most of the research in this field focuses on junctions formed by using organic self-assembled monolayers (SAM). An interesting alternative to commonly used thiol SAMs based on the Au-S junction is the use of Au-C junction with carbon in the sp hybridization (𝐴𝑢−𝐶≡𝐶− junction). However, pre-vious spectroscopic results [1-3] suggest that SAM systems based on 𝐴𝑢−𝐶≡𝐶− junction are strongly disordered and thus such alternative has rather limited range of possible applications. In this talk we will present results of combined spectroscopic (XPS, IRRAS), microscopic (STM) and spectrometric (SIMS) measurements [4, 5], which indicate that it is possible to obtain chemically clean and ordered aliphatic alkynes based SAMs (𝐻𝐶≡𝐶−(𝐶𝐻2)𝑛−𝐶𝐻3,𝑛=5,7,9,11), if a rigorous wa-ter and oxygen restrictions are fulfilled. Microscopic experiments (STM) of high-quality samples con-firmed a quasi-crystalline ordering in (√3×√3)R30° structure on the Au(111) surface. In the contrast to previous work2, our XPS results suggest that the oxidation process does not occur via oxygen reac-tion with Au-C bond after layer formation, but it is rather an oxidation reaction of triple bond 𝐶≡𝐶 catalyzed by Au. Once formed, the high-quality SAMs of alkynes are resistant to further oxidation in ambient conditions. We demonstrated that SAMs of alkynes are more stable than analogous alkanethi-ols by performing exchange experiments and monitoring the effects of thermal desorption.5 Our study indicates that the stability of alkynes on Au(111), together with their high structural order, provides the basis for potential applications of this new type of SAM. References [1] Zhang, S.; Chandra, K. L.; Gorman, C. B. J. Am. Chem. Soc. 129, 4876-4877 (2007) [2] McDonagh, A. M.; Zareie, H. M.; Ford, M. J.; Barton, C. S.; Ginic-Markovic, M.; Matisons, J. G. J. Am. Chem. Soc. 129, 3533-2528 (2007) [3] Scholz, F.; Kaletova, E.; Stensrud, E. S.; Ford, W. E.; Kohutova, A.; Mucha, M.; Stibor, I.; Michl, J.; Wrochem, F. J. Phys. Chem. Lett. 4, 2624−2629 (2013) [4] Zaba, T.; Noworolska, A.; Bowers, C.M.; Breiten, B.; Whitesides, G.M.; Cyganik, P. J. Am. Chem. Soc. 136, 11918-11921 (2014) [5] Zaba, T.; Krzykawska, A.; Ossowski, J.; Bowers, C.M.; Whitesides, G.M.; Cyganik, P. in preparation

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The frame-guided assembly

Dongsheng Liu1

1 Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education Department of Chemistry, Tsinghua University, Beijing 100084 (China)

E-mail address: [email protected] How to precisely control the shape and size of final assemblies, especially using same amphiphilic molecules and under the same environmental conditions, is always a challenge in molecular assembly. Inspired by the cytoskeletal/membrane protein/lipid bilayer system that determines the shape of eukaryotic cells, we proposed and ‘the Frame Guided Assembly’ (FGA) strategy to prepare heterovesicles with programmed geometry and dimensions. This method offers greater control over self-assembly: with same molecular system, the size of final assemblies could be tuned at 1 nm level and their shape could vary from spherical to cubic, and even given sized two dimensional sheets. Most importantly, the principle of the FGA could be applied to various materials such as bock copolymers, small molecules including surfactants and lipids, which is a general rule in self-assembly.

Figure 1. Schematic illustration of the Frame Guided Assembly References [1] Z. Zhao, C. Chen, Y. Dong, Z. Yang, Q. Fan, D. Liu, Angew. Chem. Int. Ed., 53, 13468-13470. (2014).

[2] C. Zhou, D. Wang, Y. Dong, L. Xin, Y. Sun, Z. Yang, D. Liu, Small, 11, 1161-1164. (2015). [3] Y. Dong, Y. Sun, L. Wang, D. Wang, T. Zhou, Z. Yang, Z. Chen, Q. Wang, Q. Fan, D. Liu, Angew. Chem. Int. Ed., 53, 2607-2610. (2014).

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Supramolecular polymers with multi-responsiveness based on the host‒guest

chemistry of pillararenes

Chengyou Han1

1China University of Petroleum (East China), No. 66, Changjiang West Road, Huangdao District, Qingdao, China, 266580


Controlling self-assembly and disassembly of monomers by external stimuli is of great importance in the study of supramolecular polymer chemistry and has attracted more and more attention in the past few years. Supramolecular polymers, the combination of supramolecular chemistry and traditional polymer chemistry, consist of the same or different kinds of monomers held together by reversible and directional noncovalent interactions. Based on the responsive and reversible nature of the noncovalent bonds, supramolecular polymers have shown unique and interesting properties, and have become one of the most active fields in supramolecular chemistry and material science. Now, as an important part of supramolecular chemistry, host–guest interactions have become more and more popular in the fabrication of supramolecular polymers. Pillararenes, a new kind of calixarene analogues, have become one of the hottest topics in macrocyclic chemistry since they were found in 2008. Their syntheses, functionalizations, conformations, host–guest properties and applications in different areas have been actively investigated. Interestingly, Huang and coworkers prepared an alkyl chain-based dialkylammonium salt, n-octylethyl ammonium hexafluorophosphate, and found that it complexed with 1,4-dimethoxypillar[5]arene (DMpillar[5]arene) in chloroform and in the solid state to form a [2]pseudorotaxane with N-H•••π interactions and C-H•••π interactions as the main driving forces. Based on this new molecular recognition motif, herein, we synthesized a mono-functionalized pillar[5]arene with a dialkylammonium salt as an AB-type heteroditopic monomer to construct a novel anion responsive supramolecular polymer.

References [1] Han, C.; Ma, F.; Zhang, Z.; Xia, B.; Yu, Y.; Huang, F.*, Org. Lett. 12, 4360–4363 (2010). [2] Han, C.; Yu, G.; Zheng, B.; Huang, F.*, Org. Lett. 14, 1712–1715 (2010). [3] Han, C.; Zhang, Z.; Chi, X.; Zhang M.; Yu G.; Huang, F.*, Acta Chim. Sinica 70, 1775–1778 (2012). [4] Han, C.; Zhang, Z.; Yu, G.; Huang, F.*, Chem. Commun. 48, 9876–9878 (2012). [5] Han, C.; Gao, L.; Yu, G.; Zhang, Z.; Dong, S.; Huang, F.*, Eur. J. Org. Chem., 2529–2532 (2013). [6] Han, C.; Xia, B.; Chen, J.; Yu, G.; Zhang, Z.; Dong, S.; Hu, B.; Yu, Y. and Xue, M.*, RSC Adv. 3, 16089–16094 (2013).

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Formation of metal organic nano-object by surface x-ray radiolysis

P. Fontaine1, S. Mukherjee2, M.-C. Fauré2,3, M. Goldmann2, 3, 1

1SIRIUS Beamline, Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin, BP48, 91192 Gif sur Yvette Cedex, France

2Institut des NanoSciences de Paris, Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05,France

3Faculté des Sciences Fondamentales et Biomédicales, Université Paris Descartes, 45 rue des Sts-Pères, 75006 Paris, France


We are developing an innovative method to obtain Metal Organic nano-objects. We combine the self-assembling properties of organic amphiphilic molecules to the radiolysis technique, which allows producing homogeneous metal aggregates [1]. The organic structure, which shape and size can be adjusted via the physical and chemical conditions, defines a template onto which one grows a metallic layer through the radiolysis reduction of solubilized ions into the solution. In addition to its low cost, such a procedure has the strong advantage in allowing a tuneable and homogeneous inorganic coating (monolayer, spheres, tubes, lamellar and bi-continuous phases, etc.). We already obtained nanometric thickness metallic layers (Ag, Au, Cu, Pt) anchored below an organic monolayer of amphiphilic molecules with suitable hydrophilic part: eg. fatty acid for silver [1,2]. In this 2D geometry that we called « surface radiolysis », Langmuir monolayer is irradiated with an x-ray beam in grazing incidence geometry (Figure 1). The thickness of the metal layer is defined by the penetration of the x-ray evanescent wave (about 4.5 nm), and the layer morphology (2D/3D) by the irradiation time [3]. We also obtained metallic nanoshells by coating unsaturated fatty acid micelles (organic micelles) with silver [4, 5]. We now enlarge this procedure to the use of a solution containing two types of ions to form more complex system. We will present and discuss the first results we obtained on surface x-ray radiolysis on mixture of Cu/Ag and Co/Ag In addition to structural measurements we follow the concentration of each species at the interface during the radiolysis process by surface X-ray fluorescence. The results indicate that the formation of inorganic crystal can be associated to the removal of one ion by the other.

Figure 1. Surface x-ray induced radiolysis geometry

References [1] F. Muller, P. Fontaine, S. Rémita, M.-C. Fauré, E. Lacaze, M. Goldmann Langmuir 20, 4791 (2004). [2] P. Fontaine, M.-C. Fauré, S. Rémita, F. Muller, M. Goldmann, Eur. Phys. J. Special Topics 167, 157 (2009). [3] S. Mukherjee, M.-C. Fauré, M. Goldmann and P. Fontaine, Beilstein J. Nanotechnol., 6, 2406-2411 (2015). [4] S. Remita, P. Fontaine, E. Lacaze, Y. Borensztein, H. Sellame, R. Farha, C. Rochas and M. Goldmann, Nucl. Instrum.

and Meth. B , 263 , 436 (2007). [5] J.Attia, S. Rémita, S. Jonic, E. Lacaze, M.-C. Fauré, E. Larquet, M. Goldmann, Langmuir, 23, 9523 (2007).

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Specific and non-specific binding of proteins and DNA-oligonucleotides on self-

assembled monolayers on gold studied by spectroscopic ellipsometry

I. Solano1, P. Parisse2, O. Cavalleri1, L. Casalis2, M. Castronovo2, M. Canepa1

1Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, Genova, Italy 2Sincrotrone Trieste SCpA, Area Science Park, Basovizza, Trieste, Italy


We investigated the specific vs non-specific binding of proteins and ss-DNA on thiolate Self-Assembled Monolayers (SAMs) on gold by combining Spectroscopic Ellipsometry (SE) (245-1200 nm) with Atomic Force Microscopy (AFM) nano-lithography methods (both shaving and grafting modes). SAMs bearing different functionalities, namely Oligo-Ethylene-Glycol (OEG), Nitrilotriacetic acid (NTA) and single strand DNA (ssDNA), were selected. As concerns OEG-terminated SAMs, SE measurements, analysed by simple models, confirm the formation of the S-Au interface, the transparency of the SAMs and provide a sharp picture of the ability of the EG functionality to protect the surface from non-specific adsorption of proteins [1]. The cross-check between SE and AFM, and the comparison between in-liquid and ex-situ SE measurements allowed to obtain non-perturbative information about the vertical density profile of the SAM and indicate the penetration of water amid the OEG strands. The Ni(II)-mediated affinity of NTA towards histidine was exploited to investigate the specific vs non-specific binding of hexahistidine and His-tagged Small Ubiquitine-like Modifier (SUMO) protein on NTA-terminated SAMs. Applying systematically the difference SE spectra method, which emphasizes the small changes of the SE response upon the nanoscale thickening/thinning of the molecular film, we characterised the specific molecular adsorption and the subsequent desorption after exposure to competitive ligands. The films were investigated in liquid, and ex-situ in air-ambient [2]. The most recent part of our study is devoted to detect the hybridization of gold-immobilized thiolated ssDNA (22 base pair) SAMs with their complementary strands. Differential SE data analysis of ssDNA SAMs allowed to clearly distinguish the optical spectral features related to the DNA molecules: in particular a strong DNA absorption in the UV range (260-270 nm) can be clearly observed in both in-situ and ex-situ data. Using differential SE analysis we are able to clearly detect the specific interaction of the immobilized DNA with its complementary strand in mixed SAMs of ssDNA/mercaptohexanol (MCH).

References [1] I. Solano et al., Phys. Chem. Chem. Phys. 17, 28774–28781 (2015). [2] I. Solano et al., Beilstein J Nanotechn.(submitted).

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An active plasmonic application using self-assembled gold nanoparticle film on the

hydrogel

Hideyuki Mitomo1, Kenta Horie2, Yasutaka Matsuo1, Kenichi Niikura1, and Kuniharu Ijiro1

1Research Institute for Electric Science, Hokkaido University, Sapporo, Japan 2Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Japan


Fabrication of metal nanostructures made of noble metals such as gold or silver is of considerable interest because their plasmonic phenomena can provide functional applications. One of typical examples is a surface‐enhanced Raman scattering (SERS). SERS is a phenomenon that Raman scattering signals of organic molecules can be greatly increased on these structures. Therefore SERS is a promising approach for the label‐free detections of materials. On this SERS application, gap structures and their distances of metal nanostructures are crucially important. A narrower gap can basically form a stronger electromagnetic field and enhance the signals more, but it also makes the insertion of analytes into hot spots more difficult owing to the steric hindrance on their approaches to the narrow gaps. In this study we have fabricated metal nanostructures on the hydrogel through the self-assembly of gold nanoparticles on the solid substrate and transferring them onto a water‐swollen gel. This can be a tunable plasmonic substrate because the size change of the gel is caused by the environmental changes and this could result in a dynamic control of gap distances of the gold nanopattern (Figure 1A). When the gel was immersed into a high salt solution, the gel was contracted and its plasmonic spectrum was red-shifted, and vice versa. And also these spectral shifts were reversible. Therefore, we applied this substrate to SERS measurements. When the target molecules were injected onto this device as the gap was open and SERS was measured after the gap was closed, the signals became stronger than those without any gap control as a conventional SERS substrate owing to the improvement of the insertion efficiency of target molecules to the gaps (Figure 1B). In the case of cytochrome c, which is a hemeprotein with 12 kDa of molecular weight, signal intensities of SERS increased ca. 10‐fold with this active gap control (Figure 2) [1]. It is expected that this tunable plasmonic substrate could be applied to the various kinds of plasmonic nanodevices for the optical switching or biomedical sensing.

Figure 1. Preparation of a tunable plasmonic nanostructure(A) and its Figure 2. SERS spectra of cytochrome application to SERS detection (B). c with (a) and without (b) gap control

References [1] H. Mitomo, K. Horie, Y. Matsuo, K. Niikura, T. Tani, M. Naya, and K. Ijiro, Adv. Opt. Mater., 4, 259‐263 (2016)

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SERS active substrates based on ZnO nanostructures for cupric and mercuric ions

detection in aqueous matrices

S. Bettini1, R. Pagano1, L. Valli2, G. Giancane3

1Department of Engineering for Innovation, Campus University Ecotekne, Via per Monteroni, I-73100 Lecce, Italy

2Department of Biological and Environmental Sciences and Technologies, DISTEBA, University of Salento, Via per Arnesano, I-73100 Lecce, Italy

3Department of Cultural Heritage, University of Salento, Via Birago 64, I-73100 Lecce, Italy


Presence of metal ions in aqueous solutions can be a consequence of natural causes or it is caused by anthropogenic activities, microelectronics and paper processing plants. Heavy metals can affect cell DNA, inducing modifications and cell apoptosis. For these reasons many researchers attempt to develop new methods to remove [1] and to detect metal ions from aqueous matrices. Different analytical techniques have been proposed to detect metal ions in solution. A common problem for all these techniques is the effect of interfering substances on the devices’ response. For example, food and beverage matrices are rich in chlorophylls, anthocyanins, carotenoids, biogenic amines that can strongly influence the spectroscopic features of the active layer. Tetrapyrrolic macrocycles are largely used in the sensing of various analytes both in liquid and in gaseous phase [2], but the strong electronic delocalization of this class of molecules makes difficult the realization of a selective active layer. To overcome this problem, the synthesis of a supramolecular adduct of zinc oxide nanostructure and a free-base tetra-pyridyl substituted porphyrin is proposed in this contribution. The electronic structure of the two organic/inorganic compounds allows to observe a surface-enhanced Raman scattering (SERS) of the porphyrin vibrational bands.

Figure 1. Quenching of the SERS effect of the ZnO@TPyP adduct after the interaction with mercuric and cupric ions.

This phenomenon is quenched by the presence of Hg2+ and Cu2+ according to two different mechanisms monitored and explained by means of time resolved fluorescence spectroscopy. It was demonstrated that other substances in complex matrices, such as the food extracts, do not affect the electronic communication between ZnO and porphyrin preserving the SERS effect and minimizing the effect of interfering compounds. References [1] Bettini, S.; Pagano, R.; Valli, L.; Giancane, G., Nanoscale 6 10113-10117, 2014. [2] Bettini, S.; Pagano, R.; Valli, L.; Giancane, G., J. Phys. Chem. C , 118 (23), 12384–12390, 2014.

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Characterization of solid-supported ultrathin films and molecular interactions

using MP-SPR

Niko Granqvist, Annika Jokinen, Tatu Rojalin and Janusz W. Sadowski

1BioNavis Ltd. Elopellontie 3C, Ylöjärvi, Finland


Surface Plasmon Resonance (SPR) has been used already for a few decades for label-free detection and characterization of biochemical kinetics and affinities of many different types of analytes. However, the physical phenomenon is not limited to biochemistry, but is applicable to other nanoscale characterization of thin films [1]. Multiparametric surface plasmon resonance (MP-SPR) is a new approach to the physical phenomenon, which utilizes full SPR angular spectral measurement and among other things allows new type of thin film characterization methods to be used. MP-SPR can be used to characterize ultrathin nanoscale films for both thickness and refractive index with two methods, either by measuring them in two different media with high RI difference, such as air and water [1,2], or by measuring the films with two or more wavelengths of light [2,3]. The method effectiveness has been extensively demonstrated using different ultrathin films systems [2-4]. The studied films include LB films with approximately 2.5±0.2 nm thickness. Polyelectrolyte multilayer consisting of polystyrenesulfonate and polyallylaminehydrochloride (PSS:PAH) was characterized to grow in 3-3.5 nm steps per layer pair, and self-assembled lipid bilayers spread from vesicles showed typical thickness of approximately 5 nm.Single-sheet CVD-prepared graphene has also been characterized for the thickness and RI [4]. Both of the methods are in good agreement with reference methods used in the studies such as QCM, and with previous literature values obtained with different measurement methods. Thus the MP-SPR based characterization methods for ultrathin films appear to be effective, especially for applications requiring both measurement of the film properties and interactions of different compounds with the film.

References [1] Albers, Vikholm-Lundin, Chapter4 in Nano-Bio-Sensing, Springer (2010) [2] Granqvist et al., Langmuir, 29(27), 2013,8561-8571 (2013) [3] Granqvist et al., Langmuir, 30(10), 2799–2809 (2014) [4] Jussila et al., Optica, 3(2), 151-158 (2016)

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Complex morphologies and structural details in nanoscale thin films and solutions

of functional polymers in various topologies

Moonhor Ree, Young Yong Kim, Kyungho Kwon, Jongchan Lee, Jinseok Lee, Hyunkyung Yun

Dept. of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science & Technology

(POSTECH), Pohang 790-784, Republic of Korea E-mail address: [email protected]

A series of novel polymer systems have been developed via molecular designs and well-controlled syntheses: (i) well-defined functional brush polymers (comblike polymers), (ii) well-defined brush random copolymers and diblock copolymers, (iii) miktoarm star polymers, and (iv) asymmetric ring polymers. Self-assembly characteristics of these novel polymers were investigated in nanoscale thin films as well as in solutions by using synchrotron grazing incidence X-ray scattering, solution X-ray scattering and X-ray reflectivity. These analyses provided structural details of self-assemblies. The self-assembled structures and characteristics will be discussed in aspects of the chemical structures and the conformation and chemical and physical nature of polymer chains.

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Correlation between thin films supramolecular structure and surface interactions

M. Österberg

Aalto University, School of Chemical Technology, Department of Forest Products Technology Bioproduct Chemistry group, P.O. Box 16300, 00076 Aalto, FINLAND


In this work the effect of cellulose supramolecular structure on interactions with mainly water but also other substances is discussed. With surface sensitive tools like Quartz Crystal Microbalance with Dissipation (QCM-D) and Atomic Force Microscopy (AFM) it is possible to gain in-depth understanding of surface interactions like swelling, adsorption, and interaction that are important for performance optimization in applications ranging from packaging to tissue engineering. However, model substrates have to be used with these methods. The model substrates are often self-assembled ultrathin films made using spin-coating or Langmuir Schaefer deposition. While the chemistry of these substrates is well-defined, less focus has been given the effect of roughness, porosity, and degree of order on the interactions. Cellulose films were prepared using spin-coating and Langmuir-Schaefer deposition to obtain thin films of equal thickness, identical cellulose origin, simultaneously with different supramolecular structure. The uptake/release of water molecules and swelling were followed using QCM-D, and the structural features of the films were evaluated by AFM. The influence of structural features of cellulose films, i.e. crystallinity, surface roughness and porosity on water interactions were clarified. The more crystalline cellulose film possessed nanoporosity and as a consequence higher accessible surface area (more binding sites for water) and thus, it was capable to bind more water molecules in humid air and when immersed in water when compared to amorphous cellulose film. Due to the ordered structure, more crystalline cellulose film remained rigid and elastic although the water binding ability was more pronounced compared to amorphous film [1]. Similar effects of surface accessibility was also found for ultrathin films prepared from other cellulose sources like cellulose nanocrystals and cellulose nanofibrils [2]. These results are relevant e.g. when preparing barrier or sensor materials from nanoscaled cellulose. Similarly to the cellulose case, the ultrastructure of collagen thin films has also recently been shown to affect maturation and functionality of human embryonic stem cell derived retinal pigment epithelial cells [3]. The various approaches to preparation of ordered collagen films and the effect on interactions will also be discussed. References [1] Tammelin, T, Abburi, R, Gestranius, M, Laine, C., Setälä, H, Österberg, M. Soft Matter 11, 4273-4282 (2015). [2] Aulin C, Ahola S, Josefsson P, Nishino T, Hirose Y, Österberg M, Wågberg L, Langmuir 25 7675-7685 (2009). [3] Sorkio, A, Vuorimaa-Laukkanen, E, Hakola, H., Valle Delgado, JJ, Ujula T., M. Österberg Yliperttula M., and Skottman, H. Biomaterials 51, 257-269 (2015).

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Thiolate versus selenolate: Structure, stability and charge transfer properties

Jakub Ossowski,1 Tobias Wächter,2 Laura Silies,3 Martin Kind,3 Agnieszka Noworolska,1 Florian Blobner,4 Dominika Gnatek,1 Jakub Rysz,1 Michael Bolte,3 Peter Feulner,4 Andreas Terfort,3*

Piotr Cyganik,1* and Michael Zharnikov2*

1Smoluchowski Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Krakow, Poland 2Angewandte Physikalische Chemie, Universität Heidelberg, Im Neuenheimer Feld 253, 69120 Heidelberg,

Germany 4Physikdepartment E20, Technische Universität München, 85747 Garching, Germany


Selenolate is considered as an alternative to thiolate to serve as a headgroup mediating the formation of self-assembled monolayers (SAMs) on coinage metal substrates. There are however ongoing vivid discussions regarding the advantages and disadvantages of these anchor groups, regarding, in particular, the energetics of the headgroup-substrate interface and their efficiency in terms of charge transport/transfer. Here we introduce a well-defined model system of 6-cyanonaphthalene-2-thiolate and -selenolate SAMs on Au(111) to resolve these controversies. The exact structural arrangements in both types of SAMs are somewhat different, suggesting a better SAM building ability in the case of selenolates. At the same time, both types of SAMs have similar packing densities and molecular orientations. This permitted reliable competitive exchange and ion beam induced desorption experiments which provided an unequivocal evidence for a stronger bonding of selenolates to the substrate as compared to the thiolates. Regardless of this difference, the dynamic charge transfer properties of the thiolate and selenolate based adsorbates were found to be identical as determined by the core-hole-clock approach, which is explained by a redistribution of electron density along the molecular framework, compensating the difference in the substrate-headgroup bond strength.

Figure 1. Schematic presentation of results charge transfer and bond stability experimenents.

References [1] Ossowski, J; Wächter, T.; Silies, L.; Kind, M.; Noworolska, A.; Blobner, F.; Gnatek, D.; Rysz, J.; Bolte, M.; Feulner, P.;

Terfort*, A.; Cyganik*, P.; Zharnikov*, M., ACS Nano, Thiolate versus Selenolate: Structure, Stability and Charge

Transfer Properties, 9, 4508-4526 (2015).

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Conductance enhancement at metal / molecule interface of double junctioned

molecular device

S Nishijima1, Y Otsuka1, T Matsumoto1

1Osaka Univ, 1-1 Machikaneyama-cho, Toyonaka, Osaka, 560-0043 Japan


In molecular electronics, the generation, transport and control of charges in nanostructure in which molecules are connected to electrodes are an important issues. Because ruthenium complex (Di-tetrabutylammonium cis-bis (isothiocyanato) bis (2, 2’–bipyridyl–4, 4’-dicarboxylato) ruthenium(II), N-719) used in the dye sensitized solar cell is capable of charge separation by the irradiation with visible light, it is expected to be applied to molecular electronics. We report the I-V characteristics, the temperature dependence and the photoresponsivity of molecular devices with double junction structure (Figure 1) which enables us to obtain very stable electrical contact.

We first fabricated nanogap gold electrodes (20～150 nm) on a SiO2 substrate. Next, we fabricated a layer-by-layer structure in which the self-assembled monolayer (SAM, 2-aminoethanethiol) and the N-719 layer were attached to the gold electrodes sequentially. Finally, gold nanoparticles (150 nm) modified with citric acid was deposited on the gold electrodes and dried. The I-V measurements

was conducted under a vacuum of 10-4 Pa at 10～300 K in dark condition. After I-V measurements, we measured the distance

between the electrodes with SEM, and we examined a correlation between the distance and the I-V characteristics. Fig. 2 shows the comparison of the I-V measurements to study the effect of the electrical contact by the gold nanoparticles. It was found that the nonlinear I-V characteristics were measured when the gold nanoparticles were bridged between the electrodes as shown in Fig. 1. Moreover it was found that value of the resistance increased exponentially (Fig. 3) with increasing distance between electrodes. The I-V characteristics showed different bias dependence on the current level. This unusual behavior would be due to the changing of the interface between the gold nanoparticles and the electrodes. We also report the temperature dependence and the photoresponsivity of the devices, and discuss the mechanism of this electrical conduction.

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Figure 1. Schematic diagram of the molecular device with double junction structure

Figure 2. Change of I-V characteristics before and after the bridging of gold nanoparticles.

Figure 3. The distance of electrodes and the value of resistance.


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Nonlinear electric properties of biological molecular networks in nanoscale

Yoichi Otsuka, Harumasa Yamaguchi, Saki Sumida, Riko Etoh, Hiroshi Ohyama, Dock-Chil Che, Takuya Matsumoto

Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, Japan


Toward the realization of molecular electronics, nonlinearity is a key property. In this paper, we investigated the conduction properties of single protein molecules and protein/ DNA networks to find nonlinear characteristics. Conduction measurements for single proteins have been well known in water. However, the conduction measurements under dry condition are necessary to obtain the knowledge for the potential as a device component. We have studied the electrical properties of single protein on the gold substrate by conductive probe atomic force microscope. In order to avoid denaturing of proteins at the protein/electrode interface, self-assembled monolayer was formed on the gold substrate and conductive probe. Electrical measurements of cytochrome c, cytochrome c3, apo-cytochrome c were conducted under dry condition. The nonlinear current-voltage (I-V) characteristics were obtained for all of three different proteins. This results can be explained by non-resonant tunneling model. Furthermore, we investigated conduction properties of protein/DNA networks using various proteins [1-3]. The molecular network was formed on the SiO2 substrate by dropping the mixture solution and drying. A top-contacted nanogap gold electrodes [4] were fabricated onto the networks. The studies of temperature dependences of the I-V characteristics resulted that all the cases are well explained by Coulomb blockade network model. The numerical fitting parameter ζ, which exhibit the dimensionality of conduction path inside molecular network, was clearly changed by choosing DNA bases. This indicates that DNA is useful for the template controlling the arrangement of proteins.

Figure１. Electrical measurement of DNA/lysozyme networks by top-contacted nanogap electrodes. Temperature

dependence of (a) I-V characteristics、(b) Threshold voltage (Vth).

References

[1] Y. Hirano et al., J. Phys.Chem.C. 116, 9895 (2012). [2] Y. Hirano et al., J. Phys.Chem.C. 117, 140 (2013). [3] H. Yamaguchi et al., Jpn. J. Appl. Phys. 54, 095201 (2015). [4] Y. Otsuka et al., Nanotechnology 15, 1639 (2004).

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Lipids and PEGylated lipids as tunable coatings for aqueous dispersion of carbon

nanotubes

Jukka Määttä1, Sampsa Vierros1, Seyma Aslan2, Paul R. Van Tassel2, Maria Sammalkorpi1

1Department of Chemistry, Aalto University, P.O. Box 16100, 00076 Aalto, Finland 2Department of Chemical & Environmental Engineering, Yale University, New Haven, CT, USA

E-mail address: [email protected]; [email protected]

Phospholipids and phospholipid derivatives offer efficient, noncovalent functionalization and dispersion of hydrophobic objects, e.g. therapeutic molecules and nanoparticles including carbon nanotubes (CNTs). However, the relation of lipid aggregates in bulk solution and in the presence of the object, as well as, the resulting dispersion remain important open questions. Here, we examine by combining molecular simulations, theory, and experiments lipid [1] and PEGylated-lipid [2,3] selfassembled aggregates both in aqueous solution and at interfaces. By varying the molecular shape and CNT size, we find the assembled morphology transitions from micellar-like to tubular coating with phospholipids [1] and micellar to monolayer-like with longer polymers [2]. The change in the assembly morphology drastically changes the dispersion efficiency. The transition depends mainly on the interplay of the CNT diameter and the amphiphile curvature (lysolipids vs bilayer forming lipids). The findings provide guidelines for fine-tuning CNT, as well as, other nanoscopic hydrophobic object aqueous dispersion via changing the surfactant species or PEG chain length. We compare the findings with theoretical approximations either by Helfrich membrane bending considerations (phospholipids) or by polymer scaling theories (polymeric surfactants). Finally, we show the differences in dispersive effectiveness of the surfactant coatings lead into structural differences of layer-by-layer membrane films functionalized by dispersed CNTs [3]. We show that via control of the dispersive coating of CNTs, more effective antimicrobial layer-by-layer films can be achieved [3]. In total, the findings bear significance in size and form dependent aqueous dispersion of nanoscale hydrophobic objects.

References

[1] J. Määttä, S. Vierros, and M. Sammalkorpi, J. Phys. Chem. B 119(10), 4020-4032 (2015). [2] J. Määttä, S. Vierros, P. R. Van Tassel, and M. Sammalkorpi, J. Chem. Eng. & Data 59(10), 3080–3089 (2014). [3] S. Aslan, J. Määttä, B. Z. Haznedaroglu, J. P M. Goodman, L. D. Pfefferle, M. Elimelech, E. Pauthe, M. Sammalkorpi, and P. R. Van Tassel, Soft Matter 9(7), 2136–2144 (2013).

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Graphene oxide at the air-water interface

Nathalie Bonatout1,2, Philippe Fontaine3, François Muller1 and Michel Goldmann2,3 1Laboratoire des Interfaces Complexes et de l’ORganisation Nanométrique (LICORNE), ECE-Paris, 37 Quai de

Grenelle, 75015 Paris, France 2Institut des Nanosciences de Paris, UMR 7588, 4 Place Jussieu, 75252 PARIS cedex 05, France

3Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin BP48, 91192 Gif-Sur-Yvette, France E-mail address: [email protected] Graphene-based materials are of great interest for flexible electronics [1]. In this framework, Graphene Oxide (GO) is an interesting compound, since it is cheaper than pristine Graphene. Through reduction of the GO sheets, their conductivity properties can be partially restored to be closer to the ones of Graphene [2]. Thus, obtaining thin layers of GO and characterizing their properties is important. Surface-pressure/ surface density isotherm indicates that one obtains a GO layer at the air water interface when deposing a GO solution. However, the surface density remains undefined as the amount of GO sheets adsorbed at the interface is not controlled. We probed this layer by Grazing Incidence X-Ray Diffraction (GIXD) (Figure 1) and X-Ray Reflectivity (XRR) (Figure 2) at various surface pressures to determine the structure and possible orientations of the GO sheets at the air-water interface. The out-of-plane diffraction peaks analysis could be interpreted as a signature of a curvature of the GO sheets. We also followed the adsorption process of GO at the air-water interface by XRR. The GO layer has been transferred on Silicon Oxide substrates by the LB procedure at different surface pressures. We are then able, from AFM experiments, to measure the density of GO sheets transferred on the substrates (Figure 3) with respect to the 2D pressure, the only reliable parameter. We also performed GIXD on GO films transferred on solid substrates to compare the transferred layer to the one on water subphase and characterize the transfer processes.

References [1] Gilje S., Han S., Wang M., Wang K. L., Kaner R. B., Nano letters, 7, 3394-3398 (2007) [2] Zhu Y., Murali S., Cai W., Li X., Suk J. W., Potts J. R., and Ruoff R. S., Advanced Materials, 22, 3906-3924 (2010)

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Covalently attached graphene oxide on hydrogen terminated silicon for

passivation against surface oxidation and low frictional coating

Hiroyuki Sugimura1, Sho Kokufu1, Toru Utsunomiya1, Takashi Ichii1, Harshal P. Mungse2, Om P. Khatri2

1Department of Materials Science and Engineering, Kyoto University, Japan

2Indian Institute of Petroleum, India


Chemical reactivities of hydrogen-teminated silicon (Si-H) surface have attracted much attention in order to fabricate self-assembled monolayers (SAMs) covalently attached to surface-oxide free Si substrates. There have been reported that organic molecules bearing vinyl, alcohol, aldehyde, thiol groups successfully employed as a precursor of SAM [1-3]. Graphene oxide (GO) is expected as a building block for electronic and mechano-electronic devices owing to its electrical and mechanical properties. Si is of particular importance for the substrate of GO films, however, GO physically adsorbed on Si is readily exfoliated. Thus, the immobilization of GO on Si with a sufficient adhesion strength is crucial. Since GO bears various functional groups which can react with Si-H, GO might be covalently bonded to Si as similar to the SAM formation described above. Based on this strategy, we have fabricated single-layer GO films on Si. Furthermore, their tribological and electrochemical properties will be presented. A GO film was prepared by spin-coating on SiH from an aqueous solution of GO. As shown in Figures1a

and 1b, the film is almost single-layered with its coverage 〜 90 %. Each GO sheets reacted chemically with

SiH so that the film was not exfoliated even by sonication. The film reduced by UV irradiation (rGO film) showed excellent low friction as demonstrated in Figure 1c.

Figure 1. (a) AFM image of GO/Si, (b) Magnified AFM image, (c) Frictional test result.

References [1] M. R. Linford, P. Fenter, P. M. Eisenberger, C. E. D. Chidsey, J. Am. Chem. Soc. 117, 3195 (1995). [2] R. Boukherroub, S. Morin, P. Sharpe, D. D. M. Wayner, Langmuir 16, 7429 (2000). [3] H. Sano, K. Ohno, T.i Ichii, K. Murase, and H. Sugimura, Jpn. J. Appl. Phys. 49, 01AE09 (2010).

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Graphene-based LbL deposited films: further study of electrical properties and gas

sensing applications

Alexei Nabok1, Stuart Dutton1, Frank Davis2, Nik J. Walch3, Seamus P.J. Higson2

1Sheffield Hallam University, Materials and Engineering Research Institute, Sheffield, UK 2University of Chichester , Chichester , UK

3Cranfield University, Engineering Sciences Division, School of Engineering, UK E-mail address: [email protected]

Graphene composites were prepared by a multistage sonication process of graphite powder in the presence of surfactants containing either negative or positive ionic groups, as described earlier [1, 2]. This resulted in two graphene-surfactant composites, namely graphene-CTAB, and graphene-SDS, which became soluble in both water and chloroform making them suitable for both layer-by-layer (LbL) electrostatic deposition and LB (Langmuir-Blodgett) deposition. Within this study, graphene-based films were constructed using the LbL process onto various substrates (silicon, glass, quartz, and gold interdigitated electrodes (from DropSens)). Layers of graphene-CTAB were alternated with polyanions such as PSS, while graphene-SDS layers were alternated with polycations PEI or PAH. Electrical properties of such graphene-based films deposited onto gold interdigitated electrodes (100

fringes, spaced by 5m gaps) were studied using a Keithley 4200 electrometer. The recorded I-V characteristics were linear yielding a conductivity of about 0.1 S/cm. The temperature dependence of conductivity studied in the 77-400 K range using an Oxford Instrument Cryostat revealed a band-gap of about 20 meV which is most-likely due to the presence of CTAB and SDS surfactants as well as the polyelectrolytes PSS, PAH or PEI. For gas sensing applications, layers of graphene-CTAB were alternated with water soluble nickel phthalocyanine tetra-sulfonic sodium salt, NiPc-(SO3

- Na+)4. UV-visible absorption spectra of such films showed intriguing spectral transformations of the Q-band (see Fig. 1) which indicate the interaction of NiPc

electrons with those of graphene. The combination of highly conductive graphene films with metal phthalocyanines known for their gas sensing abilities is very promising for development of novel gas sensors. Indeed, the films of graphene-NiPc produced using the LbL method display a substantial response on exposure to saturated NH3 vapours (see Fig. 2). Further studies are currently underway.

Figure 1. UV-vis absorption spectra of graphene-NiPc films. Fig. 2. Response of graphene-NiPc film to NH3 vapours

References [1] N. J. Walch, F. Davis, N. Langford, J. L. Holmes, S. D. Collyer, S. P. J. Higson, Anal. Chem. 87 (2015) 9273-9279. [2] N. J. Walch, A. V. Nabok, F. Davis, S. P. J. Higson, Beilstein J. Nanotechnol. 7 (2016) 209–219.

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Fig. 1 Fig.2

NH3

NH3 air air

heat heat


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Functionalization of graphene oxide/silver nanoparticles hybrid layers for the

detection of amyloid proteins.

M.Banchelli1, B. Tiribilli2, P. Matteini 1, G. Caminati3

1Institute of Applied Physics “Nello Carrara” CNR, Sesto Fiorentino, Florence, Italy, 2Institute for Complex Systems, CNR, Sesto Fiorentino, Florence, Italy

3University of Florence, Via della Lastruccia 3-13, I-50019, Sesto Fiorentino (Firenze), Italy


Extensive scientific effort has been recently devoted to the identification of suitable platforms for the detection of early onset of neurodegenerative disorders as Alzheimer’s and Parkinson’s diseases. These pathologies share a common pattern: the formation of misfolded aggregates of protein or oligomeric species with high content of beta-sheet conformations. Such pre-fibrillar aggregates eventually evolve in mature amiloyd fibrils that are commonly detected once the disease has proceeded to impair the patient functions. Although a variety of detections systems have been described in recent literature, a reliable procedure for early diagnosis is still lacking. In this paper we explore the possibility to use a recently proposed sensor platform [1] based on graphene oxide/silver nanocubes arrays (GO/AgNCs) for the detection of pre-fibrillar and fibrillar aggregates of a model amyloid-prone protein, i.e. lysozyme. Previous Surface Enhanced Raman Spectroscopy studies showed that the GO coating supplies the signal of a probe molecules adsorbed at the graphene oxide outer surface with additional amplification with remarkable uniformity in the distribution of the signal [2]. The hybrid GO/AgNCs layer system was obtained by Langmuir-Blodgett assembly of the silver nanocubes, AgNCs, followed by controlled adsorption of graphene oxide, GO, sheets on the AgNCs array. We followed the adsorption at the outer GO surface of lysozyme for its globular native form as well as for pre-fibrilled lysozyme with high beta-amyloid content by means of Quartz Crystal Microbalance measurements flanked by in situ cyclic voltammetry experiments. The results provided the kinetics and the mechanism of adsorption as a function of protein concentration. The experimental data also allowed for the determination of lysozyme saturation threshold as well as the thickness and the redox fingerprint of the resulting adsorbed layer of the protein. GO/AgNCs arrays covered with a saturated layer of the protein were prepared on solid support and characterized by Atomic Force Microscopy and FT/IR ATR spectroscopy. Parallel SERS experiments were also performed on the hybrid GO/AgNC arrays for increasing concentrations of native and fibrillar lysozyme to obtain a description of protein conformation, beta-sheet content and to establish the concentration limit for amyloid fibrils detection.

Acknowledgements. We acknowledge the financial support from the Tuscany Region in the framework of PARFAS 2007-2013 (Linea d’Azione 1.1 - Azione 1.1..2 -SUPREMAL ).

References [1] M. Banchelli, B. Tiribilli, R. Pini, L. Dei, P. Matteini and G. Caminati, Beilstein J. Nanotechnol. 7, 9–21 (2016) [2] M. Banchelli, B. Tiribilli, M de Angelis, R. Pini, G. Caminati and P. Matteini, ACS Appl. Mater. Interfaces 8, 2628−2634 (2016).

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Transparent conductive thin films with high flexibility prepared by UV light

irradiation on Langmuir monolayer of metal NPs

Takeshi Kawai, Tatsuya Nishimura, Makoto Nakagawa, Yoshiro Imura

Tokyo University of Science, Kagurazaka 1‐3, Shinjuku‐ku, Tokyo, JAPAN


Indium tin oxide (ITO) as transparent conductive materials has been used in a wide range of applications, however it cannot be used in optoelectronic devices for ultraviolet (UV) or infrared (IR) light because of a lack of transparency in UV and IR regions. Moreover, ITO electrodes, in general, limit their applications in flexible devices due to their inherent brittleness. One of the most successful bottom-up approaches to these problems is the use of metal nano‐materials, particularly one- or two-dimensional metal nanowires, due to their high flexibility and transparency of UV, visible and IR light. However, there have been a few reports on the synthesis methods of metal nanowires [1], and the fabrication of conductive films comprised of nanowires is inefficient because large quantities of the nanowires are requiredto ensuretheir conductivity. In this study, we show that free‐standing conductive Au films with high transparent can be prepared by irradiating with UV light onto Langmuir monolayers of Au nanoparticles (NPs). We also demonstrate that the resulting free‐standing Au films can be put on desired substrates and the sheet resistance of the Au films transferred on filter papers has remained almost constant after 100 cycles of the bending test. Au NPs monolayer were prepared by spreading a chloroform dispersion of dodecanethiol protected Au NPs with ca.4.5 nm diameter. The resulting Au NPs monolayer was blue, and UV light was irradiated on it by using an optical fiber (Figure 1). We examined the effect of UV light irradiation on the morphology of the NPs monolayer on water. The irradiation with UV light resulted in a considerable morphological change of Au NPs; Au NPs were fused each other in a few minutes, and a gradual progress of the fusion process consequently brought about a complete disappearance of Au NPs and the formation of ultrathin Au films with many tiny holes within 5 min, together with a color change from blue to pale yellow. Here, FT‐IR and XPS measurements revealed that UV light caused an oxidative decomposition of dodecanethiol as the protected molecule of Au NPs. Continuous further irradiation with UV light induced a growth of the tiny holes and the formation of nanomesh with dozen nanometers of holes, accompanied by the color change from pale yellow to pale purple. After 20 min there was no significant change in the morphology and color. When UV light was irradiated onto Au NPs monolayer on glass substrates, instead of water, as the control experiment, we obtained no ultrathin films but larger NPs. The ultrathin Au films had a thickness of 3.5 nm, and had a high transmittance of ~80 % in the spectral range of 250-900 nm. The films were transferred onto filter papers by Langmuir-Schaefer technique, and the electrical conductivity was measured by four‐terminal method. The conductivity was 5*103 S/cm and kept almost constant values after 100 cycles of the bending test, where the repeated bending radius was 0.6mm.

References [1] Y. Imura, T. Kawai, et al., Chem. Commun, 46, 9206‐9208 (2010); Chem. Commun, 47, 6380 (2011); Langmuir, 28, 14998 (2012); Langmuir, 29, 1669 (2013); Langmuir, 30, 1888 (2014); Langmuir, 30, 5026 (2014).

OP72

Figure1. Schematic illustration of the preparation method of thin films.


125

2D array of high aspect ratio TiO2 nano-pillars using direct photo-patternable TiO2

sol-gel process and colloidal photolithography

O. Dellea1, O. Shavdina1, T. Kämpfe2, I. Verrier2, M. Langlet3, F. Vocanson2, P. Fugier1, Y. Jourlin2

1CEA/LITEN, Laboratory for Innovation in New Energy Technologies and Nanomaterials, F-38054 Grenoble, France

2Laboratory Hubert Curien, University Jean Monnet, Bâtiment F, 18 Rue du Professeur Benoît, F-42000 Saint-Étienne, France

3University Grenoble Alpes, CNRS/LMGP, F-38000 Grenoble, France, F-38000 Grenoble, France


The micro-texturing of surfaces at the nanometer and micrometer size scales plays a key role to obtain new or enhanced surface properties in various domains such as tribology, optics, self-cleaning, light extraction/trapping, microfluidics, photovoltaics or photocatalysis. In the field of surface engineering, continuous, textured or structured TiO2 thin films are of special interest due to their high transparency in the visible spectrum, their high refractive index, their photocatalytic activity and their photo-induced superhydrophilicity [1]. In this work, we introduce a unique process using colloidal photolithography to obtain a 2D array of TiO2

nano-pillars with submicron period and an aspect ratio close to 2.3, never demonstrated in literature. A mono layer of silica microspheres of 1 μm diameter deposited by Langmuir Blodgett process on a specific TiO2 photosensitive xerogel layer has been illuminated by a collimated source emitting at 365 nm wavelength. Each silica microsphere acts as a convergent super-lens, focusing the light underneath the microsphere, to create a so-called photonic nanojet beam propagating in the TiO2 underlying photoresist layer. After washing in solvent, nano-pillars are revealed, according to the photonic nanojet distribution. No further process is needed since the nano-pillars are directly revealed after illumination and washing process. The sol-gel layer acts as a stable and functional negative photoresist, with optical, mechanical and physical properties. The authors will present the chemistry of the sol-gel process, modeling of the electric field distribution underneath the spheres during the illumination process with the RCWA method (Rigorous Coupled Wave Analysis) and preliminary results of hexagonal high aspect ratio TiO2 nano-pillars fabrication on planar substrate.

Figure 1. 2D array of silica spheres (1μm) on direct photopatternable xerogel layer (left), RCWA simulation of electric field distribution through spheres (centre), high aspect ratio TiO2 printed nano-pillars after UV illumination (height 700 nm, width 300 nm) (right)

References [1] O. Shavdina et al., Langmuir, 31, 7877-7884 (2015).

OP73

Poster abstracts

126

Poster abstracts

127

Poster abstracts

Poster abstracts

128

Poster abstracts

129

The selective interaction of cationic tetra-p-guanidinoethylcalix[4]arene with lipid membrane. Theoretical and experimental model studies

Beata Korchowiec1, Marcelina Gorczyca2, Ewa Rogalska3, Jean-Bernard Regnouf-de- Vains3, Jacek Korchowiec 2

1 Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, ul. R.

Ingardena 3, 30-060 Krakow, Poland 2 Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-

060 Krakow, Poland 3 Structure et Réactivité des Systèmes Moléculaires Complexes, BP 239, CNRS/Université de Lorraine, 54506

Vandoeuvre-lès-Nancy cedex, France


Behavior of cationic tetra-p-guanidinoethylcalix[4]arene (CX1) and its building block, p-guanidinoethylphenol (mCX1), in model monolayer lipid membranes were investigated using all atom molecular dynamics simulations and surface pressure measurements. Members of two classes of lipids were taken into account: zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and anionic 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine sodium salt (DMPS) as models of eukaryotic and bacterial cell membranes, respectively [1,2]. It was demonstrated that CX1 and mCX1 accumulate near the negatively charged DMPS monolayers. The adsorption to neutral monolayers was negligible (Fig.1). In contrast to mCX1, CX1 penetrated the hydrophobic part of the monolayer. The latter effect, which is possible due to a flip-flop inversion of CX1 orientation in the lipid layer compared to the aqueous phase may be responsible for its antibacterial activity.

Figure 1. Interactions of cationic tetra-p-guanidinoethylcalix[4]arene (CX1) with DMPC and DMPS model membranes.

References [1] G. Sautrey, M. Orlof, B. Korchowiec, J.-B. Regnouf de Vains, E. Rogalska, J. Phys. Chem. B 115, 2466-2476 (2011). [2] B. Korchowiec, M. Gorczyca, E. Rogalska, J.-B. Regnouf-de-Vains, M. Mourer, J. Korchowiec, Soft Matter, 12, 181-190 (2016).

OHOH

HOHO

NH

NH

HN HN

H2N

NH2

H2N

NH2

NH2

NH2

H2N

NH2

OH

HN NH2

NH2CF3CO2

CF3CO2

CF3CO2CF3CO2

CF3CO2

CX1 mCX1

DMPC DMPS

CX1

CX1 CX1

PP1

Poster abstracts

130

Interaction of daptomycin with biomimetic lipid films at the air-water interface

Dorota Konarzewska1, Slawomir Sek1

1 Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Zwirki i Wigury 101, 02089 Warsaw, Poland


The motivation of study is related to increasing demand for new active substances with antibacterial activity. Antibiotic resistance of bacteria has become a great concern of public health. As a result of this resistance, there is a urgent need for new and natural substances which have broad range of antimicrobial activity. Among many potential candidates, lipopeptides can be considered as a promising new class of antibiotics. Lipopeptides are amphiphilic molecules, where one or more lipid chains are linked to the peptide headgroup. One of them is daptomycin, which represents the family of cyclic lipopeptides. It is composed of 13 amino acids and a decanoyl chain linked to the tryptophan residue. The main target of daptomycin is the plasma membrane of Gram-positive bacteria and it depends on the presence of calcium ions. The plasma membrane of Gram-positive Streptococcus pneumoniae is composed mainly of phosphatidylglicerols and cardiolipins. In order to probe the interactions between daptomycin and lipid monolayers at air-water interface, we have prepared Langmuir films composed of lipids representative for the membrane of Gram-positive bacteria. Therefore, we have used 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (POPG); 1',3'-bis[1,2-dimyristoyl-sn-glycero-3-phospho]-sn-glycerol (CL); or a mixture of both at molar ratio of 50:50. Each system was characterized either in the absence or presence of daptomycin. Langmuir monolayer studies allowed determination of the maximum insertion pressure of the peptide into the lipid monolayers. This is very useful parameter which enables evaluation of the lipid-lipopeptide interactions. Namely, it corresponds to the maximum surface pressure, at which the insertion of peptide into the lipid film is feasible. Based on the isotherms we have also calculated the thermodynamic properties of the layers such as excess area of mixing and excess Gibbs free energy.

Figure 1. Structure of daptomycin.

References [1] I. W. Hamley, Chem. Commun. 51, 8574-8583 (2015). [2] P. Wydro, Colloids and Surfaces B: Biointerfaces 106, 217-223 (2013). [3] T. H. Zhang et. all, The Journal of Biological Chemistry 289, 11584–11591 (2014).

PP2

Poster abstracts

131

About the possibility of forming close-packed polyaromatic molecules based on Langmuir monolayers by molecular dynamics method

Safonov R.A.1, Kolesnikova A.S.1, Lukyanova V.O.1, Chumakov A.S.1, Al-Alwani Ammar J.K.1,2, Glukhovskoy E.G.1

1National Research Saratov State University named after N.G. Chernyshevsky, Education and Research

Institute of Nanostructures and Biosystems, Astrakhanskaya 83, Saratov 410012, Russia 2Babylon University, Babylon, Iraq


One of the most promising directions in nanotechnology development is the creation of methods for preparation and study of graphene, which is the monolayer (ML) of carbon atoms. In this regard, the most promising source for the synthesis of graphene are polyaromatic compounds. In the present paper, we investigated the possibility to form ML of naphthalene molecules at an interface by computer simulation, as well as determined the conditions necessary for its formation over ML-close-packed surface-active agents (SAS). The choice of naphthalene molecule as the source element for creating graphene sheets is attributable to many factors: its atomic structure is similar to the structure of graphene, it is technologically feasible (e.g. slightly soluble in water, stays in the solid phase under normal conditions, small and mobile enough to find energetically favorable positions). The use of monolayer substrates for graphene formation is more technical than many other widely used methods. For example, the graphene growth on copper substrate is carried out in temperatures up to 1000°C, which requires complex facilities and special conditions [1]. Monolayers with the prepared graphene sheet can be easily moved to any solid substrate by Langmuir-Blodgett and Langmuir-Schaeffer deposition. In the present study, arachidic acid molecules and dipalmitoyl-phosphatidylcholine (DPPC) molecules were used as surfactants. The research was carried out by molecular dynamics method at 300 K by the AMBER energy potential [2]. Three different initial distributions of molecules were considered: naphthalene molecules placed above the disordered structure of arachidic acid, naphthalene above the well-formed arachidic acid monolayer and randomly mixed disordered naphthalene and arachidic acid. It was shown that from the molecular arrangement of naphthalene on the surface layer of arachidic acid with disordered structure that naphthalene molecules do not mixi with arachidic acid molecules, but stay on the surface. Similar results were obtained with the molecular arrangement of naphthalene molecules on the surface of arachidic acid ML. It was observed that multiple naphthalene molecules were expelled to the surface of the monolayer when mixing naphthalene molecules with molecules of dipalmitoyl-phosphatidylcholine on an aqueous subphase and gradually compressing the ML by a moving barrier. In the case of a mixture of arachidic acid and naphthalene this effect was practically absent. Naphthalene molecules remain as impurities in the arachidic acid monolayer. The research was supported by grant of the Russian Science Foundation (project №14-12-00275) and the National Research Saratov State University.

References [1] Wu T., Ding G., Shen H., Wang H., Sun L., Zhu Y., Jiang D., Xie X. Nanoscale 21 5456 (2013) [2] Case D., Berryman J., Betz R., Cerutti D., Cheatham T., Darden T., Duke R., Giese T., Gohlke, Goetz A., Homeyer N., Izadi S., Janowski P., Kaus J., Kovalenko A., Lee T., LeGrand S., Li P., Luchko T., Luo R., Madej B., Merz K., Monard G., Needham P., Nguyen H., Nguyen H., Omelyan I., Onufriev A., Roe D., Roitberg A., Salomon-Ferrer R., Simmerling C., Smith W., Swails J., et.al. AMBER (San Francisco: University of California) (2015)

PP3

Poster abstracts

132

Langmuir films of europium betadicetonate complexes monitored by in situ luminescence

F.C. Santos1, H.H.S. Oliveira1,2, M.R. Davolos1

1 Instituto de Química, UNESP - Univ Estadual Paulista, Campus de Araraquara, SP, Brazil

2 Instituto Federal de Educação, Ciência e Tecnologia de São Paulo - IFSP, Campus Matão, SP, Brazil E-mail address: [email protected]

Luminescent materials based on lanthanide ions, Ln3+, have many technological applications [1] because they present intense emission in the visible region of the electromagnetic spectrum resulted from intraconfigurational 4f-4f electronic transitions. There is an increase in the emission intensities when these ions are coordinated to specific aromatic organic ligands, which absorb the excitation energy and transfer it to the Ln3+, a phenomenon known as the antenna effect. Luminescent properties depend on coordination compounds conformations [2] and aggregation states. Langmuir films are useful to investigate different aggregation states, since it is possible to control the molecules organization [3]. In this work in situ luminescent properties of [Eu(tta)3(phen)], [Eu(tta)3(bipy)] and [Eu(tta)3(H2O)2] complexes with stearic acid Langmuir mixed films were studied on the air-water interface. Different complexes concentrations and complex/stearic acid ratios were used to assemble Langmuir films, and during the formation of these films, luminescence intensities excited at 318 nm were monitored by spectra of each 10 mm change barriers position. In situ photoluminescence spectroscopy measurements were performed using the new instrumentation developed by the research group of the Luminescent Materials Laboratory (Unesp, Brazil). As closer the molecules are of the neighbouring the luminescence intensity increases due to the emitting molecules per area, up to the solid state Langmuir film in which the variation is high, excepted when the quenching mechanisms take place. The luminescence monitored during the formation of Langmuir films of [Eu(tta)3(phen)] is in the Figure 1. In this case, as higher the surface pressure higher is the area of integrated emission assigned to the 5D0→7F2 transition, the most intense in the spectrum. Different behaviours of [Eu(tta)3(H2O)2] and [Eu(tta)3(bipy)] were also remarked, and this study shows the strong correlation between the complexes conformations on Langmuir films and luminescent intensities.

Figure 1. In situ luminescence (λex = 318 nm) monitoring of Langmuir film of [Eu(tta)3(phen)]/stearic acid (1/1).

References

[1] KITAI, A. Luminescent Materials and Applications. John Wiley & Sons Ltd, West Sussex (2008).

[2] ADATI, R. A. et al. New Journal of Chemistry. 36, 1978-1984 (2012).

[3] WU, S. et al. Journal of Photochemistry and Photobiology A. 188, 218-225 (2007).

PP4

Poster abstracts

133

FT-IR Spectra of Gold Nanoparticle Monolayers Prepared at the Air-Water

Interface

H. Sakai1, A. Matsuzawa1, T. Kawai2

1National Institute of Technology, Oyama College, Nakakuki Oyama Tochigi Japan 2Tokyo University of Science, Kagurazaka Tokyo Japan


Construction of 2D arrays of nanoparticles (NPs) is of great importance for their potential applications in electronic, magnetic, and optical devices. NP monolayers at the air-water interface have recently attracted widespread attention because of their tunable lateral surface density and their ability to form 3D assemblies via the Langmuir-Blodgett method. However, compared to NP monolayers prepared by spreading highly hydrophobized NPs over the air-water interface, those prepared by adsorption of hydrophilized NPs, through the solution, onto Langmuir monolayers of amphiphilic organic molecules at the air-water interface have not been examined in as much detail [1]. This preparation method allows the fabrication of Janus particles through the addition of different ligands from under particles partially covered with Langmuir monolayer molecules. In this research, the infrared external reflection (IER) spectra of AuNPs covered with dodecyltrimethylammonium bromide (DTAB) and Langmuir monolayers of polyion complexes of deuterated stearic acid (d-STA) and polyallylamine (PAA) were recorded, and the structures of the ligands were examined. The absorbance of the antisymmetric CD2 stretching band of d-STA in the IER spectra increased for several tens of minutes, probably due to surface-enhanced infrared absorption because of AuNPs adsorbed underneath the Langmuir monolayer. The wavenumber of the band indicated that the conformation of the d-STA molecule was all-trans. The absorbance and wavenumber of this band remained largely unchanged on replacing the AuNP solution with water. Subsequently, on adding DTAB molecules to the water, the peak of the antisymmetric CH2 stretching band of DTAB appeared quickly. The wavenumber of the band was lower than that of DTAB molecules at the air-water interface, which indicates that DTAB was quickly adsorbed underneath the AuNPs and that DTAB molecules are more ordered on AuNPs than on the water surface. On the other hand, the absorbance of the d-STA band decreased slightly while the wavenumber increased, indicating that d-STA molecules on the AuNPs became somewhat disordered on adding DTAB. IER spectra obtained after replacing the DTAB solution with water confirmed that AuNPs were covered with both d-STA and DTAB molecules in a highly ordered fashion. References [1] S. Pang et al, J. Colloid Interf. Sci. 285, 634-639 (2005).

PP5

Figure. 1. IER spectra of (A)

STA/PAA/AuNPs on AuNP solution, (B)

STA/PAA/AuNPs on water, (C)

STA/PAA/AuNPs/DTAB on DTAB solution,

and (D) STA/PAA/AuNPs/DTAB on water.

Poster abstracts

134

Thermally induced intramolecular charge transfer by J-aggregates in merocyanine

dye LB films

Chang Heon Yang1, Hoon-Kyu Shin2,*

1R&D Center, Maple semiconductor Inc., Bucheon 301-908, Korea 2National Institute for Nanomaterials Technology, Pohang University of Science and Technology, Pohang

790-784, Korea


In this study, for the development of future molecular electronic devices, we have investigated the characteristics of the aggregates of Langmuir-Blodgett(LB) films. The characteristics of intramolecular charge transfer by J-aggregates in merocyanine dye LB films have been studied experimentally by using UV irradiation and heat treatment. In addition to intramolecular charge transfer, we also studied the conjugation and energy changes of the molecules [1]. In case a dye is thinned by LB method, the alkyl chain is often displaced in order to form a mono-molecular film with ease. Since the molecular association form is often made by self-organization of molecules themselves, in case the dye and the alkyl chain are strongly bonded by the covalent bond, it may be said that the properties of the LB film to be built up are almost determined at the time of synthesis of film-forming molecules. Meanwhile, in case LB film is fabricated by the diffusion absorption method, the cohesive force between the water-soluble dye and the surface-active mono-molecular film is electrostatic, the dye molecule can move relatively freely on the air/water interface, which may be regarded as a two-dimensional crystal growth process [2]. In other words, it is possible to make various dye association forms by the combination of dyes and amphipathic molecules and the adsorption conditions. The dye LB film was fabricated by mixing the merocyanine dye, as a water-soluble dye, of which the association state and relevant subjects have been actively researched and a fatty acid, the representative film-forming molecule for LB film, as an amphipathic molecule, and then the formation of dye aggregates was investigated [3]. We have investigated that intramolecular energy transfers by heat. In this study, by measuring the behavioral state of molecules due to heat treatment, the heat treatment was confirmed to destroy the structure of molecules and this result was predicted to affect the characteristics of intramolecular charge transfer.

References

[1] A. Nakamura, Y. Mizutani, N. Okuyama, Y. Hamanaka, S. Kuroda, Colloids and Surfaces A: Physicochem. Eng.

284, 89 (2006). [2] Keiichi Ikegami, Current Applied Physics 6, 813 (2006) [2] H.-K. Shin, Y.-S. Kwon, Optical Materials 21, 401 (2002)

PP6

Poster abstracts

135

Efficient Langmuir-Blodgett assembly of colloids using water-miscible spreading solvents

Huali Nie1,2, Jiaxing Huang1

1Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208,

United States 2College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620,

China


Langmuir−Blodgett (LB) assembly is a classical molecular thin-film processing technique, in which the material is spread onto water surface from a volatile, water-immiscible solvent to create floating monolayers that can be later transferred to solid substrates. Volatile, water-immiscible solvents are convenient for spreading, but they also greatly limit the versatility of the assembly technique and bring environmental and safety concerns. The use of water-miscible spreading solvents has not been effective or reproducible, and tends to lose most materials to water subphase due to intermixing. Electrospray (E-spray) spreading solves the intermixing problems by depleting the volume of the droplets during the initial spreading step, thus leaving little solvent for mixing [1]. Here we use three "problematic" model colloids to demonstrate that E-spray can effectively spread colloidal materials on water surface from their dispersions in ethanol, ethanol/water mixture, and even water itself. Figure 1 (A) shows LB monolayer of Au/PVP nanoparticle prepared by E-spray spreading using ethanol. Here it is challenging to use common spreading solvents such as chloroform and toluene due to poor colloidal stability of Au/PVP in these solvents. Spreading water-dispersed colloids directly on water by E-spray using GO as an example is shown in Figure 1 (B). Figure 1 (C) shows E-spray-assisted LB assembly of PS colloids using ethanol as the spreading solvent. Here common spreading solvents cannot be used because they will dissolved these polymer colloids. The new strategy drastically reduces the burden of material processing prior to assembly and broadens the scope of LB assembly to previously hard-to-process materials. It also avoids the use of toxic volatile organic spreading solvents, improves the reproducibility.

Figure 1. E-spray assisted LB assembly of three categories of "problematic" colloids that have been hard to process with conventional spreading solvents. (A) LB monolayer of Au/PVP nanoparticle representing unstable colloids prepared by E-spray spreading using ethanol. (B) Spreading water-dispersed colloids directly on water by E-spray using GO as an example. (C) E-spray LB assembly of PS colloids representing soluble polymer or organic colloids using ethanol as the spreading solvent. References [1] Nie, H.L.; Dou X; Tang Z.H.; Jang, H.D.; Huang J.X. J. Am. Chem. Soc. 137, 10683−10688 (2015).

PP7

Poster abstracts

136

The influence of cholesterol precursor – desmosterol – on artificial lipid

membranes

K. Węder, M. Mach, P. Wydro

Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060, Kraków, Poland

E-mail address: [email protected] Cholesterol is a fundamental sterol prevalent in eukaryotic membranes and plays a radical role in membrane organization. It is the final product of the long and multistep sterol biosynthetic pathway. Its immediate precursor in Bloch pathway is desmosterol which differs from the animal sterol only in the presence of the additional double bond located between C24 and C25 carbon atoms. The protein that catalyzes the reduction of the double bond is 3β-hydroxysterol Δ24-reductase (DHCR24)[1]. Mutations in the gene encoding this protein result in inhibition of the enzymatic activity of DHCR24, causing an accumulation of desmosterol in cells and lead to the lethal disorder called desmosterolosis. The increase of desmosterol concentration in membranes raises the question of the effect of this substance on the biological membranes organization. The analysis of the interactions between desmosterol and phospholipids present in the human erythrocyte membrane was performed in order to compare the effect of cholesterol and its precursor on model membranes and to investigate the influence of lipid hydrophilic group structure on the membrane properties. The investigations were performed for desmosterol (Desmo) and membrane lipids: sphingomyelin (SM), palmitoyloleoylphosphatidylcholine (POPC), palmitoyloleoylphosphatidylethanolamine (POPE) and palmitoyloleoylphosphatidylserine (POPS). The experiments were done for POPC/Desmo, POPE/Desmo, POPS/Desmo, SM/Desmo mixtures differing in the lipid proportion and for one-component monolayers of desmosterol, cholesterol and phospholipids. Then the influence of desmosterol on binary SM/POPC = 1:1 was studied at 10, 33, 50, 67 and 90% of the sterol in the systems. Finally, in the SM/POPC/Chol = 1:1:1 monolayer the animal sterol was gradually substituted by desmosterol. From the Langmuir monolayers technique the surface pressure–area isotherms were received and then the excess area of mixing values and the compression modulus values were estimated. This analysis was completed by Brewster Angle Microscopy experiments in order to describe the morphology of the investigated films. The obtained results indicate that desmosterol causes a lower contraction of the area per lipid, a weaker ordering effect and shows weaker domains-promoting properties than cholesterol. Furthermore, the gradual replacement of cholesterol by its precursor in mixed monolayers leads to an increase in fluidity of the investigated films. There was also found that the substitution of 2% of cholesterol in the foregoing system by desmosterol only slightly increases the excess area per molecule values and does not change the morphology of the studied system. Therefore it can be suggest that the properties of these films are similar to the properties of the native monolayer. However, further substitution of cholesterol generate serious alterations in the membrane organization. It was also found that the condensing and ordering effect of desmosterol depends on the type of the phospholipids polar head. References [1] E. J. Zerenturka, L. J. Sharpea, E. Ikonenc, A. J. Brown, Progress in Lipid Research 52, 666–680 (2013)

PP8

Poster abstracts

137

The affinity of selected monodesmosidic saponins to cholesterol monolayer

M. Janikowska1,2,K. Kwiecińska3, S. Trojan1, B. Korchowiec3, J. Korchowiec1

1Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, ul. R.Ingardena 3, 30-060 Kraków, Poland

2Faculty of Physics, Astronomy and Applied Computer Science, ul. prof. Stanisława Łojasiewicza 11, 30-348 Kraków, Poland

3Department of Physical Chemistry and Electrochemistry, Faculty of Chemistry, Jagiellonian University, ul. R.Ingardena 3, 30-060 Kraków, Poland

E-mail address: [email protected]:

Saponins are naturally occurring glycosides in plants, invertebrates and marines, where they play

antibacterial and antifugial role. A characteristic feature of many saponins is their ability to increase

membranes permeability, which is associated with saponin/lipid complex formation. A digitonin and a

diosgenin, two monodesmosidic saponins possess amphiphilic structure. These saponins play important

role in tumor therapy because of their ability to pore formation and also their membrane permeability

properties [1,2]. Cell membrane consists of lipids and proteins, whereas the cholesterol constitutes 30% of

the lipid content. Cholesterol increases membrane rigidity. Diosgenin is saponin which structure is relatively

similar to cholesterol. The compound is insoluble in water and forms a monolayer on the water subphase.

The main goal of the study was to determine the relationship between the sterol structure and their

interaction with digitonin. The interaction was investigated using the Langmuir monolayer technique. Π-A

isotherms and adsorption kinetics has been carried out. Measurements were performed for monolayers of

the pure components: cholesterol or diosgenin and their equimolar mixture. Moreover theoretical models

have been prepared in NAMD program. The models consist of cholesterol or diosgenin monolayer placed

on top of the water subphase containing digitonin molecules.

The obtained results show that digitonin interacts with both cholesterol and diosgenin. The affinity of

digitonin to cholesterol monolayer is higher compared to diosgenin monolayer. Moreover experiments in

situ have shown that digitonin is able to adsorb or penetrate to the cholesterol monolayer, what is in good

agreement with the experimental data.

References [1] Bachran C., Bachran S., Sutherland M., Bachran D. and Fuchs H., Saponins in Tumor Therapy, Mini-Reviews in

Medicinal Chemistry, 2008, 8, 575-584. [2] Korchowiec, B., Gorczyca, M., Wojszko, K., Janikowska, M., Henry, M., & Rogalska, E., Impact of two different

saponins on the organization of model lipid membranes. Biochimica et Biophysica Acta (BBA) - Biomembranes, 1848(10, Part A), 1963–1973.

PP9

http://www.fais.uj.edu.pl/en_GB/start

Poster abstracts

138

The 2D properties of cardiolipin under exposure to different pH values

M. Sturm 1,2, G. Brezesinski 2

1Ernst Moritz Arndt University, Institute for Physics, Greifswald, Germany 2Max Planck Institute of Colloids and Interfaces, Science Park Potsdam-Golm, Germany


As Cardiolipin typifies one of the most common anionic phospholipids of cytoplasmic bacterial membranes it can readily serve as a component for model membranes. In the present work, various properties of tetramyristoylcardiolipin (TMCL) have been investigated in 2D model systems with regard to the exposure to different pH values [1]. Such changes of the subphase conditions allow the study of the pH dependent dissociation behavior of the cardiolipin head group and give a deeper insight into the influence of the bulk pH on the phase state of the phospholipid. Increasing the pH will lead to a higher charge density. At low pH, the head group should be protonated whereas at high pH the phosphate groups are expected to be deprotonated. The selected buffer for these experiments was a 1mM cesium buffer. To avoid competition between cations the used buffer contains only one sort of cation. Measurements were carried out at four different pH values (pH 3, pH 5, pH 7.4 and pH 9). The recording of surface pressure versus molecular area isotherms was coupled with infrared-reflection-absorption spectroscopy (IRRAS), grazing incidence x-ray diffraction (GIXD) and total reflection x-ray fluorescence (TRXF). These combined measurements allow a more detailed study of the TMCL at the air/water interface. At pH 3, the measured isotherms indicate a liquid condensed phase (LC) at temperatures up to 30 °C. This could be based on the fact that a protonated head group (no electrostatic repulsion) enables a tight packing of the molecules. Isotherms measured above 30 °C showed a first-order transition from a liquid expanded (LE) to a LC phase. Measurements at pH 5, 7.4 and 9 showed phase transition from the LE to the LC phase at all measured temperatures. At all pH values, the Langmuir isotherms indicate that the LE-LC transition pressure increases with increasing temperature. This is characteristic for an exothermic first-order phase transition. The chain conformation has been analyzed by IRRAS. It was shown that the band of the CH2-stretching vibration changes from higher to lower wavenumbers during the phase transition, indicating a conformation change from gauche to all-trans. The characterization of the OH-band gave information about a thickening of the layer. GIXD, measured at external synchrotron radiation beamlines, has been used to obtain information about the tilt angle of the chains. GIXD measurements of TMCL on water proved the transition from an orthorhombic structure with tilted chains to a hexagonal arrangement of non-tilted chains between 15 and 20 mNm-1 in accordance with a kink observed in the isotherm. With the TRXF measurements we get information about the ionization state of the head group by determining the amount of cesium bound as the counterion to the charged head group at different pressures and pH values [2].

Acknowledgements: The experiments were carried out at the Max Planck Institute of Colloids and Interfaces in the group of Prof. Dr. Gerald Brezesinski. The project is financially supported by the DFG within the Research training group 1947.

References [1] S. Sidiq, I. Verma, S.K. Pal, Langmuir 31, 4741-4751 (2015). [2] M.N. Antipina, B. Dobner, O.V. Konovalov, V. L. Shapovalov, G. Brezesinski, J. Phys. Chem. B 111, 13845-13850

(2007).

PP10

Poster abstracts

139

The effect of structural factors on the properties of artificial cell membranes

M. Mach, K. Węder, P. Wydro

Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-060 Kraków, Poland


The main sterol occurring in mammalian cell membranes is cholesterol. Its biosynthesis, which passes through a lot of intermediate stages, involves with enzymatic reactions. Disorders in the correct functioning of enzymes lead to the accumulation of cholesterol precursors in tissues and cell membranes. This contribute to the occurence of many incorrectness in the human body, such as: desmosterolosis [1], CHILD syndrom or CDPX2 disorder [2]. The aim of the research was determine the effect of desmosterol, zymosterol and lanosterol on the model biological membranes. The studies involved the analysis of Langmuir films in terms of a miscibility and interactions of three cholesterol precursors with two phospholipids monolayers (dipalmitoylphosphatidylcholine - DPPC and dipalmitoylphosphatidylethanolamine - DPPE). The analysis of a properties of examined systems was based on π/A isotherms, mean molecular area (A12), excess area per molecule (AExc), compression modulus (CS-1) and BAM images. The negative values of excess area per molecule for PC/Zymosterol and PC/Desmosterol systems indicate the miscibility of components in mixed films, an occurrence of favorable, attracting interactions and condensing influence on DPPC monolayer. It is only the system that contains 90% of Zymosterol shows a deviation. The positive value of AExc indicates the unfavorable interactions between lipids, a phase separation and the expansion of an area regarding the pure PC film. In the case of PC/Lanosterol mixtures a lack of miscibility, repulsive interactions and the expansion of the area are observed. Only the PC/Lanosterol=1:2 film demonstrates the negative value of AExc. It shows that the created system is thermodynamically favorable. PE/sterol monolayers demonstrate positive deviations from the ideal state. Interactions between lipids in these mixed systems are less attractive than those in the respective one-component films. This contributes to the separation of components of mixed films. Desmosterol shows the smallest deviations from the ideality, while Lanosterol demonstrates very high positive values of AExc. Furthermore, the addition of sterols to DPPE causes the expansion of molecular area of phosphatidylethanolamine film. The addition of investigated sterols to PC monolayer causes the increase of the values of the compression modulus. Merely PC/sterol=9:1 systems prove lower values of CS-1. This suggest that the small amount of sterol disrupts the order of acyl chains of DPPC. Further the addition of sterols to PC film contributes to the growth of ordering with the increasing of concentration of sterols. For PE/sterol films the values of CS-1 rise with the growth of content of sterols in PE monolayer. This increase is caused by the growth of stiffness of PE film after the addition of sterols. The studies shows also that type of phospholipids polar head has a huge influence on the interaction between the components of Langmuir films. This is due to the ability to form hydrogen bonds between PE molecules which is not occur between PC molecules. References [1] E. J. Zerenturk, L. J. Sharpe, E. Ikonen, A. J. Brown, Prog. Lipid Res. 52, 666–680 (2013) [2] F. D. Porter, G. E. Herman, J. Lipid Res.52, 6-34 (2011)

PP11

Poster abstracts

140

Organization of pyrazole derivative ionic liquids at the air-water interface

Nathalie Bonatout1, 2, Ignacio Gascon3, 4, Raquel Giménez3, Philippe Fontaine5, François Muller1 Oleg Konovalov6 and Michel Goldmann2, 5

1Laboratoire des Interfaces Complexes et de l’ORganisation Nanométrique (LICORNE), ECE-Paris, Paris,

France 2Institut des Nanosciences de Paris, UMR, Paris, France

3Departamento de Quimica Fisica, Universidad de Zaragoza, C/ Pedro Cerbuna, 12, 50009 Zaragoza, Spain 4Instituto de Nanociencia de Aragon, C/ Mariano Esquillor s/n, 50018 Zaragoza, Spain

5Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin BP48, 91192 Gif-Sur-Yvette, France 6 ESRF, 71 av des martyrs 38043, Grenoble, France


ILs are organic salts with the outstanding property to be liquid around ambient temperature. This results from a competition between electrostatic, Van der Waals and hydrogen-bond interactions. Such balance is known to impose mesoscopic organization in the bulk [1, 2]. However, very few studies on the meso-structuration of IL films have been performed [3]. We have probed the structure of lpz and Ipz-2 [4,5] (Figure 1) at the air-water interface by X-Ray Reflectivity (XRR) and Grazing Incidence X-Ray Diffraction (GIXD) ), at various surface pressures. At low surface pressures, GIXD (Figure 2) and XRR (Figure 3) measurements indicate a disorganized monolayer for both molecules. lpz-2 has been characterized after the collapse plateau. The XRR indicates a trilayer structure. In the first layer in contact with the water surface, the molecules are well oriented with the chains upright. However in the two overlayers the molecules are randomly oriented up or down, with the alkyl chains interdigited between the neighboring layers. The diffraction scans show the appearance of an organized structure which could correspond to the columnar stacking of the molecules. However, the rod shapes analysis leads to a characteristic distance of 1nm which may indicate that this structure correspond to the interdigited alkyl chains.

References [1] Sloutskin E et al., Journal of the American Chemical Society, 127, 7796-7804 (2005). [2] Triolo, A. et al., J. Phys. Chem. B, 111, 4641−4644 (2007). [3] Tamam, L.et al., Physical Review Letters, 106, 197801 (2011) [4] Giner, I. et al., Journal of Physical Chemistry C, 113, 18827-18834 (2008). [5] Pérez-Gregorio, V. et al., Journal of colloid and interface science, 375, 94-101 (2012).

Figure 5. Diffraction patterns of Ipz-2 before and after collapse

Figure 6. Reflectivity Scans of Ipz-2 before and after collapse

PP12

Figure 4. Ipz-2 structural formula

Poster abstracts

141

In situ silver nanoparticles synthesis for Langmuir-Blodgett films

D.R. Assis1, H.H.S. Oliveira1,2, M.R. Davolos1, M. Jafelicci Jr1

1Instituto de Química, UNESP Univ - Estadual Paulista, Campus de Araraquara, SP, Brazil 2Instituto Federal de Educação, Ciência e Tecnologia de São Paulo - IFSP, Campus Matão, SP, Brazil


Langmuir- Blodgett (LB) technique is the most promising method for the production of organized films of surfactants, polymers, and nanoparticles, because it provides good control of the thickness and homogeneity of the monolayer and multilayer [1]. In this context, films with new properties are acquired due to nanoparticles organization. Therefore, the LB films are of great scientific and technological interest such as, optical devices fabrication, sensors and biosensors development, transistors, memories, and other applications. [1,2] The nanoparticulate LB films can be prepared in two ways: (i) nanoparticles are prepared before the incorporation in the film, followed by self-organization of such nanoparticles in the gas-liquid interface; (ii) nanoparticles are synthesized on the interface using Langmuir film surfactants as carriers for growth of the nanoparticles. The advantage of the second approach is the combination of the synthesis of nanoparticles with the LB film preparation enabling the control of their organization, their size and their arrangement in the film, followed by controlling the number of monolayers deposited on the substrate. [3,4] This work describes the synthesis of silver nanoparticles in the air-water interface using a Langmuir film as a template and a hydrophobic metalorganic compound. [4] The particles were synthesized in situ in a Langmuir through by spreading of the mixture of silver sulfadiazine and stearic acid solutions in chloroform, on a sodium borohydride solution used as the subphase. Sample films have also been prepared only by spreading the solution of silver sulfadiazine and silver sulfadiazine and stearic acid solutions (molar ratio 1: 1). The chemical composition of silver nanoparticles was determined by energy dispersive X-ray spectroscopy attached to the electron microscope operating in scan mode. The scanning electron microscopy images show that silver sulfadiazine is efficient for the LB films formation and they exhibit an organization long range seen in the film samples images field. Results demonstrate that silver sulfadiazine is a precursor reactant and also stabilizes colloidal silver nanoparticles, preventing their aggregation. It was obtained silver nanoparticles in the air-water interface template and organized them for the collecting of silver nanoparticle LB film. References [1] TAO, A. R.; HUANG, J.; YANG, P., Accounts of Chemical Research v. 41, p. 1662-1673 (2008) [2] PARK, J. et al., The Journal of Physical Chemistry B v. 109, p. 13119-13123 (2011) [3] SANFELICE, R. C. et al., Journal of Physical Chemistry C v. 118, p. 12944-12951 (2014) [4] KHOMUTOV, G. B.; GUBIN, S., Materials Science and Engineering C v.22, p.141–146(2002)

PP13

Poster abstracts

142

Surface pressure-induced alpha-beta transition of amphiphilic peptides in a lipid monolayer

N. Kato and K. Kishida

School of Science and Technology, Meiji University, Kawasaki 214-8571, Japan


To apply the Langmuir–Blodgett (LB) technique as a platform for investigating the fundamental properties of amphiphilic peptides (APs) [1], we have investigated the structure of LB films using the APs. To vertically orient the helical APs like transmembrane proteins in the membrane, the primary structure of the APs was designed to have two domains: a hydrophilic domain (three amino acids) and a hydrophobic domain (ca. 20 amino acids) [2-4]. However, full controls of their orientation and conformation are hardly realized. This study reports the alpha-beta transition of the AP (NH2- HSSALALALALGLGLGLGLALA-CONH2, HS2-19, underline = hydrophobic domain) in the lipid monolayer at the air-water interface. The hydrophobic domain of the present AP is designed to have a smaller hydrophobic moment and a slightly higher average hydropathy and its hydrophilic domain is designed to be constituted by shorter-chain residues compared to the reported AP [4], and this AP is insoluble in water. Dipalmitoyl phosphatidic acid (DPPA) was mixed at the molar ratio of HS2-19:DPPA = 1:3. The π-A isotherm of the mixed monolayer on the 5 mM citric acid buffer (pH 6.0, 41.5 oC) was observed. One layer of the mixed monolayer was deposited on the substrate by the vertical dipping method (Z-type). The fraction of conformations of the APs and the orientation of the alpha helices were analysed by the circular dichroism (CD) spectroscopy. The surface morphology was investigated by atomic force microscope (AFM). Fig. 1(a) shows the π-A isotherm and two kinks are observed around 20 and 40 mN/m. These two kinks corresponded to the pressures, where the fraction of conformations of APs in the monolayer was changed. As shown in Fig. 1(b), the beta conformation at 10 mN/m changed to the beta/random mixed conformation at 20 mN/m upon compression. Subsequently, this mixed conformation changed to the alpha conformation at 45 mN/m and the orientation of the helical axis was ca. 20o

from the film normal as the helixes of TM proteins orient in the membrane. A structural model of the mixed monolayer and the mechanism of the transition will be discussed. References [1] S. R. Dennison, F. Harris and D. A. Phoenix, Protein Peptide Lett. 17, 1363 (2010). [2] K. Togashi, T. Iizuka, N. Kato, T. Sasaki, Y. Mukai, J. Nanosci. Nanotechnol. 12, 568 (2012). [3] K. Togashi, T. Iizuka, S. Yanagiya, N. Kato, T. Sasaki, Y. Mukai, e-J. Surface Sci. Nanotechnol. 10, 379 (2012). [4] N. Kato, T. Sasaki, Y. Mukai, BBA-Biomembranes 1848, 967 (2015).

PP14

Figure 1. (a) π-A isotherm of the mixed

monolayer of HS2-19:DPPA = 1:3. (b)

Fraction of Alpha-, beta-, and random

conformations of HS2-19 in the mixed

monolayer at different deposition pressures

of the mixed monolayer.

Poster abstracts

143

Particle structure orientation analysis by angular color imaging of monolayers of

silica spheres deposited by the Langmuir-Blodgett method

Mathieu Hébert1, Renée Charrière1, Jean-Marie Becker1, O. Dellea2

1Laboratory Hubert Curien, University Jean Monnet, Bâtiment F, 18 Rue du Professeur Benoît, F-42000 Saint-Étienne, France

2CEA/LITEN, Laboratory for Innovation in New Energy Technologies and Nanomaterials, F-38054 Grenoble, France


For many years, the area of photonic crystal research has attracted considerable interest due to its tremendous importance in nanoscience and nanotechnology. Among these materials, colloidal crystals composed of monodisperse spherical particles with hexagonally close-packed (HCP) structure are often synthetized because of their potential applications and low fabrication complexity on surfaces of a few cm². In this theme, Langmuir-Blodgett technique is a simple method to fabricate 2D or 3D photonic crystals having specific color response, called structural color [1], resulting from interference, diffraction and scattering of light. In this work, we consider a monolayer of HCP silica beads with a diameter of 1.1 μm deposited on a silicon wafer. This 2D photonic crystal produces a rich palette of iridescent colors due to the diffraction of light by the hexagonal particle structure (Figure 1). The colors depend on the orientation of incident light, the viewing orientation, as well as the orientation of the hexagonal structure. The latter is fairly homogeneous within areas of a few square millimeters, called grains, but varies significantly from one grain to another. The juxtaposition of grains on the surface thus displays a mosaic of colors, each color resulting from a certain spectrum of the light related to the diffraction phenomenon in the corresponding angular geometry. The orientation of the particles in grains is generally studied by microscopy and very few studies investigate the analysis of grain structure which plays a key role related to optical performances [2]. The authors will present a first attempt to measure microstructure properties of particle deposits through macroscopic measurements, i.e. color captured by a photo camera. The promising results show that a color analysis, combined with the light diffraction theory by hexagonal structures, enables measuring the orientation of the particle structures in grains with less than 5° of error.

Figure 1. 2D photonic crystal of silica microspheres 1.1 μm on Si substrate (left), color response of a monolayer of HCP silica beads on 4’’ Si wafer for different positions of the non-collimated white light source (right)

References [1] S. Kinoshita et al. , ChemPhysChem, 6, 1442–1459 (2005). [2] R. Hillebrand et al. , ACS Nano 2 (5), 913–920 (2008).

PP15

Poster abstracts

144

Surface properties of binary components of partially fluorinated alkanes and

DPPC: A PM-IRRAS study

Hiromichi Nakahara1, M. P. Krafft2, Osamu Shibata1

1Department of Biophysical Chemistry, Faculty of Pharmaceutical Sciences, Nagasaki International University, Huis Ten Bosch, Sasebo 859-3298, Japan

2Systèmes Organisés Fluorés a Finalités Thérapeutiques (SOFFT), Université de Strasbourg, Institut Charles Sadron (CNRS), 23 rue du Loess, 67034 Strasbourg Cedex 2, France


The interfacial behavior of partially fluorinated alkanes [CnF2n+1CmH2m+1 or (FnHm)] and the gemini-type

alkanes [(CnF2n+1CH2)(Cm−2H2m−3)CH−CH(CnF2n+1CH2)(Cm−2H2m−3) or di(FnHm)] has been investigated

employing the monolayer technique[1]. It is noticed that these (including gemini-type) alkanes can form a monolayer at the air-water interface as opposed to the corresponding hydrogenated alkanes. In previous work, it has been implied that F10Hm and di(F10Hm) tends to form densely packed surface micelles on water, where dipalmitoylphosphatidyl-choline (DPPC) molecules which is a major component in pulmonary

surfactants are spread at the same time. Surface pressure (π)– molecular area (A) and surface potential

(V)–A isotherms indicated the kink points corresponding to the surface micelle formation. Moreover, the formation was supported by morphological studies with Brewster angle microscopy (BAM), fluorescence microscopy (FM), and atomic force microscopy (AFM). In the present study, we have investigated the surface micelle formation of F10Hm and di(F10Hm) in the DPPC monolayer from the spectroscopic aspect employing in situ polarization modulation-infrared reflection adsorption spectroscopy (PM-IRRAS). References [1] C. de Gracia Lux, M.P. Krafft, Chem. Eur. J.16, 11539-11542, (2010).

PP16

Poster abstracts

145

SIRIUS, an x-ray beamline devoted to the study of organic Films by x-ray scattering

and fluorescence techniques: first results

P. Fontaine1, N. Aubert1, G. Ciatto1, M. Goldmann2, 3, 1

1SIRIUS Beamline, Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin, BP48, 91192 Gif sur Yvette Cedex, France

2Institut des NanoSciences de Paris, Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05,France

3Faculté des Sciences Fondamentales et Biomédicales, Université Paris Descartes, 45 rue des Sts-Pères, 75006 Paris, France


Since the early 1990s Grazing Incidence X-ray Techniques (Wide Angle Diffraction – GIXD, Small Angle Scattering GISAXS, Total External Reflection Fluorescence – TRXF, Off-specular scattering) on synchrotron beamlines led to major breakthrough in the understanding of organic Molecular films. On the French Synchrotron facility (SOLEIL), SIRIUS is a beamline devoted to the application of these methods on organic molecular films [1]. SIRIUS beamline uses an undulator x-ray source optimized to provide photons in the energy range 1.4 - 12keV that covers most absorption edges of chemical element involved in soft condensed matter. This will provide a unique facility for absorption spectroscopy combined with x-ray scattering. The optics is designed to provide an incident beam adapted to grazing incidence experiment on horizontal, liquid surfaces. The diffractometer enables to host large, cumbersome sample environment (eg. Langmuir through, rheometer, microfluidic cells …) and to measure simultaneously scattering at large (GIXD) and small (GISAXS) angles thanks to two detector arms besides x-ray fluorescence. The SIRIUS beamline will provide new opportunities for studying organic molecular films on liquid or solid. We will present the possibility of the beamline for organized molecular films [2], and illustrate them by some new results obtained for biomimetic films, nanostructured co-polymers films doped with gold nanoparticles for use as metamaterials, x-ray surface radiolysis, in-situ liquid surface rheometry.

Figure 1. Lleft : GISAXS spectra of PS-b-PMMA diblocks copolymer lamellas on silicon wafer. Center : GIXD spectra of a perfluorinated fatty acid monolayer on the air/water interface. Right : Mn2+ and Mg2+ adsorption/desorption under a Langmuir monolayer of behenic acid followed by TRXF.

References [1] http://www.synchrotron-soleil.fr/portal/page/portal/Recherche/LignesLumiere/SIRIUS [2] P. Fontaine, G. Ciatto, N. Aubert, and M. Goldmann, Sci. Adv. Mater. , 6 , 2312-2316 (2014).

PP17

Poster abstracts

146

Spread Films of human serum albumin at the air-water interface: Optimization,

morphology & durability

Richard A. Campbell1, Joo C. Ang2, Federica Sebastiani1, Andrea Tummino1, John W. White2

1Institut Laue-Langevin, 71 avenue des Martyrs, CS20156, 38.042 Grenoble Cedex 9, France 2Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia


In addition to the obvious biological relevance of proteins, they are in widespread use as stabilizing agents for foams, emulsions in foods, and in deposition-based technologies such as antifouling coatings [1]. Interestingly, it has been known for almost one hundred years that a lower surface tension can be achieved at the air-water interface by spreading protein from a concentrated solution than by adsorption from an equivalent total bulk concentration [2,3]. Indeed the nonequilibrium properties of these films have been demonstrated using a flow trough where a stable protein film has been shown to be impervious to subphase dilution [4]. Nevertheless the factors that control this non-equilibrium process have not been fully understood. In the present work [5], we show using a range of surface-sensitive techniques that the dominant contribution to the surface loading of human serum albumin (HSA) is Marangoni spreading from the bulk of the droplets. Loaded films can be spread on a dilute sub-phase only if the concentration of the spreading solution is sufficient. The morphology of the films comprises an extended network with regions of less textured material or gaps. Lastly, mechanical cycling of the surface area of the spread films anneal the network into a membrane that approach constant compressibility and has increased durability. The scope for optimization of the surface loading mechanism in a range of systems leading to its exploitation in deposition-based technologies in the future is discussed.

Figure: (left) Higher surface excess of a spread film than an adsorbed layer of HSA; a Brewster angle microscopy image of the adsorbed layer is shown above; (right) increased durability of the spread films during mechanical cycling of the surface area; a Brewster angle microscopy image of the spread film is shown above.

References [1] P. A. Wierenga & H. Gruppen, Curr. Opin. Colloid Interface Sci. 15, 365 (2010). [2] E. Gorter & F. Grendel, Trans. Faraday Soc. 22, 477 (1926). [3] E. Hughes & E. K. Rideal, Proc. Roy. Soc. A (London) 137, 62 (1932). [4] A. W.Perriman, D. J. McGillivray & J. W. White, Soft Matter 4, 2192 (2008). [5] R. A. Campbell, J. C. Ang, F. Sebastiani, A. Tummino & J. W. White, Langmuir 31, 13535 (2015).

PP18

Poster abstracts

147

Tribological properties of Langmuir–Blodgett films of copper complex of 2,4-heneicosanedione with molybdenum disulfide particles

A.E. Salamianski, K.I. Dubatouka, V.E. Agabekov

Institute of Chemistry of New Materials, NAS of Belarus, 36 Fr. Skaryna Street, Minsk BY-220141, Republic of Belarus


Miniaturization of precision friction units requires the development of more effective wear proof coatings [1]. Composite Langmuir–Blodgett (LB) films of fatty acids, diketones with molybdenum disulfide particles can be used as such protective layers because their formation does not require vacuum conditions and high temperatures [1 – 3]. The goal of this work is to create protective coatings for precision friction units based on composite LB monolayers of 2,4-heneicosanedione copper complex (HDCu) with molybdenum disulfide particles (MoS2). The LT – 201 device (Microtestmachines, Belarus) was used for the deposition of HDCu and HDCu – MoS2 coatings on silicon plates of rectangular shape with area ~ 2 cm2 by horizontal precipitation method [2] under surface pressure of 30 mN/m. Composite HDCu Langmuir layer with particles of molybdenum disulfide (CAS 1317-33-5 TG, the average particles size ~ 600 nm) was formed from the suspension of MoS2 and HDCu in chloroform. The components were taken in mass ratio 1.0:1.0. Linear microtribometer RPT-02 (V.A. Belyi Metal-Polymer Research Institute NAS of Belarus) was used for the tribotechnical testing. Conditions of the testing included normal load of 0.5 N, a 3 mm diameter stainless steel ball as indenter, 3 mm stroke, linear speed of 4 mm/s. The destruction of oxide layer on silicon substrate at friction coefficient ~ 0.4 was the threshold of the experiment [3]. In tribological tests under normal 0.5 N load the uncoated silicon surface was destroyed immediately after the first sliding cycle (Fig. 1, curve 1), whereas HDCu and HDCu – MoS2 monolayers were stable for ~260 and 1955 sliding cycles respectively (Fig. 1). The MoS2 particles and their aggregates remained in contact area of surfaces and protected them from wear resulted in an increase of wear resistance of HDCu – MoS2 coating [3]. Thus composite LB films of 2,4-heneicosanedione copper complex with molybdenum disulfide particles can be used as protective coatings in precision friction units.

Figure 1. The friction coefficient as a function of number of sliding cycles: 1 - unmodified silicon surface, 2 – HDCu monolayer, 3 – HDCu – MoS2 coating

References [1] D.-I. Kim et al., Tribology Letters 17, 169–177 (2004). [2] G. Zhavnerko, V.Agabekov, А. Salamianski, S. Chizhik, А. Suslov, V. Chikunov, Patent BY № 15411 (2012). [3] A. Salamianski G. Zhavnerko, V. Agabekov, Surface & Coatings Technology 227, 62–64 (2013).

PP19

Poster abstracts

148

The influence of benzo[a]pyrene on model pulmonary surfactant monolayers

composed of phosphatidylcholine and phosphatidylglycerol

S. Trojan1, A. Stachowicz-Kuśnierz1, M. Janikowska1, B. Korchowiec2, J. Korchowiec1

1 Department of Theoretical Chemistry, Faculty Of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Cracow, Poland

2 Department of Physical Chemistry and Electrochemistry, Faculty Of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Cracow, Poland


Pulmonary surfactant (PS) released by alveolar type II cells fulfils a wide range of functions. Its main role is to reduce surface tension at the air-liquid interface of the alveoli. It allows both the proper gas exchange and protect lungs from collapsing during expiration. Pulmonary surfactant is composed of about 85% of phospholipids, 10% of surfactant associated proteins and 5% of neutral lipids. Phosphatidylcholine (PC) is the main phospholipid which occurs in pulmonary surfactant. PCs are mainly responsible for surface active properties as they play the primary role in lowering of the surface tension. The second most abundant phospholipid is phosphatidylglycerol (PG) present at 7-15%. PGs are important for spreading of surfactant monolayer on alveolar surface. Chemical molecules present in air pollution can affect both the morphology and composition of PS film. In general air pollution is defined as heterogenous mixture of compounds including particulate matter (PM), which can easily penetrate into lungs during ventilation. One of the most dangerous components of PMs are polycyclic aromatic hydrocarbons (PAHs), representative of which is benzo[a]pyrene (BaP) [1]. In human body BaP is metabolized to highly reactive derivative benzopyrene diol epoxide. This cancerogen interacts with DNA by covalent binding and fitting to the DNA helix. This leads to DNA damage which is essential in carcinogenic processes [2]. The aim of this work was to investigate interactions between benzo[a]pyrene and pulmonary surfactant monolayers. In our research the mixture of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1’-rac-glycerol) (sodium salt) (DPPG) in a molar ratio of 8:2 was used as a model of a lung surfactant monolayer. The percentage content of BaP in the final mixture was 1 or 10%. The properties of molecular films were investigated using the Langmuir monolayer technique. Monolayers were formed on water subphase and on aqueous solution of NaCl. Moreover the interactions between BaP and phospholipids were analysed using the molecular dynamic method. The obtained results indicate that the higher the BaP concentration the stronger the influence on the interfacial properties of mixed monolayers. BaP affects the surfactant monolayer by changing its fluidity, the organization of the film and interactions between compounds.

Acknowledgements This research was financed by NCN project number UMO-2014/13/B/ST4/04995 This research was supported in part by PLGrid Infrastructure References [1] B. Korchowiec, Y. Corvis, T. Viitala, C. Feidt, Y. Guiavarch, C. Corbier, Journal of Physical Chemistry B, 112, 13518-13531 (2008). [2] M. C. Poirier, Nature Review Cancer, 4, 630-637 (2004)

PP20

Poster abstracts

149

A method for determination of polydiacetylene concentration in partially po-

lymerized films used in the field of bio or chemio sensors.

S. Spagnoli1, E. Briand2, I. Vickridge2, M. Schott2

1LIPhy: 140 avenue de la physique, BP87, 38402 Saint Martin d’Hères France. 2INSP: 4 place Jussieu 75252 Paris Cedex 05 France.


Polydiacetylenes (PDA) are a class of conjugated polymers currently actively studied for the devel-opment of biological or environmental sensors using Langmuir films or vesicles [1]. Detection relies on a structural transition of the polymer chain, causing a ≈ 630 to ≈ 540 nm shift in the optical ab-sorption peak and conventionally called the blue to red color transition. It is triggered by various stimuli: pH, temperature, pressure or in the case of sensors, by the binding of a chosen target with a specific receptor in the film. Since polymerization of PDA films is usually incomplete [2] the polymer content in the film remains unknown. This precludes the development of such sensors for quantitative titration. In this work we develop a method allowing an accurate determination of the film polymer content for in-soluble polymer which is almost always the case, using only the absorption spectrum of the film. However, this method requires the knowledge of absolute absorptivities, and absorption cross section per repeat unit of the polymer. We show that Nuclear Reaction Analysis (NRA), which determines absolute areal atomic densities, can be used to determine these absolute absorptivities. Films of various thicknesses (30 to 250 nm) were prepared by evaporation of the monomer under vacuum and photopolymerized to various polymer contents X. Such films are blue. Extraction of residual monomer by dissolution gives pure polymer films in the red phase. With NRA the total number of C atoms per unit area Nm and Np respectively, are determined on a monomer film and on the same sample after UV irradiation and extraction of residual monomer by dissolution. X is given by X=Np/Nm. One now has a series of polymer absorption spectra, blue and red, corresponding to known X, from which the absorptivities and molecular absorption cross sections are determined. The method is general and can be used for any film forming PDA. The method has been validated using one of the very few soluble PDAs, 4BCMU, of known absorp-tivity [2]. It was then applied to 10-12,pentacosadiynoic acid (PCDA), the most often used PDA in sensor studies. The quantitative relationships obtained between X and absorption spectra now allow the determination of X in any PDA film just from absorption spectra. The method can be readily ex-tended to other films, and has already been used on a trilayer Langmuir film of PCDA using absorp-tion spectra obtained in situ. This method is applicable to all kind of films, including Langmuir or LB films, for which samples can be prepared with a known thickness. References [1] X. Chen, G. Zhou, X. Peng and J. Yoon, Chem. Soc. Rev. 41, 4610 (2012) [2] S. Spagnoli, J-L. Fave, M. Schott, Macromolecules. 44, 2613 (2011)

PP21

Poster abstracts

150

Formation and properties of LbL films based on pectin and pectin-Ag

nanocomposite

K.S. Hileuskaya, A.N. Kraskouski, V.I. Kulikouskaya, V.E. Agabekov

Institute of Chemistry of New Materials of NAS of Belarus, 36 Fr. Skariny St., 220141, Minsk, Belarus


LbL films based on biocompatible and biodegradable polysaccharides, polypeptides and nanoparticles are of great interest for producing nontoxic polymeric delivery systems of biologically active substances, including antitumor compounds [1]. The formation of a biocompatible polymeric film based on pectin (Pect) and protamine (PtS) by alternate deposition (LbL technique) of PtS and Pect was investigated. The PtS/Pect ultrathin film containing silver was obtained by using nanocomposite pectin-Ag0 previously synthesized by «green chemistry» method [2]. It was demonstrated by QCM technique that the PtS/Pect film is characterized by an exponential growth of the mass in comparison to linear growth of the PtS/Pect-Ag film. The thickness of the PtS/Pect bilayer increases from 8,0 to 280,0 nm for the first and eighth adsorption cycle, respectively. The thickness of the wet PtS/Pect-Ag bilayer is 5,2±0,3 nm. PtS/Pect-Ag film is characterized by a low water content (≤10 wt.%), whereas the film without Ag nanoparticles contains water up to 60 wt.%. QCM measurements showed that the viscoelastic properties changed during film formation. The film based on protamine and nanocomposite pectin-Ag0 has a smooth surface with a typical roughness of 1-3 nm, while the PtS/Pect film has the highest surface roughness of up to 25 nm (figure 1). The in vitro biological performance demonstrates that microcapsules based on PtS/Pect and PtS/Pect-Ag films are applicable for effective antitumoral drug encapsulation. The imatinib loaded PtS/Pect-Ag microcapsules exhibited higher cytotoxicity against K-562 cancer cells than native imatinib and its IC50 value decreased 50%.

Figure 1. AFM image of LbL (PtS/Pect)4 (a) and (PtS/Pect-Ag)4 (b) films

Acknowledgement The work is partially supported by BRFFR project X14-137.

References [1] C. Monge, J. Almodóvar, T. Boudou, C. Picart, Adv. Healthcare Mater. 4, 811-30 (2015). [2] Muhanna K. A. Al-Muhanna, K. S. Hileuskaya, V. I. Kulikouskaya , A. N. Kraskouski, V. E. Agabekov, Colloid Journal 77, 677-684 (2015).

PP22

Poster abstracts

151

Pillar[6]arene containing multilayer films: Reversible uptake and release of guest molecules with methyl viologen moieties

B. Yuan1, J.F. Xu1, H. Nicolas2, M. Schonhoff2, X. Zhang1

1Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China

2Institute of Physical Chemistry, University of Muenster, Correnstraße 28/30, 48149 Munster, Germany


By combining unconventional layer-by-layer assembly method and molecular imprinting technique, surface imprinted multilayer films have been obtained [1]. However, the loading capacity as well as the robust of the imprinted site cannot be well retained during the loading and release processes. To solve this problem, macrocycles with rigid structure are introduced into multilayer films acting as artificial binding sites to realize guest uptake and selectivity [2]. Pillar[6]arene derivatives were first bound with methyl viologen (MV) to get a binary supramolecular complexes, then the complexes were employed as building blocks to fabricate multilayer films with a photo reactive polyelectrolyte, DAR, as shown in Figure 1 [3]. After photoinduced crosslinking of the multilayer films, one of the component, MV, can be removed from the films to obtain surface imprinted films with artificial binding sites. The films show good properties for molecular uptake and release as well as selectivity for guests with methyl viologen moieties due to molecule geometries. A novelty in contrast to previous approaches is the fact that here the free containers are assembled without a precomplexation to a polymeric component, such that larger surface densities can be achieved. It is anticipated that this kind of multilayer films may have future applications in the fields of enrichment of molecular dyes and purification of methyl viologen-polluted water.

Figure 1. Schematic representation of (DAR/WP6-MV)xDAR multilayer films and the structures of the building blocks for the layer-by-layer assembly

References [1] F. Shi, Z. Liu, G.L. Wu, M. Zhang, H. Chen, Z.Q. Wang, X. Zhang and I. Willner, Adv. Funct. Mater. 17, 1821-1827 (2007). [2] J.W. Zhang, Y.L. Liu, B. Yuan, Z.Q. Wang, M. Schönhoff, and X. Zhang, Chem. Eur. J., 18, 14968-14973 (2012). [3] B. Yuan, J.F. Xu, C.L. Sun, H. Nicolas, M. Schönhoff, Q.Z. Yang and X. Zhang, ACS Appl. Mater. Interfaces, 8, 3679-3685 (2016).

PP23

Poster abstracts

152

Langmuir Monolayers of Molecular Silica Sol and Stöber Particles with Ethylene Oxide Shell

Yu. N. Malakhova1,2, A.I. Buzin2, D.R. Streltsov2, D.N. Kholodkov2,3, O.B. Gorbatsevitch2, V.V. Kazakova2, A.M. Muzafarov2,3

1Moscow Technological University, Institute of Fine Chemical Technology, 86 Vernadskogo Av., Moscow,

Russia 2Enikolopov Institute of Synthetic Polymer Materials, Russian Academy of Sciences, 70 Profsoyuznaya St.,

Moscow, Russia 3Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova St.,

Moscow, Russia


The behavior of silica nanoparticles with core-shell structure in Langmuir monolayers was studied. Two different synthetic approaches were applied. Amorphous cores of the silica nanoparticles were synthesized in an alkaline medium using Stöber method. Regular cores of the molecular silica sol were synthesized in acetic acid. Their size (Rh = 1–1.3 nm) is easily adjustable by duration of tetraethoxysilane condensation. All types of the cores were modified by grafting of branches with three ethylene oxide units and various terminal groups. The particles with trimethylsilyl groups (blocked) are not water soluble. The shell of the particles with hydroxyl terminal groups becomes hydrophilic and facilitates their solubility in water. The reactions were monitored by 1H-NMR spectra. The reliability of the modifier grafting was proven by IR spectroscopy. By their size and nature of the shell the silica nanoparticles studied complement a number of macromolecular silicone compounds with different structure of a hydrophobic core with attached short ethylene oxide sequences [1, 2]. It has been found that the stability of the molecular silica sol and Stöber silica nanoparticle Langmuir monolayers is largely determined by the nature of the terminal groups and not by the core structure or molecular weight. A monolayer collapse was observed near the surface pressure of 9 mN/m for the soluble particles and at 20–40 mN/m for the blocked ones, depending on their size. The maximum value of the surface potential achieved on compression of molecular silica sol is significantly higher than that of Stöber silica nanoparticles. The Brewster angle micrographs demonstrate different morphology of the monolayers of blocked and water soluble nanoparticles. The Langmuir monolayers of silica nanoparticles were transferred onto the silicon substrates by the LB-technique at surface pressures below the monolayer collapse. The results obtained by scanning probe microscopy correlate with impaired hexagonal packing and aggregation during the LB transfer of silica nanoparticles.

Acknowledgement This work was supported by Russian Foundation for Basic Researches (projects 16-33-60194, 15-03-07718, 13-03-00997).

References [1] Novozhilova N.A., Malakhova Yu.N., Buzin M.I., Buzin A.I., Tatarinova E.A., Vasilenko N.G., Muzafarov A.M., Russ. Chem. Bull. (Int.Ed.), 62, 2514–2526 (2013). [2] Zhemchugov P.V., Peregudov A.S., Malakhova Yu.N., Buzin M.I., Buzin A.I., Shchegolikhina O.I., Muzafarov A.M., Russ. Chem. Bull. (Int.Ed.), 64, 1394–1399 (2015).

PP24

Poster abstracts

153

Multi-parametric surface plasmon resonance platform for studying liposome-

serum interactions and protein corona formation

O.K. Kari1,‡, T. Rojalin1,‡, S. Salmaso2, M. Barattin2, H. Jarva3, S. Meri3, M. Yliperttula1, T. Viitala1*, and A. Urtti1,4

1Centre for Drug Research and Division of Pharmaceutical Biosciences, Faculty of Pharmacy, University of

Helsinki, Viikinkaari 5, P.O. Box 56, FI-00014, Finland 2Department of Pharmaceutical and Pharmacological Sciences, University of Padova, Via F. Marzolo 5,

35131 Padova, Italy 3Department of Bacteriology and Immunology, Immunobiology Research Program, Faculty of Medicine, and HUSLAB, Division of Clinical Microbiology, University of Helsinki, Haartmaninkatu 3, P.O. Box 21, FI-00014,

Finland 4School of Pharmacy, University of Eastern Finland, Yliopistonranta 1, FI-70211 Kuopio, Finland

‡O.K.K and T.R. contributed equally to this work. E-mail address: [email protected]

A protein corona associates rapidly with the surface of nanocarriers administered into blood circulation and mediates their biological interactions. Label-free optical methods provide information on the drivers of corona formation without interfering with its dynamics. We demonstrate the proof-of-concept for a multi-parametric surface plasmon resonance (MP-SPR) technique in monitoring the formation of a protein corona on surface-immobilized liposomes in dynamic settings. Cationic liposomes coated in situ on the biosensor with and without polyethylene glycol (OGD±PEG) subjected to undiluted human serum were compared to Doxil replica liposomes with PEG. The affinity (KD,C3b) and surface mass density (ΓC3b) of opsonin C3b was determined with OGD±PEG. The formation of formulation dependent soft (II) and hard (II) coronas was observed with distinct refractive indices and layer thicknesses determined using layer-by-layer modeling (Figure 1).

Figure 1. Schematic representation of the MP-SPR setting (left). Real-time sensorgram of soft (II) and hard (III) protein corona

formation on liposomes with and without PEG (right).

The tendency to create a thick corona correlated with a higher KD,C3b for the surface and absence of PEG. The label-free MP-SPR platform is suitable for optical characterization of the formation and evolution of protein coronas on nanocarrier surfaces. It provides a fast and robust preclinical tool for tuning nanocarrier surface architecture and composition to control protein corona formation.

PP25

Poster abstracts

154

Application of hierarchically-structured latex polymer coatings and self-supporting films in the fabrication of cell culture platforms

E. Rosqvist1, E. Niemelä2, A. Määttänen1, A.P. Venu2, H. Abdelkader2, F. Cheng2, P. Kankaanpää2, J. Eriksson2, J. Peltonen1, P. Ihalainen1

11Laboratory of Physical Chemistry, Centre for Functional Materials, Åbo Akademi University,

Porthansgatan 3-5, FI-20500 Åbo, Finland 2Laboratory of Cell Biology, Åbo Akademi University, Artillerigatan 6, FI-20520 Åbo, Finland


Hierarchically-structured latex polymer coatings and self-supporting films for the fabrication of cell culturing platforms with multi-modal (optical, electrochemical) detection possibilities are characterised and utilised in this study. The use of latex coatings or self-supporting films as transparent support materials or substrates in active scaffold platforms enables continuous and real-time regulation, modulation and monitoring of cellular processes and behaviour. The latex surface component passively regulates cellular behaviour through controlled structuring, and can be applied on rigid or flexible substrates by coating or printing, thus enabling high-throughput fabrication of coated and patterned films. Further, latex offers excellent adhesive support for biomolecules and ultra-thin conducting metallic and polymeric films - facilitating the introduction of additional passive or active components in the scaffold platforms, for e.g. continuous electrochemical monitoring of glucose levels, pH, ion concentrations, antibody-antigen binding and DNA hybridization. Actual utilisation of latex coatings in cell-culture scaffold platform fabrication is demonstrated with a case study using Human Dermal Fibroblast (HDF) cells; Coverslip glass substrates were coated with blends of two different aqueous latex dispersions, hydrophobic polystyrene (PS) and hydrophilic carboxylated acrylonitrile butadiene styrene (ABS). The ratio of components in the blend controls the surface’s nano-structured morphology and topography, and compositional hydrophilic/hydrophobic property. Thin latex-coatings retain high transparency on coverslip glass allowing optical microscopy imaging of cell growth on the platform. In addition, due to relatively low background autofluorescence of the latex, confocal microscopy can be used for high-resolution study of cell morphology. The results show that HDF cell growth and viability is enhanced up to 150-250 % on latex surfaces with bimodal morphology, and specific step-height and spacing of nanofeatures, compared to coverslip glass and commercial cell assay micro-plates. In addition, high-resolution confocal imaging clearly indicates less stress-fibre development of the cells on the latex surface compared to coverslip glass.

PP26

Poster abstracts

155

Understanding hydrated polyelectrolyte complexes and multilayers via molecular simulations

Piotr Batys1,2, Ran Zhang1,3, Maria Sammalkorpi1

1Department of Chemistry, Aalto University, P.O. Box 16100, 00076 Aalto, Finland

2Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Krakow, Poland 3State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese

Academy of Sciences, Changchun, P.R. China


Polyelectrolyte complexes and layer-by-layer (LbL) assemblies, also known as polyelectrolyte multilayers are versatile materials which are receiving increasing attention because of their stimuli-responsive behaviour with ionic strength, pH, and temperature. While hydrated polyelectrolyte assemblies are employed as biological and energy systems, smart surfaces, sensors, and drug delivery, significant open questions remain regarding the role of salt (ions), hydration, and intrinsic vs. extrinsic charge compensation on the assembly structure, binding strength and resulting mechanical characteristics of the resulting films and assemblies. Here, we present molecular simulations characterization of hydrated polyelectrolyte assemblies. Our system of interest is mainly poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) interactions as a function of pH, water content and presence of ions. We find the role of water hydrogen bond network, ion hydration, ion species, as well as, ion-ion pairs in determining the mechanical properties, as well as, the thermal response of polyelectrolyte assemblies. We compare the findings with our earlier work on strongly charged polyelectrolytes, namely poly(diallyldimethylammonium chloride) (PDAC) and poly(styrene sulfonate) (PSS) and experimental characterization of the corresponding assemblies. Finally, we discuss the extent and limitations of information that can be drawn via simulations of these complex molecular materials.

PP27

Poster abstracts

156

Polypyrrol/AuNP films: Development and sensing properties towards catechol

Celia García-Hernandez1, Cristina García-Cabezón2, Cristina Medina-García1, Yolanda Blanco2, Fernando Martín-Pedrosa1,Silvia Rodríguez1, Maria Luz Rodríguez-Méndez1

1Dept. Inorganic Chemistry, Engineers School, Universidad de Valladolid, 47011 Valladolid, Spain

2Dept. Materials Science, Engineers School, Universidad de Valladolid, 47011 Valladolid, Spain


Polypyrrole (Ppy) is one of the most extensively studied conducting polymers due to its good electrical conductivity and redox properties [1]. Ppy films can be easily generated by electropolymerization as a strong adherent layer using different electrochemical techniques. Electrodes chemically modified with Ppy have a good electrocatalytic activity. The structure and sensing properties of the Ppy films are considerably influenced by the electrochemical method used for the polymerization, by the electrochemical conditions, and by the other experimental conditions such as the nature and concentration of the doping agent or the nature of the substrate. Recently, composite nanomaterials based on conducting polymers and metal nanoparticles (NPs) have been developed [2]. Conducting PPy/AuNP composites exhibit improved physical and chemical properties over their single-component counterparts and are the focus of intensive research. The objective of this work was to develop new voltammetric sensors based on electrodeposited Ppy/AuNPs for the detection of catechol (an antioxidant of interest in the food industry) and to evaluate the influence of the electrodeposition method in their performance. Therefore, Ppy/AuNP films doped with 1-decanesulfonic acid (DSA) were deposited using different electropolymerization methods (chronoamperometry and chronopotentiometry) and approaches of insertion of the AuNPs. Particular attention was paid to the study of the influence of the substrate used for the electrodeposition that was carried out onto classical platinum electrodes and on stainless steel substrates. This aspect could play a crucial role not only in the structure, properties and performance of the sensor but also in the final price. Scanning electron microscopy (SEM) demonstrated that in all cases gold nanoparticles of similar size (30-40 nm) were uniformly dispersed in the Ppy matrix (Fig. 1). Electrochemical impedance spectroscopy (EIS) experiments demonstrated that the insertion of AuNPs modified the electrical behavior and increased the conductivity. The electrocatalytic and sensing properties towards catechol of Ppy/AuNP electrodes were analyzed. Catechol produced the expected well-shaped redox pair generated by the two-electron oxidation/reduction of the orto-dihydroquinone to benzoquinone. The limits of detection were in the range from 10−5 to 10−6 mol/L.

Figure 1. SEM image of Ppy/AuNP films deposited on stainless steel by chronopotentiometry.

Acknowledgments: Financial support from CICYT (Grant nº AGL2015-67482-R) and Junta de Castilla y León (VA-052A06) is gratefully acknowledged. CGH thanks for the grant of JCYL (D-24112015-9).

References [1] Ramanavicius, A.; Ramanaviciene, A; Malinauskas, A. Electrochimica Acta 51 6025-6037 (2006). [2] Yoon, H. Nanomaterials 3 524-549 (2013).

PP28

Poster abstracts

157

Phthalocyanine Layer-by-Layer film as sensor for polyphenol detection in tea samples

Mateus Dassie Maximino1, Cibely Silva Martin1, Fernando Vieira Paulovich2, Priscila Alessio1

1Physics Department, Faculty of Science and Technology, Univ Estadual Paulista, Presidente Prudente, SP, 19060-900, Brazil

2Institute for Mathematics and Computer Science, University of São Paulo, São Carlos, SP, CP 668, 13560-970, Brazil


Polyphenols have attracted attention due to their antioxidant capacity and beneficial effects to health.1 Therefore, fast, inexpensive and efficient methods to discriminate and to quantify polyphenols are of interest for food industry. In this work, Layer-by-Layer (LbL) films of poly(allylamine hydrochloride) and iron tetrasulfonated phthalocyanine (PAH/FeTsPc) were employed as a sensing layer for determination of polyphenols in green tea (camellia sinensis), and green and roasted mate teas (ilex paraguariensis). The polyphenol sensor was tested in catechol standard solution by differential pulse voltammetry (DPV), reaching a limit of detection of 1.76x10-7 mol L-1. The determination of polyphenols in the tea samples was obtained by an analytical curve and catechol standard addition using electrochemical techniques. A projection technique called Sammon’s mapping (information visualization) from DPV results of the tea samples shows a separation pattern dependent on the phenolic content, with the green tea sample showing the highest phenolic content. (Figure 1). The pattern observed is in agreement with the phenolic contents obtained from the Folin-Ciocalteu method. The results support the application of the sensor in fast classification of beverages according to their polyphenol content.

Figure 1. Sammon’s mapping from DPV data of tea samples using different ITO electrodes modified with 5 bilayers of PAH/FeTsPc.

References [1] Preedy VR. Tea in Health and Disease Prevention, Academic Press, London (2013).

PP29

Poster abstracts

158

Voltammetric studies of thin films transport properties

Piotr Batys1,2, Magdalena Nosek2, Michał Skoczek2, Paweł Weroński2


2 Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Krakow, Poland


Adsorption of colloidal particles at a solid/liquid interface leads to a spontaneous formation of a porous layer, which may have a noticeable effect on the ion transport from the bulk solution to the adsorption surface. Recently, following the application of electrochemical techniques in studies of ion transport through gel layers, we have proposed a novel method for quantitative description of colloidal particle films, based on cyclic voltammetry measurements of limiting diffusion current at rotating disk electrode [1-4]. Here, we have presented a short review of our recent research on the application of this technique in studies of diffusion in layers of spherical particles. We have discussed our theoretical model for the description of adsorbed particle-monolayer effect on the limiting diffusion current at a rotating disk electrode [3]. We have demonstrated that electrochemical measurements of the limiting diffusion current at a rotating disk electrode with a monolayer of adsorbed particles provide means for the determination of the electrode surface coverage. Then, we have verified our predictions experimentally and determined the application range of our theoretical model [3,4]. We have also presented results of our theoretical and experimental research on multilayers of spherical particles assembled layer by layer. We have used a Monte Carlo model [5-8] to create a number of virtual multilayers of hard spheres at a solid-liquid interface, at various surface coverages and numbers of single layers. For each of the multilayers, we have determined its mean thickness, porosity, tortuosity, and equivalent thickness of stagnant solution layer [3,7]. From our simulation results, we have determined the equivalent layer thickness as a function of the mean surface coverage and layer number of multilayer. We have also tested our theoretical results experimentally [6,8]. We have found a good agreement between the numerical simulations and experiments. We have also demonstrated that our approach provides means to study the kinetics of colloidal particle adsorption at the rotating disk electrode [9]. With the novel method, we can estimate the surface-charge heterogeneity of colloidal particle as well.

References

[1] Nosek, M.; Weroński, P.; Nowak, P.; Barbasz, J. Colloids Surf. A 403, 62 (2012). [2] Nosek, M.; Weroński, P.; Nowak, P.; Barbasz, J. Colloids Surf. A 429, 159 (2013). [3] Weroński, P.; Nosek, M.; Batys, P. J. Chem. Phys. 139, 124705 (2013). [4] Nosek, M.; Batys, P.; Skoczek, M.; Weroński, P. Electrochim. Acta 133, 241 (2014). [5] Batys, P.; Weroński, P. J. Chem. Phys. 137, 214706 (2012). [6] Batys, P.; Nosek, M.; Weroński, P. Appl. Surf. Sci. 332, 318 (2015). [7] Batys, P.; Weroński, P. Modelling Simul. Mater. Sci. Eng. 22, 065017 (2014). [8] Batys, P.; Nosek, M.; Skoczek, M.; Weroński, P. Electrochimica Acta 164, 71 (2015). [9] Skoczek, M.; Nosek, M.; Weroński, P. Electrochim. Acta 190, 1078 (2016).

PP30

Poster abstracts

159

Dissimilar surface propertiesof Hemoglobincombined with O2and CO

Ai Maehira1, Dock-Chil Che1, Akito Shimouchi2, Makoto Sawano3, Takuya Matsumoto1

1Osaka Univ., Toyonaka, Osaka, 560-0043, Japan 2NCVC, Suita, Osaka, 565-0873, Japan

3Saitama Med. Univ., Iruma-gun, Saitama, 350-0495, Japan E-mail address: [email protected]

It is known that the structure of hemoglobin(Hb) changes by being bounded with oxygen(O2) orcarbon monoxide(CO). By measuring the vibrational spectra between the hemiron and the bounded molecules,

the local structure and stability for hemoglobin have been found to varyby changingthe bounded molecules. However, the physicalproperties of overall surface structure depending on the bounded molecules are not clear in detail. In order to clarify the surface propertiesfor hemoglobin with O2(HbO2)or CO(HbCO)are examined by the AFM measurement, zeta potential measurement and precipitate with ethanol experiment. To observethephysical properties of the molecular level for hemoglobin, the images of HbO2and HbCO by using AFMaremeasured.It was found that the height of observed HbO2images arehigher than thoseof

HbCO, and the imagesof HbCOshow self-aggregation. To clarify the adhesion behavior, we measured the occurrenceof each moleculeat the given area. Asthe result, it was found that the number of adhesion of HbCOis smaller than that of HbO2.These resultssuggest that the surface properties for HbO2and HbCOon the mica, which is hydrophilic, aredifferent from each other.It may be caused by the dissimilarsurface propertiesof HbO2and HbCO. To clarifythe superficialphysicalproperties forhemoglobin, the zeta potentialsdepending on the pH of

HbO2and HbCO are measured. It was found that the zeta potential for HbCO is higher than that of HbO2.

This result tellsus that the interaction of HbCOwith water molecules is stronger than that of HbO2. In

addition, the precipitate with ethanol experiment was carried outto examine the stabilities for HbO2and

HbCO. Results show that the chemical bond of CO with hem is more stable than that of O2, and that the

structure of porphyrin ring in HbCO is more stable than that in HbO2. We conclude that the stabilities for

HbCO may be caused by the stronger interaction of water molecules leading to the dissimilarsurface

physical properties between HbO2and HbCO.

PP31

Poster abstracts

160

DNA multilayer film for loading and release of DNA oligomers

Y. Kamimura and N. Kato

Graduate School of Science and Technology, Meiji University, Kawasaki 214-8571, Japan


The template-assisted Layer-by-Layer (LbL) method is a typical strategy for preparing functional polymeric capsules such as smart drug carriers [1]. Besides the polyelectrolyte-based LbL film, the DNA LbL film, which was assembled via partial hybridization between the alternating layers of DNA oligomers, is attracting attention as a material for drug carriers due to its biocompatibility and versatility [2-4]. Here we report the DNA LbL film, where the specific oligomer can be released by a stimulus. The film structure is as follows: 5’(CT)203’ is adsorbed via electrostatic interaction on the substrate. 5’G(AG)7T15*3’ is the 1st layer adsorbed via hybridization force (HF) between the G(AG)7 block of 5’G(AG)7T15*3’ and 5’(CT)203’. 5’G15*A15*3’ is the 2nd layer adsorbed via HF between the A15* block of 5’G15*A15*3’ and the T15* block of 5’G(AG)7T15*3’. 5’C15*XT15*3’ is the 4th layer adsorbed via HF between the C15* block of 5’C15*XT15*3’ and the G15* block of 5’G15*A15*3’. The 2nd and 3rd layers were alternatively adsorbed up to the 8th layer. The A15* and C15* blocks are the A- and C-rich 15-base sequences, respectively, and their complementary blocks are the T15* and G15* blocks, respectively. X in 5’C15*XT15*3’ is complementary to Y (5’GGGAGAGAAC3’) that is designed to be released after the stimulation; exposure to the aqueous NaCl (150 mM, 40 oC). The layer growth and the release of Y were monitored by quartz crystal microbalance (QCM). Y was bound to 5’C15*XT15*3’ prior to the film formation, and the film was built in the citrate buffer (50 mM Na3C6H5O7, 0.5 M NaCl) at 25 C. Fig. 1(a) shows the linear decrease in the resonant frequency of QCM, indicating the almost equal amount of DNA absorbed in each layer. When the stimulation was applied to the as-prepared film, the frequency was decreased more than the calculated value for the release of Y, indicating that few building blocks other than Y came off. After the application of the first stimulation, post-loading of Y was carried out to the film and the stimulation was applied again. When Y was loaded to the film whose mass corresponds to the frequency shift of - 384 Hz, the frequency should change by -63 Hz. Fig. 1(b) shows that the frequency changed as expected over two cycles of the loading of Y and the stimulation. Thus, once the stimulation was applied to the as-prepared film, the DNA LbL film performed the function for loading and release of the specific oligomers. References [1] S. De Koker, R. Hoogenboomc, B. G. De Geest, Chem. Soc. Rev. 41, 2867 (2012). [2] A. P. R. Johnston, E. S. Read, F. Caruso, Nano Lett. 5, 953 (2005). [3] N. Kato, L. Lee, R. Chandrawati, A. P. R. Johnston, F. Caruso, Small 10, 2902 (2014).

PP32

Figure 1. (a) Frequency change as a

function of layer number. (b) Frequency

change upon the supplement of Y and the

stimulation cycle applied to the film after

the first stimulation.

Poster abstracts

161

Stability and reversibility of tear film polar lipid layer biomimetics: Understanding

the role of major tear film proteins

D.A. Haley, M.J. Patterson, H.J. Vogel and E.J. Prenner

University of Calgary, 2500 University Dr. NW, Calgary, Alberta, Canada T2N 1N4 E-mail address: [email protected]

The precorneal tear film is a three layered structure that allows high visual acuity and protects the corneal epithelium. [1] Adjoining the epithelial cells is the glycocalyx layer, followed by an aqueous layer, and a lipid layer. This lipid film assists in stabilizing the aqueous layer by lowering its surface tension. Importantly, the lipid layer has the ability to resist collapse, and to reversibly compress and expand during a blink, preventing the formation of gaps. The lipid layer is composed mostly of non-polar lipids, but a polar lipid layer provides an essential interface between the hydrophobic non-polar lipids and the aqueous phase. Proteins are abundant in the aqueous layer and insert into the lipid layer, or adsorb to the lipids at the interphase between the two layers. Major polar lipids and proteins identified in the tear film were investigated in order to further understand how they affect stability and reversibility of the tear film. Synthetic lipids used in single systems and mixtures were dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylethanolamine (DPPE), palmitoylglucocerebroside (PGC), and palmitoyl-sphingomyelin (PSM). To mimic blinking, surface pressure-area isocycles were generated by repeated compression and expansion of the monolayer systems using a Langmuir trough. Additionally, the lipid systems have been imaged by Brewster angle microscopy (BAM) to see changes in lateral configuration. The tear film proteins lysozyme, lactoferrin, and tear lipocalin have also been injected into the subphase during Langmuir trough experiments to investigate their role in stabilizing the lipid layer. Results from lipid-only mixed biomimetics show that especially systems containing PGC had increased reversibility, suggesting that hydrogen bonding is important for stable film cycling. A 3D analysis of BAM images for the 3DPPC:2DPPE:3PGC system showed possible multilayer structures, which may be important for reversibility (Figure 1).

Figure 1. (Left) Brewster Angle Microscopy (BAM) image (218 by 271 μm) for the compression of the 3DPPC:2DPPE:3PGC system. (Right) 3D analysis of the BAM image, representing possible multilayer formation.[2]

References [1] Green-Church, K. B., Butovich, I., Willcox, M., Borchman, D., Paulsen, F., Barabino, S., & Glasgow, B. J., Visual Science 52(4), 1979–1993 (2011). [2] Patterson, M., Vogel, H. J., & Prenner, E. J., Biochimica et Biophysica Acta (BBA) - Biomembranes, 1858(2), 403–414

(2016).

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Poster abstracts

162

pH responsive gold nanoparticles for anticancer drug delivery: Novel characterization by surface plasmon resonance

A. Kartal-Hodzic1, S. Bisso1,2, C. Brazzale2, S. Salmaso2, T. Viitala1

1 University of Helsinki, Division of Pharmaceutical Biosciences, Faculty of Pharmacy, Viikinkaari 5E (P.O. Box 56), 00014 University of Helsinki, Finland

2 Department of Pharmaceutical and Pharmacological Sciences, University of Padova, F. Marzolo 5, 35131 Padova, Italy


Controlled drug delivery systems realized with stimuli-responsive materials are innovative systems that can be tightly modulated by stimuli, in order to treat particular and often severe diseases. This study was focused on the use of gold nanoparticles (GNPs) as a platform for the development of a pH responsive targeted system for anticancer drug delivery [1]. The system was here studied in vitro with a novel analytical approach, namely Surface Plasmon Resonance (SPR), to investigate the association of the particles with cancer cells. KB cells from human epithelial cervix carcinoma were chosen as model cell line since they overexpress the folate receptor, to which the particles are directed by the targeting agent. It is known that after receptor finding of folate, internalization occurs via caveolae, in a receptor-mediated endocytosis. Folate targeted nanoparticles, together with non-targeted nanoparticles, that may be internalized by cells by other mechanisms, were investigated in a comparative study with SPR. KB cells were successfully immobilized on an SPR gold sensor in a fully confluent monolayer, by using fibronectin as an adhesion promoter. The cellular response was measured after injection of GNPs modified with the pH responsive copolymerpoly (MCH –co - GMA) and the targeting agent, FA-PEG2 kDa-SH at two different pHs, 7.4 and 6.5. GNPs decorated with mPEG2 kDa-SH and the pH sensitive polymer, naked GNPs and GNPs decorated with only mPEG-SH 5 kDa were used as control. Pure medium injection without GNPs was shown to have no effect in term of SPR response on cells. Furthermore, the injection of particles on a non-treated, clean SPR sensor yields no response or to a positive shift of the SPR angle, indicating that unspecific interactions with the gold surface may occur. When KB cells were exposed to the particles, alterations of the resonance angle were correlated to dynamic mass redistribution within the cell, while changes in the intensity of the SPR peak were associated to vesicles formation into the cell. The results demonstrated that the SPR response reflects real-time events occurring in living cells, describing the different interaction and uptake pathways of particles. The results of this study open unexplored application of SPR technique to study cell interaction with colloidal carriers providing for less time consuming, real-time, and label free approaches. The SPR technique for cell based sensing is a very promising technique that can offer unquestionable advantages for label free detection of cellular mechanisms. This technique is now under validation, and a complete understanding of the SPR response is still a matter of investigation. Further studies are required to define all details of the method and achieve a better understanding of the dynamics involved in cell/particles interactions. References [1] Bisso Sofia, pH responsive gold nanoparticles for anticancer drug delivery: novel characterization by Surface Plasmon Resonance, Master thesis, 2014

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Poster abstracts

163

Biomimetic Collagen I and IV double layer Langmuir-Schaeffer films as

microenvironment for cells

Elina Vuorimaa-Laukkanen1, Anni Sorkio2,Hanna Hakola1, Huamin Liang1, Tiina Ujula3, Juan José Valle-Delgado3, Monika Österberg3, Marjo Yliperttula4,5 and Heli Skottman2

1 Department of Chemistry and Bioengineering, Tampere University of Technology, Korkeakoulunkatu 8,

33720 Tampere, Finland 2 BioMediTech, University of Tampere, Biokatu 12, 33520 Tampere, Finland

3 Department of Forest Products Technology, School of Chemical Technology, Aalto University, P.O. Box 16300, 00076 Aalto, Finland

4Division of Biopharmaceutical Sciences, Centre for Drug Research, Faculty of Pharmacy, University of Helsinki, Viikinkaari 5, 00790 Helsinki, Finland

5Department of Pharmaceutical and Pharmacological Sciences, via F.Marzolo, 5, University of Padova, Padova, Italy

E-mail address):[email protected]

The environmental cues received by the cells from synthetic substrates in vitro are very different from those they receive in vivo. In this study, we applied the Langmuir-Schaeffer (LS) technique, to fabricate a biomimetic microenvironment mimicking the structure and organization of native Bruch’s membrane for the production of the functional human embryonic stem cell derived retinal pigment epithelial (hESC-RPE) cells. Surface pressure-area isotherms were measured simultaneously with Brewster angle microscopy to investigate the self-assembly of human collagens type I and IV on air-subphase interface. Furthermore, the structure of the prepared collagen LS films was characterized with scanning electron microscopy, atomic force microscopy, surface plasmon resonance measurements and immunofluorescent staining. The integrity of hESC-RPE on double layer LS films was investigated by measuring transepithelial resistance and permeability of small molecular weight substance. Maturation and functionality of hESC-RPE cells on double layer collagen LS films was further assessed by RPE-specific gene and protein expression, growth factor secretion, and phagocytic activity. The prepared thin films showed layered structure with oriented fibers resembling the architecture of the inner collagenous layer and basement membrane of the Bruch’s membrane. This study is the first to show successful preparation of organized collagen IV films with fiber-like networks using LS technique as well as the first study to successfully mimic the organized structure and composition of the two uppermost layers of the Bruch’s membrane. Furthermore, the prepared double layer collagen LS films were superior in supporting the hESC-RPE maturation and functionality compared to the dip-coated collagen control. Hence, this study demonstrates that the prepared double layer collagen LS films provide a biomimetic microenvironment for the efficient production of hESC-RPE cells in vitro potentially increasing their functionality in tissue engineering applications.

References [1] A. Sorkio*, E. Vuorimaa-Laukkanen, H. Hakola, T. Ujula, J. J. Valle Delgado M. Österberg, M. Yliperttula and H. Skottman, Biomaterials 51, 257 (2015).

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Poster abstracts

164

Self-assembly-assisted biomolecule-enriched surface and high selectivity

performance of biomimicking copolymers

Heesoo Kim1, Kyungho Kwon2, Changsub Kim2, Jongchan Lee2

1Department of Microbiology and Dongguk Medical Institute, Dongguk University College of Medicine, Gyeongju 780-714, Republic of Korea

2Department of Chemistry, Division of Advanced Materials Science, Pohang Accelerator Laboratory, Polymer Research Institute, and BK School of Molecular Science, Pohang University of Science and

Technology, Pohang 790-784, Republic of Korea E-mail address: [email protected]

Poly(oxy(11-(biotinyl)undecylthiomethyl)ethylene-co-oxy(11-phosphoryl-cholineundecylthiomethyl)-ethylene)s (PECH-BTmPCn: m = 0~100 mol% biotin (BT) containing bristle; n = 100~0 mol% phosphorylcholine (PC) containing bristle) were newly synthesized. All polymers exhibited excellent solution processability. They favorably self-assembled horizontal multi-bilayer structures in thin films with BT- and PC-enriched surfaces, which were driven by the lateral ordering of the fully extended upright bristles and the partial inter-digitation between the BT and PC end groups of the bristles. Both hydrophilicity and water sorption of the films increased with the PC content. The PECH-BT100 films revealed remarkably distinctive sensitivity, selectivity, and adsorption ability for avidin against other proteins. Such remarkable performance was further significantly enhanced on the PECH-BTmPCn films in which PC moieties were incorporated to the BT-rich surface; in particular, the PECH-BT75PC25 films demonstrated the highest performance. Overall, the self-assembly brush copolymers of this study are very suitable for use in the high performance detection, adsorption, and separation of proteins and receptors, including avidin, which can reveal high affinity and selectivity to BT moiety.

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Poster abstracts

165

Preparations of the anisotropic hierarchical microstructures by using self-

organization

Hirotoshi Mori, Yuji Hirai, Masatsugu Shimomura

Chitose Institute of Science and Technology, 758‐65, Bibi, Chitose, Hokkaido 066‐8655, Japan E-mail address: y‐[email protected]

The surfaces of the lotus leaves and dragonfly wings form a hierarchical structure, and their surface generates functions of superhydrophobicity. Preparations of the artificial microstructures by lithographical technology required a lot of energy. Other hand, many biological surfaces have functional structured surfaces prepared by low energy processes of the self‐organization. There is a famous self‐organization process of dewetting phenomenon, which is the periodic recession of the solution interface due to concentrate and precipitate the solute. In this report, we attempted to fabricate the anisotropic hierarchical micro‐structured surfaces by the self‐organization process of dewetting phenomenon and octadecyl trichlorosilane (OTS). OTS/hexane solution (concentration of 89.5 g/L) was prepared. After UV‐O3 treatment, two glass slides were fixed on substrate holders of the dewetting equipment (Figure 1 (a)). Then, the solution was dropped between the gap of about 1 mm of the two glass substrates, and one glass slide was slided at a slide speed 3.0 mm/min. After dewetting of OTS/hexane solution, the surfaces were observed by laser microscopy and field‐emission scanning electron microscopy (FE-SEM), and surface wettabilities were measured by water contact angle (WCA) analyzer. As results, stripe patterns were formed on the surface by dewetting phenomenon (Figure 2 (a,b)). Surface observations of FE‐SEM revealed that hierarchical structures were formed on the stripe patternes (Figure 2 (c,d)). The results of WCA measurements, WCAs were up to 152.6°. And also, sliding angles of water droplets were different between the tilted directions of glass slides. These results suggested that superhydrophobic hierarchical micro‐structured surfaces of OTS were successfully prepared by dewetting. And also, it surface showed water droplet sliding angle anisotropy by their anisotropic hierarchical microstructures.

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Poster abstracts

166

Surface plasmon resonance microscopy of liposomes and liposome encapsulates

Lauri Viitala1, Adam Maley2, Millie Fung2, Robert Corn2, Lasse Murtomäki1

1Department of Chemistry, Aalto University. P.O. Box 16100, FI-00076 Aalto, Finland 2Department of Chemistry, University of California-Irvine, Irvine, California 92697, United States


Photothermally driven drug release from liposomal drug delivery systems can be obtained by adding gold nanoparticles (AuNPs) into the cavity of the liposomes [1]. In terms of producing such systems, one of the most important parameters is the encapsulation efficiency (EE) that is normally determined by e.g. cryo-TEM or by fluorescence after breaking the liposomes with a non-ionic surfactant, such as Triton X-100. In this work, we show that 1) single liposomes can be studied with surface plasmon resonance microscopy (SPRM) and 2) SPRM can be used to determine the AuNP EE from liposomes in room temperature without interfering the system with any additives. The EE is obtained by measuring a set of single liposome binding SPRM intensities and scattering patterns on the surface. Difference images are constructed as in Halpern et al.[2]. Each liposome is detected from the FFT filtrated image, and the intensities are presented as a cumulative distribution function (CDF) where two statistically relevant binding types can be found for the liposomes with AuNPs (that were not visible by themselves) whereas only one binding type is detected in the case of bare liposomes (see Figure1).

Figure 1. From left to right: the SPRM difference image; FFT filtrated difference image; cumulative distribution function and (finally) probability distribution function (PDF) of the liposomes with and without gold nanoparticles. One-particle-type fits and two-particle-type fits are shown as dashed lines and normal lines respectively. Best fits are presented as PDFs, in the last figure, where like in the CDFs, blue line represents the fit for liposomes without gold, and red and yellow line are the fits for the liposomes with 10 nm and 40 nm GNPs respectively. Black dots in the third figure (CDF) are the observed SPRM intensities for each particle.

References [1] Lajunen, T.; Viitala, L.; Kontturi, L.; Laaksonen, T.; Liang, H.; Vuorimaa-Laukkanen, E.; Viitala, T.; Le Guével, X.;

Yliperttula, M.; Murtomäki, L.; Urtti, A. J. Contr. Rel. 203, 85 (2015). [2] Halpern, A. R., Wood, J. B., Wang, Y. & Corn, R. M. Single-Nanoparticle Near-Infrared Surface Plasmon Resonance

Microscopy for Real-Time Measurements of DNA Hybridization Adsorption. ACS Nano 8, 1022 (2014).

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Poster abstracts

167

Friction measurements of firebrat scale surfaces

Naoto Okuda1, Yuji Hirai1, Ryuichiro Machida2, Nomura Shûhei3, Masahiro Ôhara4, Masatugu Shimomura1

1Graduate School of Photonics and Sience, Chitose Institute of Science and Technology, 758-65 Bibi,Chitose,

Hokkaido 066-8655, Japan 2Sugadaira Montane Research Center, University of Tsukuba, Sugadaira Kogen Ueda, 386-2204, Japan

3Department of Zoology, National Museum of Nature and Science, Amakubo 4-1-1, Tsukuba-shi, Ibaraki, 305-0005, Japan

4The Hokkaido University Museum, N 10, W8, Sapporo, 060-0810, Japan


Friction and wear causes a lot of problems in a wide variety of fields, such as energy loss. In nature, there are friction reduction surfaces realized by surface microstructures[1]. In the present study, we focused on firebrats, which lives in narrow spaces such as under barks or between piled papers. Their body surface is scratched there, and so they would have been evolved against wearing. Here, we show surface observations and friction measurements of firebrats by using field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM).

We examined the firebrat’s surfaces of 5 different regions: head (A in Fig. 1), prothorax (B), metathorax (C), 8th (D), and 9th (E) abdominal segments. Scale surfaces are with parallel grooves, Although groove periods were almost uniform within each scale, they vary much between the scales in the anterior regions of the body, especially around the head (Fig. 2). We measured the friction force of a scale with ca. 3.5 µm periodic groove by using AFM with colloidal probes (colloidal diameter: 2.0, 3.5 and 6.6 µm). Fig. 3 shows friction force images of the scale surface. It was revealed that the friction force was the highest in the colloidal probe of 3.5 µm diameter and the lowest in that of 6.6 µm one. Details will be presented in the paper to be published in near future.

Acknowlegdement This work was supported by the Japanese Ministry of Education, Culture, Sports, Science and Technology (MEXT) via Grants-in-Aid for Scientific Research on Innovations Areas (Grant no. 24120003) and Grant-in-Aid for Young Scientists A (Grant no. 26712028). References [1] R.A.Berthe, et al., journal of comparative physiology A, 195 (3), 311318.

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Figure 3. Friction force images of a firebrat scale with ca. 3.5 µm periodic groove (Bars: 5µm). Blue and red broken lines respectively show the top and bottom of grooves.

Figure 1. A laser microscope image of a firebrat. A to E are the regions observed by FE-SEM.

Figure 2. FE-SEM images of scales of a firebrat at the different regions: head (a), thorax (b) and posterior abdomen (c) (Bars: 30 µm).

Poster abstracts

168

Polymer Microparticles coated with a thin metal layer from wrinkles upon electron bean irradiation

Olaf Karthaus1, Konomi Uchiya1, Antonia Herzog2

1Department of Applied Chemistry and Bioscience, Chitose Institute of Science and Technology, Bibi 65-758, Chitose, Hokkaido 066-8655, Japan

2Freie Universität Berlin, Faculty of Biology, Chemistry, Pharmacy, Takustraße 3, 14195 Berlin, Germany


Pollens are microscopic particles of plants that transport DNA from the anther to the pistil. There are more than 400 000 flowering plants and each plant has its characteristic pollen surface structure. The outer shell consist of a crosslinked lignin-like polymer that is thermally as well as mechanically extremely stable. Its biosynthesis as well as pollen morphogenesis is still poorly understood, but from the viewpoint of material science, it would be interesting to see if similar surface structures could be formed by non-biogenic pathways. Of the many different types of surface decorations, several pollen surfaces look as if the pollen particle is covered by wrinkles. Wrinkling is a well know phenomenon that is caused either by swelling of a soft surface layer on a harder bulk material, or by shrinking of a soft material that is covered by a hard layer. In planar samples, wrinkles can be produced by applying a lateral force to a soft material (e.g. PDMS) that is covered with a thin layer of a harder material (e.g. SiO2). A lateral force in a film corresponds to a tangential force in spherical particles. This force can be induced by shrinking the bulk material of the sphere that has been covered with a thin skin-layer of a hard material, e.g. PDMS core and silicate shell1. Here we propose a new method for producing and controlling surface wrinkle patterns. We use spherical PMMA microparticles that are covered with a thin metal layer by vacuum sputtering. The thickness of the metal layer can be controlled by sputtering time, when the other parameters, such as electrical current and sample position is kept constant. PMMA is known to decompose upon irradiation with an electron beam2. Thus, the polymer particle should shrink, leading to a force perpendicular to the particle surface that then produces the wrinkles.

Figure 1. Temporal development of the wrinkle pattern during irradiation (left). Dependence of the wrinkle pattern on the sputtering time of the meatl coating (metal layer thickness).

References 1. Derek Breid, Alfred J. Crosby: Curvature-controlled wrinkle morphologies, Soft Matter (2013) 9, 3624. 2. M. Tabata, J. Sohma: Degradation of poly(methyl methacrylate) by ionizing radiation and mechanical forces, Developments in Polymer Degradation, Elsevier Applied Science Publishers 1987.

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Poster abstracts

169

The membrane mimetic matrix affects the adsorption of tyrosinase and influences the biosensors’ performance for polyphenols detection

Matheus Santos Pereira, Cibely da Silva Martin, Priscila Alessio

Univ Estadual Paulista – UNESP/Faculty of Science and Technology – Pres. Prudente, SP, Brazil


Biosensors are devices that present biological recognition elements such as enzymes in the composition. The immobilization of the enzyme on devices should preserve its enzymatic activity. Mimetic membranes have been used as adequate systems to this end1. In order to optimize the fabrication of biosensors for polyphenols, the interaction between the enzyme tyrosinase (Ty) and three membrane mimetic models: arachidic acid (AA), dipalmitoylphosphatidylglycerol (DPPG) and dipalmitoylphosphatidylcholine (DPPC) was studied using Langmuir films. The adsorption kinetics of Ty to the air-water interface was performed by monitoring the surface pressure as a function of time. The Langmuir films of the lipids which were either pure or contained Ty were characterized bysurface pressure vs mean molecular area isotherms, and surface compression module. The deposition of LB films onto ITO substrates was performed at a surface pressure of 30 mN/m. The performance of the films as an active layer in biosensors was evaluated by cyclic voltammetry (CV) using catechol standard solution with concentrations of 1x10-3mol/L and 1x10-4mol/L. An increase in the mean molecular area was observed in the liquid and gaseous phases when comparing pure AA, DPPC and DPPG isotherms with isotherms containing Ty. This indicates that the enzyme is incorporated im the lipid membranes. DPPG showed the biggest difference in the extrapolated area. The surface compression module confirmed that the addition of Ty affects the mechanical properties of the films by decreasing the elasticity for both DPPC and DPPG monolayers. By comparing the CV results for plain ITO with ITO coated with DPPC and DPPC/Ty LB films it was observed that the enzyme has a electrocatalytic effect, as expected. CV results in catechol solution for DPPC/Ty films composed of 1, 3 and 5 LB layers indicated that the electrocatalytic effect is greater for the film with 3 LB layers. When evaluating the effect of the membrane mimetic matrix of AA, DDPG and DPPC on Ty immobilization and sensor performance it was found that the DPPG/Ty LB film produced the best electrocatalytic effect in relation to both the current intensity and the displacement of catechol redox couple for lower potential.

References [1] Villaverde, A. FEBES Letters, 554, 169-172 (2003).

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Poster abstracts

170

Preparations of superhydrophobic rubber surfaces

Riku Tamura1, Yuji Hirai1, Masatsugu Shimomura1, Yasutaka Matsuo2, Takahiro Okamatu3, Toshihiko Arita4

1Chitose Institute of Science and Technology, 758‐65 Bibi, Chitose Hokkaido 066‐8655, Japan

2RIES, Hokkaido University, Kita 20, Nishi 10, Kita‐ku, Sapporo 060‐8628, Japan 3R&D Center, The Yokohama Rubber Co. Ltd., Hiratsuka, Kanagawa 254‐8601, Japan

4IMRAM, Tohoku University, Katahira 2‐1‐1, Aoba‐ku, Sendai 980‐8577, Japan E-mail address: y‐[email protected]

There are a lot of functional surfaces in nature, for example, superhydrophobic surface of lotus leaves. Various artificial superhydrophobic surfaces have been reported, those have been built on brittle and breakable materials’ surface, so those are difficult to use in daily purposes[1,2]. In this study, we have focused on durable hydrophobic material of a vulcanized rubber, and attempted to prepare durable superhydrophobic rubber surfaces. An unvulcanized rubber sheet containing carbon black, sulfer, and so on, was placed on single crystalline silicon (Si) molds, which has hollow structures prepared by conventional photo‐lithographical technique (Figure 1). The sheet was heated at 80

C for 10 min then it was easily pressed into the small hollows.

After vulcanization at 160 C for 10 min, the surface structure of Si molds were transferred to the rubber sheet surface. Surface structures were observed by using field emission scanning electron microscope (FE‐SEM), and surface wettabilities were measured by using water contact angle (WCA) analyzer with 1 μL purified water. According to the surface observation by FE‐SEM, the rubber surface had fine arranged spiky structure, which are inverse structures of the Si mold hollow (Figure 2). WCA analysis revealed that the rubber surface still kept hydrophobicity after vulcanization, and flat vulcanized rubber surface showed WCA

of 104 (Figure 3 (a)). The spiky rubber surface showed

superhydrophobicity, and WCA was more than 158 (Figure 3 (b)). As the result, we suggest superhydrophobic rubber sheet can be obtained by simple molding process. References [1] H. Yabu, M. Takebayashi, M. Tanaka and M. Shimomura, Langmuir, 21 (3) 3236‐3237 (2005). [2] Y. Hirai, H. Yabu, Y. Matsuo, K. Ijiro, M. Shimomura, Jour. Mater. Chem., 20(48), 10804‐10808 (2010).

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Figure 1. (a) A photograph, (b) a laser microscope image, and (c) a laser microscope 3D image of the Si mold.

Figure 2. (a) A photograph, (b) a laser microscope image, and (c) a laser microscope 3D image of the microstructured spiky rubber surfaces.

Figre 3. Water contact angles of (a) a flat and (b) the microstructured rubber surface after vulcanization.

Poster abstracts

171

Internalization mechanism of micorparticles in HeLa cells

S. Yoshitake, R. Kondo, N. Kato

Graduate school of science and technology, Meiji University, Kawasaki 214-8571, Japan E-mail address: [email protected]

Drug delivery systems using drug carriers are of interest to improve the effectiveness and to reduce the side-effects of therapeutic drugs [1]. Studies of internalization of the carriers and particles into the cells have been extensively performed, and we have recently found that not only nanoparticles but also microparticles were internalized in HeLa cells. An endocytosis rout to uptake the microparticles should be macropinocytosis (MPC), because the size of macropinosome (MPS, 1 to 5 μm) is large enough to encapsulate the micron-sized particles. Herein, our aim is to clarify whether the 1-μm particles are internalized by the MPC. HeLa cells were cultured in the Eagle’s minimal essential medium (EMEM). To visualize the MPSs and to investigate the number of cells that internalized the particles, the medium was exchanged to the EMEM that contained rhodamine B-labelled dextran (RB-Dex, Mw 70,000) and the fluorescent 1-μm particles, the cells were incubated for 15 min, and the extracellular RB-Dex and particles were then removed by exchanging the medium [2]. To inhibit the MPC, the inhibiter, amiloride, was added to the EMEM and the cells were incubated for 30 min prior to the incubation in the medium containing the RB-Dex and the particles. The fluorescence images and the bright field images were obtained by laser scanning confocal microscope (FV1000MPE, Olympus). Fig. 1(a) indicates HeLa cells after the 15-min incubation without amiloride. Red and green colours correspond the fluorescence signals of RB-Dex and particles, respectively. In Fig. 1(a), there are one MPS (2 μm) and several particles internalized in HeLa cells and the fraction of the cell that internalized the particles (Fin) was 27.6 %. Almost all of the internalized particles were not encapsulated in the MPS and the particle in MPS was rare. Fig. 1(b) indicates the cells after the 15-min incubation with amiloride. The MPSs were not observed and the Fin was reduce to 15.0 %. These results indicates that HeLa cells internalized the 1-μm particles by MPC but the half of the particles were internalized by another route. The route by which the particles were internalized under the inhibition of MPC was also investigated. References [1] A. Prokop, J. M. Davidson, J. Pharm. Sci. 97, 3518 (2008). [2] J. Zaro, T. Rajapaksa, C. Okamoto, W. Shen, Mol. Pharm. 3, 182 (2005).

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Figure 1. Fluorescence images of RB-Dex (red) and

particles (green) are superposed on the bright

field image. (a) HeLa cells incubated for 15 min

with RB-Dex and particles. The yellow arrow

indicats the RB-Dex loaded macropinosome. (b)

HeLa cells incubated for 15 min with RB-Dex and

particles under the inhibition of macropinocytosis.

Poster abstracts

172

Living Cell Sensing Using Multi-Parametric Surface Plasmon Resonance in Drug

Development and Drug Research

T. Suutari1, T. Silén1, M. Hanzliková1, D.S. Karaman2, J. Rosenholm2, M. Yliperttula1, T. Viitala1 1University of Helsinki, Faculty of Pharmacy, Department of Pharmaceutical Biosciences, Centre for Drug Research, Viikinkaari 5E, 00014, Helsinki, Finland. 2Åbo Akademi Univeristy, Faculty of Science and Engineering, Pharmaceutical Sciences Laboratory, BioCity, Artillerigatan 6A, FI 20500 Turku, Finland. E-mail address: [email protected]

Nanoparticles (NPs) have been studied extensively as drug carriers, because they offer unique possibilities to improve intracellular delivery, efficacy and reduce toxicity of drugs and therapeutic biomacromolecules (e.g. proteins). The potency of a therapeutic product is often demonstrated by using in vitro cell cultures, tissue preparations, or whole animals. These methods are static and rely on labelled materials as well as on secondary detection techniques, while animal experiments are time consuming, expensive and ethically questionable. Hence, there is a clear need for developing new complementary in vitro tools in order to build a better mechanistic understanding of the quantitative structure-activity relationship of NP based drug delivery systems. The multi-parametric surface plasmon resonance (MP-SPR) technique in living cell sensing is a viable platform for novel real-time label-free cell based in vitro tool for pharmaceutical and life science research. Our approach utilizes cells attached on SPR sensor surface under a constant buffer/sample flow (Figure 1). MP-SPR provides a complete SPR spectrum in real-time, which allow the monitoring of several parameters upon cell response to stimulus. Surface modification of polyethyleneimine (PEI)-DNA polyplexes can influence the polyplex-cell interaction and cell uptake of the particles [1]. MP-SPR shows a clear difference in signal response with HeLa cells for surface modified and unmodified PEI-DNA polyplexes (Fig. 1). We have also recorded responses for silica nanoparticles, liposomes and small molecular drugs. This has enabled us to study the targeting efficacy, overall kinetic constant as well as the activation energy of the cell uptake process of NPs, as well as to separate between paracellular and transcellular drug absorption routes [2]. Our results collectively show that MP-SPR living cell sensing is a promising new in vitro tool for drug development and research purposes. It offers advantages over currently existing methods and could partially replace some of them in the future.

Figure 1. The experimental setup of cell based SPR is depicted on the left. The right image shows the SPR response to coated and uncoated PEI-DNA polyplexes with HeLa cells.

References [1] Y. Wang, Z. Xu, R. Zhang, W. Li, L. Yang, Q. Hu, Colloid Surface B 84, 259-266 (2011). [2] T. Viitala, N. Granqvist, S. Hallila, M. Raviña, M. Yliperttula, PLoS ONE 8, e72192 (2013).

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Poster abstracts

173

Biopolymer Layer-by-Layer films as substrate for mesenchymal stem cells adhesion

A.N. Kraskouski1, K.S. Hileuskaya1, V.I. Kulikouskaya1, S.V. Pinchuk2, I.B. Vasilevich2, V.E. Agabekov1, I.D. Volotovski2

1 Institute of Chemistry of New Materials of National Academy of Sciences of Belarus, 36 Skariny str.,

220141, Minsk, Belarus 2 Institute of Biophysics and Cell Engineering of National Academy of Sciences of Belarus, 27

Academicheskaya str., 220072, Minsk, Belarus


Mesenchymal stem cells (MSCs) possess multi-potential differentiation capacities and therefore they can be used in regenerative medicine for restoring damaged tissues. Creating a biocompatible scaffold providing high adhesion of MSCs without losing their functional properties will significantly improve the results of clinical applications of cell transplants based on bioengineering constructions [1, 2]. Multilayer ultrathin (<100 nm) polysaccharide containing films ((chitosan/pectin)n, (chitosan/dextran)n, (chitosan/carboxymethyl cellulose)n, (polyethylenimine/pectin)n, (polyethylenimine/dextran)n, (polyethylenimine/carboxymethyl cellulose)n) were obtained by using the Layer-by-Layer technique. These films were shown to be stable in phosphate buffer, sterilization solutions and culture medium: their integrity and homogeneity were preserved, and roughness varied slightly. It was also shown that the films containing chitosan exhibit more viscoelastic properties compared to films containing polyethylenimine. The MSCs adhere effectively to the multilayer viscoelastic films containing chitosan: (chitosan/pectin)4, (chitosan/dextran)4, (chitosan/pectin)4/chitosan, (chitosan/dextran)4/chitosan (Fig. 1b). MSCs form a monolayer culture of fibroblast-like cells with high viability (the amount of viable cells were ≥95%) on such substrates. MSCs adhere less on polyethylenimine containing films compared to chitosan containing films (Fig. 1c). MSC cultures on polyethylenimine containing substrates presented single viable cells with a large number of necrotic and apoptotic cells (about 70-80%).

Figure 1. Phase-contrast microscopy image of initial MSCs cultures (30 min after plating, a) and MSCs cultures on a surface of (chitosan/pectin)4/chitosan (b) and (polyethylenimine /pectin)4/ polyethylenimine (c) films after 3 days of cells culturing. Magnification is x200 (a) and x100 (b, c).

References [1] Zh.-M. Liu, Q. Gu, Zh.-K. Xu, Th. Groth, Macromolecular Bioscience 10, 1043-1054 (2010).

PP45

a b с

Poster abstracts

174

Fabrications of the durable wrinkle structures by embedding self-organized network structures

Yuji Hirai1, Takuya Ohzono2, Yasutaka Matsuo3, Masatsugu Shimomura1

1 Chitose Institute of Science and Technology, 758-65 Bibi, Chitose, Hokkaido 066-8655, Japan

2 Nanosystem Research Institute, Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan

3 Research Institute for Electronic Science, Hokkaido University, N20W10, Kita-Ward Sapporo 001-0020, Japan


Wrinkle structures have been exploited in a wide variety of applications, such as micropatterning1, tunable optics2, and so on. One of the characteristic properties of wrinkled surfaces is their shape-tunability in response to changes in the applied strain. However, the adhesion between elastic films and the substrate often cannot withstand the internal stress associated with the formation of wrinkles, leading to partial delamination known as buckling delamination. In this report, we show a fabrication of durable micro wrinkle structures by using self-organized honeycomb-patterned porous polymer films as embedded hard top layers. We prepared honeycomb-patterned porous polymer films with polystyrene by breath figure method (Figure 1(a)). After UV-O3 treatment, honeycomb-patterned films were fixed upside down to glass substrate with poly(vinyl alcohol) as adhesive. After peeling off the bottom layer of the films by an adhesive tape, the fixed top layer on the glass substrate was turned upside down in water, and put on a glass substrate (Figure 1(b)). Poly(dimethylsiloxane) (PDMS) precursor mixed with the catalyst was poured into the top layer, and cross-linked by heat treatment (80 oC, 3h). And then, the porous network structure embedded in the PDMS substrate was obtained. By applying in-plane strain, successfully micro wrinkle structures were formed repeatedly3 (Figure 1(c)). However, wrinkle periods were depended on periodicity of honeycomb-patterned films. To control the wrinkle period, aluminum was sputtered on the only top of honeycomb-patterned films before dividing into top and bottom layers. After that, same embedding processes were carried out. As a result, wrinkle structures were also formed (Fig. 1(d)), and wrinkle periods can be controlled by thickness of aluminum layers.

Figure 1. Scanning electron microscope images of (a) honeycomb-patterned films and (b) the top layer of the films (network structures). Laser microscope images of wrinkle structures (c) without and (d) with a metallic layer on the top of the network structures.

References [1] Ohzono, T. & Shimomura, Phys. Rev. B, 69, 132202 (2004). [2] Ohzono, T., Suzuki, K., Yamaguchi, T. & Fukuda, Advanced Optical Materials, 1, 374-380 (2013). [3] Ohzono, T., Hirai, Y., Suzuki, K., Shimomura, M. & Uchida, N., Soft Matter, 10, 7165-7169 (2014)

10#µm 8#µm 50#µm 50#µm

PP46

Poster abstracts

175

Preparation of moth eye structures by using self-organization

Yuta Segawa, Yuji Hirai, Masatsugu Shimomura Graduate School of Photonics and Science, Chitose Institute of Science and Technology 758‐65 Bibi, Chitose,

Hokkaido 066‐8655, Japan E-mail address: y‐[email protected]

In nature, there are many organisms which express the functions by various surface structures, and it is possible to produce new functional materials by mimicking these surface structures. For example, moth can fly at dark night and not discovered from other organisms, because moth eyes have two excellent structures and functions. The moth compound eye is composed of hexagonal lens arrays, which can collect the light in all directions. In addition, nanoscale spiky structures are formed on the moth compound eye surface. Because the reflactive index is gradually changed from air to nanoscale spiky surfaces, irradiated light can not reflect at the surface. However, there are no products, which mimic not only nanoscale spiky structures but also compound eye for anti‐reflection and light harvesting surfaces. In this study, we will show the preparations of the hierarchical microlens array(MLAs) structures that mimics the moth compound eye structures with nanospiky array structures by a self‐organized porous polymer film. Honeyconb‐patterned films and pincushion films, which are the template of MLAs were prepared[1]. Then, pincushion films were covered by PSt nanoparticle monolayers[2]. After that, MLAs were prepared by pincushion films as template of a sol‐gel method[3]. Finally, the top layer of MLAs was peeled off by using an adhesive tape. The sample surfaces were observed by using Field emission‐scanning electron microscope (FE‐SEM). FE‐SEM images of the sample surface of each process are shown in Figure 1. Honeycomb-patterned films have hexagonal close‐packed structure with pore size of about 5 μm(Figure 1, (a)). According to Figure 1 (c), it was confirmed to be spread PSt particle all over a MLAs surface. MLAs surface had pinhole of honeycomb. Finaliy, nanoscale spiky‐MLAs were successfully prepared by top layer separation of MLAs. We will measure optical property of transparency in future.

Figure 1. FE‐SEM images of (a) honeycomb‐patterned films, (b) pincushion films, (c) pincushion films covered with a PSt nanoparticle monolayer, (d) pore‐MLAs, and (e) nanoscale spiky‐MLAs.

References

[1] H. Yabu, M. Kojima, Y. Hirai and M. Shimomura, Chemistry of Materials, 21(9), 1787‐1789 (2009). [2] Y. Sawai, B. Takimoto, H. Nabika, K. Ajitoc and K. Murakoshi, Faraday Discuss., 132, 179-190 (2006). [3] Y. Murakami and Y. Kawabe, e‐J. Surf. Sci. Nanotech., 13, 51-53, (2015).

PP47

Poster abstracts

176

Quantum Chemical Studies of the Catalyst Effect on Naphthalene Condensation

M.V. Pozharov1, A.S. Chumakov2,3, Ammar J.K. Al-Alwani2,4, O. Shinkarenko2, E.G. Glukhovskoy3

1 National Research Saratov State University named after N.G. Chernyshevsky, Institute of Chemistry, Saratov, Astrakhanskaya 83, 410012, Russia

2 National Research Saratov State University named after N.G. Chernyshevsky, Faculty of Nano- and Biomedical technologies, Astrakhanskaya 83, Saratov 410012, Russia

3 National Research Saratov State University named after N.G. Chernyshevsky, Education and Research Institute of Nanostructures and Biosystems, Astrakhanskaya 83, Saratov 410012, Russia

4 Babylon University, Babylon, Iraq


Graphene and its derivatives are one of most promising and heavily studied nanomaterials possessing a wide range of physical and chemical characteristics leading to their application in photoelectronics [1], medicine [2], material science [3] etc. However, one of the common problems related to graphene is finding a cheap and reliable method of synthesis for it. One possible variant is catalytic condensation of aromatic polycyclic hydrocarbons such as naphthalene. Although these reactions are well-known and have been studied since the beginning of XXth сentury, quantum chemical computations of such processes have not been performed yet. Therefore, the aim of this study is to examine the effect of various catalysts (Pt, Pd, Ni, PdCl4 and AlCl3) on the path of reaction of naphthalene condensation in order to choose the most promising catalyst for future synthesis using quantum chemical methods. Both semi-empirical and DFT (density functional theory) methods have been considered. According to calculation results, Ni and Pd appear to be the most effective catalysts for the studied process. The research is supported by grant of the Russian Science Foundation (project №14-12-00275) and the National Research Saratov State University.

Figure 1. Scheme of the studied process (kat. = Pt, Pd, Ni, PdCl4, AlCl3)

References [1] L. Ma, H. Niu, J. Cai, P. Zhao, C. Wang, X. Bai, Y. Lian, W. Wang Carbon. 67, 488-499 (2014) [2] S. Mahanta, S. Paul Colloids and Surfaces B: Biointerfaces. 134, 178-187 (2015)

[3] Y. Cao, G. Li, X. Li Chemical Engineering Journal. 292, 207-223 (2016)

PP48

Poster abstracts

177

Producing perfect, ordered graphene from natural Finnish flake graphite

J. Palosaari1, S. Raunio1, J. Kauppila2, S. Lund3

1 Geology and mineralogy, Åbo Akademi University. Domkyrkotorget 1, 20500 Turku, Finland. 2 Laboratory of Physical Chemistry, Åbo Akademi University. Porthansgatan 3-5, 20500 Turku, Finland.

3 Laboratory of Analytical Chemistry, Åbo Akademi University. Biskopsgatan 8, 20500 Turku, Finland.


Graphene is a one-atom thick layer of graphite. The carbon atoms in graphene are connected by strong covalent bonds and by connecting millions of graphene layers by weak van der Waals –bonds they build up the mineral graphite (Fig. 1A) [1]. Graphite and graphene derive from sediments rich in organic matter in a process called graphitization. This transformation from organic matter to well-ordered graphite is irreversible and requires time and increasing temperature and pressure (For example, 5 kbar, 700°C and 1900 million years in Piippumäki, southern Savonia, Finland). The process starts with diagenesis of the initial material and is followed by metamorphism [2]. The project FennoFlakes is a consortium between Geology and Mineralogy, Physical Chemistry and Analytical Chemistry from Åbo Akademi University and the Geological Survey of Finland, started in 2015. The aim in this project is to create a functioning working plan to obtain exfoliated and usable flake graphite from the field to the laboratory. This is possible by careful geological fieldwork, sampling, analyses and characterization (SEM, XRD, Raman spectroscopy) of the graphite material (Fig. 1B). These initial steps are followed by selective fragmentation (selFrag) and production of a graphite concentrate by using shaking table and froth flotation. The goal is that the flake graphite concentrate is ready for utilization in different applications after the mineral processing.

Figure 1. High-quality flake graphite as seen in SEM from Piippumäki, southern Savonia, Finland (A). Raman spectra for the sample seen in Fig. 1A. The spectra indicate well-ordered and nearly defect-free flake graphite (B).

References [1] Hazen, R.M., Downs, R.T., Jones, A.P. & Kah, L., Reviews in Mineralogy & Geochemistry 75, pp. 7-46 (2013). [2] Buseck, P.R. & Beyssac, O., Elements 10, pp. 421-426 (2014).

PP49

A B

Poster abstracts

178

Properties and applications of graphene exfoliated from Finnish graphite ore

J. Kauppila1, S. Lund1,2, P. Ihalainen1, T. Lindfors2, O. Eklund3, J. Peltonen1

1 Åbo Akademi University, Laboratory of Physical Chemistry, Porthansgatan 3-5, FI-20500 Turku Finland 2 Åbo Akademi University, Laboratory of Analytical Chemistry, Biskopsgatan 8, FI-20500 Turku Finland

3 Åbo Akademi University, Geologi och mineralogy, Domkyrkotorget 1, FI-20500 Turku Finland


In our multi-level project, called FennoFlakes, the aim is to localize natural flake graphite sites, collect and refine graphite ore, and further to exfoliate the purified graphite into graphene. Finally the applicability of the refined graphene is studied. Here, results of graphene exfoliation and some preliminary applications are presented. For graphene preparation we used a high speed mixer to mechanically exfoliate graphene sheets from natural graphite in an aqueous solution. In the mechanical exfoliation graphene sheets are peeled off from graphite and made soluble using suitable surface-active molecules. The advantage of mechanical exfoliation over chemical methods is that the structure of the formed graphene sheets contains fewer defects. The produced graphene material was a few hundred nanometres in diameter and a few nanometres in thickness. With this method solutions with 1.0 mg/ml of few layer graphene could be made. There are many surface species to choose from for graphene stabilisation. Sodium cholate (SC), one of the bile acids, is an effective surfactant molecule for graphene.[1] Graphene/SC can be used for a variety of applications like preparing flexible conductors and electrodes, or to be used as a humidity sensor (Fig. 1).

Figure 1. A proof-of-concept -type humidity sensor made from graphene/SC on paper (left) and its response to humidity changes (middle). A flexible graphene conductor (right).

References [1] A. Viinikanoja, J. Kauppila, P. Damlin, E. Mäkilä, J. Leiro, T. Ääritalo, J. Lukkari, Carbon 68, 195-209 (2014).

PP50

Poster abstracts

179

Synthesis and characterization of ZnO / a-Si: H / Si as absorber window for visible

light

S. Sali1,2, S. Kermadi1,*, L. Zougar1, M. Boumaour1, M. Kechouane2, A. Keffous1, Y. Belkacem1

1CRTSE — Division DDCS, 02 Bd Dr. Frantz Fanon BP, 140, les 07 merveilles, 16038, Algiers, Algeria Tel./Fax.: +213 21 43 35 11 / +213 21 43 24 88

2Houari Boumediene University, faculty of physics, BP 32 El Alia Algiers, Algeria.


We investigated the structural; optical and electrical properties of silicon a-Si: H / Si heterojunction photodiodes using ZnO as the n-type semiconductor, with different ZnO Spray conditions were fabricated. The effects of substrate temperature condition on device performance were evaluated. The results show that the optimized substrate temperature as 480°C and 80 nm by measuring reflectance and sheet resistance of ZnO layer on a-Si:H / Si. A high transmittance (85%) and a large band gap (3,29 eV) are obtained using optimal ZnO condition of ZnO layer deposited on glass and a-Si:H/glass. Dark I-V curves and quantum efficiency of ZnO/ a-Si:H/Si structure showed large difference, which means there is a kind of barrier to current flow between ZnO and a-Si:H layer. Modified condition was applied and lower series resistance could be reached. The improvement is attributed to a higher number of generated carriers in the nanostructure (due to the lower surface reflectivity and a higher luminescence) that increases the probability of collisions.

Figure 1. Effet of substrate temperature of ZnO elaboration on Current-voltage characteristic of ZnO/a-Si:H/Si(100) heterojunction photodiode

References [1] U. Ozgur, Ya.I. Alikov, C. Liu, A. Teke, M.A. Reshchikov, S. Dogan, V. Avrutin, S.J. Cho, H. Morko, J. Appl. Phys, 98, 1 (2005). [2] B.Y. Oh, M.C. Jeong, W. Lee, J.M. Myoung, J. Cryst. Growth, 274, 453 (2005). [3] A. Nuruddin, J.R. Abelson, Thin Solid Films, 394, 48 (2001) [4] M.C. Carotta, A. Cervi, V. di Natale, S. Gherardi, A. Giberti, V. Guidi, Sensors and Actuators B: Chemical, 137, 164 (2009). [5] J.M. Szarko, J.K. Song, C.W. Blackledge, I. Swart, S.R. Leone, S. Li, Chem Phys Lett, 404, 171 (2005).

PP51

Poster abstracts

180

Crystalline analysis of poly-Si thin films with various sequences of deposits of Al

and a-Si: H obtained by AIC method.

F. Kezzoula1 *, H. Zegtouf2, M. Kechouane2, N. Kaddouri1, H. Menari1

1 CRTSE — Division DDCS, 02 Bd Dr. Frantz Fanon BP, 140, les 07 merveilles, 16038, Algiers, Algeria Tel./Fax.: +213 21 43 35 11 / +213 21 43 24 88

2 Houari Boumediene University, faculty of physics, BP 32 El Alia Algiers, Algeria.


The method of aluminum-induced crystallization (AIC) is being investigated for the preparation of poly-Si thin films for thin film transistors, solar cells and bio-applications [1-3]. The parameters for the crystallization of a-Si using the AIC method are Al/a-Si interface, annealing temperature, and thickness ratio of Al to a-Si. To study the influence of the oxide coating which is formed at the interface between Al and Si on the crystallization of the amorphous silicon thin film, we deposited a-Si: H by sputtering Dc according two structures Corning/Al/a-Si: H and Corning/a-Si: H/Al. After annealing at a temperature of 550°C for a variable times (1, 2, 3 and 4 hours), we noted from Raman measurements the crystallization of all the layers of a-Si: H as function the time. But the rates of Cristallisation for the layers a-Si: H directly deposited on the substrate is better. This crystallization was confirmed by measurements DRX and SEM.

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Figure 1. Raman spectra of the thin films of a-Si: H annealed at 550°C for different duration for tow structures: a) Corning/Al/a-Si: H, b) Corning/a-Si: H.

References [1] A. Straub, P. Widenborg, A. Sproul, Y. Huang, N. Harder, and A. Aberle, J. Cryst. Growth, 168, 265 (2004). [2] T. Voutsas, Thin Solid Films 515, 7406 (2007). [3] L. Pramatarova, E. Pecheva, P. Montgomery, D. Dimova-Malinovska, T. Petrov, A. Toth, and M. Dimitrova, J. Nanosci. Nanotechnol. 8, 924 (2008).

PP52

Poster abstracts

181

Heteroepitaxial growth of SiC films by carbonization of polyimide Langmuir-Blodgett films on Si

S.I. Goloudina1, V.V. Luchinin1, V.M. Pasyuta1, M.F.Panov1, A.N.Smirnov2, D.A.Kirilenko2, T.F.Semenova3,V.P. Sklizkova4, I.V. Gofman4, V.M. Svetlychnyi4,V.V. Kudryavtsev4

1 St. Petersburg State Electrotechnical University, 5 Prof. Popov st., 197376 St. Petersburg, Russia

2 Ioffe Institut, RAS, 26 Politekhnicheskaya, 194021 St Petersburg, Russia 3 St. Petersburg State University, 7-9 Universitetskaya nab., 199034 St. Petersburg, Russia

4 Institute of Macromolecular Compounds, 31 RAS, Bol’shoy pr., 199004 St.Petersburg, Russia


Among various semiconductor materials, silicon carbide (SiC) is an attractive material for high power, high frequency, and high temperature microelectronics, owing in part to its wide band gap, high thermal conductivity, high break down field, and high saturation velocity. The motivation for the hetero-epitaxial growth of SiC-on-Si has been to provide relatively inexpensive and large-area substrates of SiC for electronic devices and micro-electromechanical system. The usual techniques to grow SiC-on-Si are chemical vapor deposition (CVD), laser sputtering, and molecular beam epitaxy (MBE). For the first time a method for producing thin 3C-SiC films by using carbonization of a polyimide (PMDA-ODA) Langmuir-Blodgett (LB) film on silicon substrate was reported by B. Yang, et.al. [1]. In the present work polyimide films were obtained by the thermal imidization of LB films of polyimide precursor – alkylammonium salts of polyamic acid (PAAS). Rigid-chain polyamic acid and tert-amine as o,o',o''-trihexadecanoyltriethanolamine were used to prepare PAAS. Polyamic acid (BPDA/OTD) was produced on the base of dianhydride of 3,3',4,4'-biphenyltetracarboxylic acid and o-tolidine . The PAAS forms well-ordered and stable monolayers at the air-water interface that can be transferred by Y-type onto a silicon substrate [2]. To prepare SiC polyimide films was heated in vacuum (1×10-5 mbar) in three steps: 1) slow heat up to 1000˚C, 2) rapid heat up to 1100˚C, 3) rapid heat up to 1200˚C. The SiC films were studied by fourier transform-infrared spectroscopy, x-ray diffraction, Raman-spectroscopy, high-resolution transmission electron, and scanning electron microscopy, optical microscopy. Investigation of SiC films by x-ray diffraction revealed that a crystal of 3C-SiC(111) films was grown on Si(111) and the single crystal of 3C-SiC(100) films was grown on Si(100). The interesting details of formation of SiC on Si were found by Raman spectroscopy. It was shown that after heat treatment at 1000 ˚C the film on Si surface consist mainly of amorphous carbon. After annealing at 1100 ˚C the film contains both the carbon and SiC phases mainly the SiC phase was formed at 1200 ˚C. The cross-sectional HRTEM images of SiC film have shown that the SiC nanocrystals are formed on the SiC/Si interface. These nanocrystals are the nucleuses of microcrystals of SiC that appears on the film surface after annealing polyimide films at 1100 and 1200 ˚C. References

[1] B.Yang, Y.Zhou, W.Cai, et.al. Appl.Phys.Lett. 64(11), 1994, 1445- 1447. [2] S. Goloudina, V. Luchinin, V. Pasyuta, et.al.Crystallography Reports.54(3),2009, 468-476.

PP53

Poster abstracts

182

Carrier-inside-carrier: polyelectrolyte microcapsules as reservoir for drug-loaded liposomes

Ofelia Maniti1, Dave Diamond1, Samuel Rebaud1, Olivier Marcillat3, Thierry Granjon3, Loïc Blum1, Junbai Li2, Agnès Girard Egrot1

1 Univ Lyon, Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, ICBMS,

UMR CNRS 5246, GEMBAS and MEM2 team, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne, France 2 Key Lab of Colloid & Surface Science, CAS Institute of Chemistry, Zhong Guan Cun, Bei Yi Jie N°2, Beijing

100190, China E-mail address: [email protected]

Conventional liposomes have a short life-time in blood, unless they are protected by a polymer envelope, most often polyethylene glycol. However, these stabilizing polymers frequently interfere with cellular uptake, impede liposome-membrane fusion and inhibit escape of liposome content from endosomes. To overcome such drawbacks, polymer-based systems as carriers for liposomes are currently developed [1]. Conforming to this approach, we propose a new and convenient method of embedding small size liposomes, 30-100 nm, inside porous CaCO3 microparticles. These microparticles served as templates for deposition of various polyelectrolytes to form a protective shell (Figure 1). The carbonate particle was then dissolved to yield hollow polyelectrolyte microcapsules. The main advantage of using this method for liposome encapsulation is that carbonate particles can serve as a sacrificial template for deposition of virtually any polyelectrolyte. By carefully choosing the shell composition, bioavailability of the liposomes and of the encapsulated drug might be modulated to respond to biological requirements and to improve drug delivery to the cytoplasm and avoid endosomal escape.

Figure 1. Steps in liposome loading inside polyelectolyte microcapsules

Reference: [1] Ofelia Maniti, Samuel Rebaud, Joe Sarkis, Yi Jia, Jie Zhao, Olivier Marcillat, Thierry Granjon, Loïc Blum, Junbai Li, and Agnès Girard-Egrot, Journal of Liposome research 25(2), 122-130 (2015).

PP54

Poster abstracts

183

Hydrophobin film structure for HFBI and HFBII and possible mechanism for accelerated film formation

Aniket Magarkar1, Nawel Mele1, Noha Abdel-Rahman2, Sarah Butcher2, Mika Torkkeli3, Ritva Serimaa3, Arja Paananen4, Markus Linder4,5, Alex Bunker1

1 Division of Pharmaceutical Biosciences, Faculty of Pharmacy, University of Helsinki, Helsinki, Finland

2 Institute of Biotechnology, University of Helsinki, Helsinki, Finland 3 Department of Physics, University of Helsinki, Helsinki, Finland

4 VTT Technical Research Centre of Finland, Espoo, Finland 5 School of Chemical Technology, Aalto University, Espoo, Finland


Hydrophobin proteins, released by filamentous fungi, are the means through which they effect their environment in order to promote growth through interfaces. Additionally there are many industrial applications based on their effect on the air water interface. Their mechanism of action is to form a film at the interface that alters its properties in order to promote growth of mycelia through it. There are two classes of hydrophobins, delineated by the nature of the flim they create: class I hydrophobins form highly characteristic mesoscale structures, known as rodlets, while class II hydrophobins are amphiphilic and form 2D crystalline films at air water interfaces. Our study (1) involves a combination of protein docking, molecular dynamics simulation, and electron cryo-microscopy to determine the structure of films composed of two class II hydrophobins: HFBI and HFBII produced by Trichoderma reesei. Combined, our results indicate a unit cell composed of six proteins; however, our computational results suggest P6 symmetry, while our experimental results show P3 symmetry, in both cases with a unit cell size of 56 Å. Our computational results indicate the possibility of an alternate ordering with a three protein unit cell with P3 symmetry and a smaller unit cell size, and we have made use of a Monte Carlo simulation of a spin model representing the hydrophobin film to present a possible mechanism through which the alternate metastable structure may play a role in increasing the rate of surface coverage by hydrophobin films, possibly indicating a mechanism of more general significance to both biology and nanotechnology. References

[1] Aniket Magarkar, Nawel Mele, Noha Abdel-Rahman, Sarah Butcher, Mika Torkkeli, Ritva Serimaa, Arja Paananen,

Markus Linder, Alex Bunker, PLoS Comput. Biol. 10, e1003745 (2014)

PP55

Poster abstracts

184

Dynamic surface properties of mixed monolayers of particles and lipids

A.G. Bykov1, A.K. Panda2, B.A. Noskov 1

1 St. Petersburg State University, St. Petersburg, Russia 2 Vidyasagar University, Midnapore, India


Self-organization of mixed nanoparticle-phospholipid layers at liquid/fluid interfaces and the interactions of nanoparticles with cellular membranes are attracting increasing attention nowadays due to their relevance to the problems of ecological safety. For example, the surface segregation of nanoparticles modifies the behavior of lung surfactants [1]. In this work we investigated the surface properties of pure and mixed monolayers of charged polystyrene nanoparticles (PS) and dipalmitoylphosphatidylcholine (DPPC) at the air/water interface. The properties of the monolayers of PS particles with diameter of 20 nm strongly depend on the ionic strength of subphase. At relatively high ionic strength (0.1 M NaCl) the compression of the monolayer led to the increase of surface pressure up to 72 mN/m. At the same time, the dilational surface elasticity went through a maximum (500 mN/m) during compression. This behavior resembles the results for PS particles with diameter of 100 and 1000 nm [2, 3]. In the last case the surface rheological measurements together with the data of optical methods allow dividing the whole range of surface pressures into three zones characterized by different monolayer structures. During compression of the monolayer of PS nanoparticles with diameter 20 nm the surface pressure and surface elasticity did not exceed 35mN/m and 80mN/m, respectively, a low ionic strength of the subphase (0.01M NaCl). These strong discrepancies can be explained by the formation of two-dimensional aggregates. The properties of mixed monolayers depended also on the ionic strength of subphase. At the low ionic strength one could observe an inflection point of the surface compression isotherms at the surface pressure of 35 mN/m, which corresponded to the displacement of nanoparticles from the surface. However, some particles were preserved at the surface even after compression up to high surface pressures (60 - 70 mN/m). Moreover, the dynamic surface properties of DPPC monolayers changed significantly after the addition of PS nanoparticles. A minimum of the dependence of the dynamic surface elasticity on surface pressure for monolayers of DPPC disappeared in presence of nanoparticles. The particles hinder the ordering of lipid molecules and thereby the formation of solidlike surface phase. The dependencies of the surface elasticity on surface pressure for these systems agree qualitatively with the corresponding results for mixed monolayers of silica nanoparticles and lipids [1]. In agreement with these results we can assume that PS nanoparticles lead to the formation of a two-dimensional analogue of a Pickering emulsion. Acknowledgement The work was financially supported by the RFBR (No. 15-53-45043 ИНД_а and 16-33-00255 мол_а ) and St. Petersburg State University (project No. 12.38.241.2014)

References [1] E. Guzman, D. Orsi, L. Cristofolini, L. Liggieri, F. Ravera, Langmuir, 30, 11504-11512 (2014). [2] A.G. Bykov, B.A. Noskov, G. Loglio, V.V. Lyadinskaya, R. Miller, Soft Matter, 10, 6499-6505 (2014). [3] A.G. Bykov, G. Loglio, R. Miller, B.A. Noskov, Colloids and Surfaces A, 485, 42–48 (2015).

PP56

Poster abstracts

185

Titania nanostructures for osseointegration

A. Boucheham1,2, A. Karaali1, A. Manseri2, S. Kermadi2

1LTTSM,University of Frères Mentouri, Constantine1, Route de Ein el Bey, 25000 Constantine-Algeria 2Centre de Recherche en Technologie des Semi-conducteurs pour l’Energetique, 02 Bd Frantz Fanon, les 07

merveilles BP: 140, 16038 Algiers-Algeria


Nanostructured titania layers formed on the surface of titanium and titanium alloys by anodicand thermal oxidation play an important role for the enhancement of their biocompatibility and osseointegration in thehuman body [1-4]. The current workfocuses on the investigation oftwo different surface modificationsof Ti6Al4V substrates. Firstly,highly ordered titania nanotube array films were elaborated on Ti6Al4V medical grade alloys in organic electrolyte containing ethylene glycol, 0,2 wt. % NH4F and 4 vol. % H2O at different applied potentials in the range of 20-60V for a constant duration of 2,5 hours. The diameters, lengths and wall thicknesses of the obtained nanotubes were characterized by scanning electronic microscopy (SEM). The high diameter and length of respectively, 120 nm and 1,9 μm were foundon nanotubes elaborated at

60V as reported in Fig. 1. Secondly,thermaloxidation process was performed on Ti6Al4V alloy in temperature range of 500°C-800°C for duration of 4 hours in air. The morphology, roughness and phase composition of the formed layers were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). The wettability and tribological behaviour in dry friction werealsoevaluated.

Figure 1. SEM images of the top view of the nanotubes elaborated at 60V on the right and the morphology for sample oxidized at 800°C for 4hon the left.

References [1] John Grotberg, Azhang Hamlekhan, Arman Butt, Sweetu Patel, Dmitry Royhman, Tolou Shokuhfar, Cortino Sukotjo, Christos Takoudis, Mathew T. Mathew, Materials Science and Engineering: C 59, 677–689 (2016). [2] Lidia Benea, Eliza Mardare-Danaila, Marilena Mardare , Jean-Pierre Celis,Corrosion Science80, 331–338 (2014). [3]Balakrishnan Munirathinam, Haveela Pydimukkala, Narayanan Ramaswamy, Lakshman Neelakantan, Applied Surface Science 355, 1245–1253 (2015). [4] Song Wang, Yuhong Liu, Caixia Zhang, Zhenhua Liao, Weiqiang Liu, Tribology International 79, 174–182 (2014).

PP57

Poster abstracts

186

Conduction via LUMOof huge ring polyoxometalate

H. Kishimoto1, H. Yamaguchi1, D.-C.Che1, H. Ohoyama1, I. Nakamura2, R. Tsunashima2, T.Matsumoto1

1Osaka Univ. , , Toyonaka, Osaka 560-0043, Japan 2Yamagichi Univ., Tokiwadai, Yamaguchi, 755-8611, Japan


Polyoxometalate (POM) is a mixed-valence oxomolybdateanionic-cluster. POM is expected to act as the catalysis and a modified electrode material due to its high redox potential.[1]It has been reported that POM shows the semiconductive properties and negative differential resistance.In this work, I-Vcharacteristics for network structure of {Mo154/152}-ring, which is a donut shape of POM, are investigated in high vacuum condition in order to clarify the detail transport mechanism of POM. Network structure of POM is fabricated by air blow on SiO2substrate. The image of sample surfaces is measured by the atomic force microscope (AFM). AFM image shows the network-like structure with the height of 1.4 nm, which is in good agreement with the molecular size of POM. Therefore, we concluded that the observed network structure is formed by monomolecular layer of POM. I-V curvesfor network structures of POM were measured in high (10-5Pa) vacuum condition at a room temperature. It was found that thecurrent intensities and the curve shape vary with time, and thatthey are stable after 72 hours. Itsuggests that I-V curvesin earlier measurement may be reflected the character of POM influenced by ambient condition of sample.In order to clarify the conduction mechanism of POM, temperature dependence of I-V curves was measured the sample, which left after 72 hoursin vacuum. Fig. 1shows the temperature dependence of I-V curves. Observed results could be reproduced by the chargingenergy limited tunneling (CELT) model based on the electron transfer mechanism through the tunneling mechanism. From the analysis of CELT model, we calculatethe charging energy of POM network system, and it is estimated to be about 0.03 meV. Additionally, Ithas been reported that the energy level of LUMO for POM is lower than Fermi level of Au, which is used as the electrodes in this study. Therefore, we conclude that the electron transfer of tunneling may proceed through the LUMO level of POM. References [1] Achim MuÈller et al. Z. Anorg. Allg. Chem.1999,625, 1187-1192 [2] R. Parthasarathy et al., Phys. Rev. Lett., 2001, 87, 186807-1

PP68

Figure 1. Temperature dependence of I-V curves for POM.

PP58

Poster abstracts

187

Fabrication, characterization, optical and electrochemical properties of functionalized carbon nanotube@nanoSiO2 hybrid materials

Dong-Jin Qian, Wen-Li He, Jing Wang

Department of Chemistry, Fudan University, 220 Handan Road 200433, China


Organic-inorganic hybrid nano-materials have attracted growing attention due to their various applications

such as the development of novel optoelectronic nano-devices, sensors, and heterogeneous catalysts.

Here, we reported self-assembled hybrid materials on the functionalized carbon nanotubes (CNTs), silica

nanoparticles (nanoSiO2) and the CNT-nanoSiO2 composites, based on intermolecular electrostatic

interaction (Fig. 1), or on the coordination bonding with the use of transition metal ions as connectors and

porphyrin or viologen derivatives as linkers. The CNTs, nanoSiO2 and CNT-nanoSiO2 composites were firstly

covalent binding with multi-pyridyl compounds, such as poly(4-vinylpyridine) (P4VP), to form the P4VP-

functionalized hybrids, which were then used as a platform for assembling organic-inorganic hybrid

nanocomposites. After the composition, structure and morphology characterized, the optical,

electrochemical and catalytic properties of the materials as-prepared were investigated.

Figure 1. Schematic drawing for the preparation of phosphomolybdic acid-Viologen functionalized CNT-nanoSiO2

composites used as heterogeneous catalysts for bromate reduction.

PP59

Poster abstracts

188

Planar arrays of polymer nanoparticles as emitting layer in White-PHOLED

E. Benvenuti 1, G. Barile 2, G. Caminati3

1 CNR-ISMN, Via P. Gobetti, 101 Bologna, Italy 2 Sirio Panel SpA, Levanella I-52025 Montevarchi (AR), Italy

3 Department of Chemistry “Ugo Schiff”/CSGI, University of Florence, Via della Lastruccia 3-13, I-50019 Sesto Fiorentino (FI), Italy


Recent research on single color and white-light emitting organic devices revealed the leading role of nanofabrication on rigid and flexible surfaces. The aim of the present work is the design and the realization of novel phosphorescent nanomaterials where dopant molecules are organized in conducting polymer nanostructures. We assembled Phosphorescent Organic Light Emitting Devices (PhOLED) composed of poly(9-vinylcarbazole) (PVK) nanostructures doped with Iridium(III) complexes emitting in the red, green and blue region of the visible spectrum. We employed core–shell nanoparticles where a shell of PVK surrounds the surface of polypyrrole (PPy) nanoparticles (NPs) and compared the results with those obtained with single compartment PVK-NPs. The rationale for the construction of the proposed nanodevices is reported in figure 1 .

Figure 1. Spatial colocalization of single color (RGB) nanoparticles results in white emitting nano-domains

Successful doping of the PVK shell surrounding the PPY nanoparticles with Ir(III) complexes was obtained by the re-precipitation method as shown by a combination of different techniques such as particle sizing, AFM, SEM and photophysical characterization of the system. The results showed that the dimensions and morphology of the aggregates correlate with the structure and concentration of the specific Iridium complex used. The photophysical characterization of the PVK/Ir NPs demonstrated the occurrence of the desired energy transfer process between PVK and the Iridium complexes both in aqueous suspension and after deposition on solid supports. Steady-state and time resolved fluorescence spectroscopy evidenced that energy transfer from PVK to the selected Iridium complexes occur in all cases but with efficiencies that depend also on the concentration and geometry of the excimeric form of the fluorophore in the polymeric chain and thence on the polymer conformation. Co-localization of the different Ir complexes in the NP system was obtained with two different procedures: incorporation of a balanced mixture of the complexes in the same NP shell or construction of single color nanoparticles further combined and closely immobilized onto an ITO covered flexible sheet. Immobilization of the emitting nanoparticles in a single layer was obtained by spin-coating and, with higher coverage, drop-casting techniques. Confocal Laser Scanning Microscopy allowed for the collection of the emission fingerprint on selected domains of the NP shell and, more importantly, showed that light-excitation of these systems resulted in the production of light with colors that followed the expected additive synthesis rules in spatial-additting averaging.

PP60

Poster abstracts

189

Gradient formation in coordination-based molecular assemblies

Hodaya Keisar, Graham de Ruiter, Michal Lahav, and Milko E. van der Boom

The Weizmann Institute of Science, Department of Organic Chemistry, 76100 Rehovot, Israel


Organizing molecular components into well-defined 2D and 3D supramolecular assemblies allows one to construct various nanoscale structures in solution and on surfaces.[1,2] The composition of surface-confined multicomponent assemblies depends on different factors related to the dimensionality of the molecular precursors. In this study we report on a new approach to control the composition of multicomponent assemblies by varying the structure and the reactivity of the template monolayers. Our assemblies were formed stepwise from an equimolar mixture of osmium and ruthenium polypyridyl complexes on these template layers. A palladium salt was used to cross-link these metal complexes (Figure 1). We found that the composition of the assemblies is directly dependent on the structure of the template monolayer: a constant ratio between the polypyridyl complexes was achieved when the assemblies were generated on metal complexes, and Os:Ru ratios of 1:10 to 1:2 (after 8 deposition steps) were obtained when conjugated organic molecules were used as template monolayers. The increased Os:Ru ratio resulted in a vertical gradient along the growth direction of the assembly. These findings indicate the significance of the composition of the template layer when determining the molecular composition of supramolecular assemblies.

Figure 1. Formation of the multicomponent molecular assemblies

References [1] J. M. Lehn, Supramolecular Chemistry –concepts and perspectives, VCH, Weinheim, Germany (1995). [2] G. de Ruiter, M. Lahav, H. Keisar, M. E. van der Boom, Angew. Chem. Int. Ed., 52, 704-709 (2013).

PP61

Poster abstracts

190

Formation of extracellular matrix network and its potential medical application

Y. Kim1, S. Ahn1, S. Nam1, S. Lee1, H. Ko1, C. –J. Kim2, K. Shin1*

1 Department of Chemistry and Institute of Biological Interfaces, Sogang University, 35, Baekbeom-ro, Mapo-gu, Seoul 04107, Korea

2 Department of Physiology, College of Medicine, Kyung Hee University, 26, Kyungheedae-ro, Dongdaemun-gu, Seoul 02447, Korea


Spontaneous, highly ordered large-scale fibronectin networks driven by electrostatic polymer patterns are fabricated, and these precisely controlled protein connections are demonstrated. It is examined whether this scheme, universal to various fibrillar extracellular matrix proteins beyond fibronectin, collagen, and laminin, can be self-organized. These data reveal a novel bottom-up method to form anisotropic, free-standing protein networks to be used as flexible, transferrable substrates for cardiac and neuronal tissue engineering. We further demonstrated applications of these networks to template the formation of ECM composite fibers and cell patches, so-called “cell-patches”. Collectively, our results suggest that proteins that are endowed with β-sheet molecular domains and do not require external crosslinking to form insoluble fibers are capable of self-assembling into networks and that these precisely controlled connections provide a flexible, transferable substrate customized for tissue engineered cardiac and neuronal scaffolds. In this method, one of the most advantageous points is that one can use patient’s own cells to produce patient-specific patches, while minimizing severe inflammation. Therefore, we will present our recent application, applying self-healing patches for dermatological, and organ-specific application.

Figure 7. (1) Schematic of ECM network, (2) confocal image of FN network, (3) free-standing ECM network and (4) cardiac cellular patches grown on the network

[1] Seungkuk Ahn, Leila F. Deravi, Sung-Jin Park, Borna E. Dabiri, Joon-Seop Kim, Kevin Kit Parker and Kwanwoo Shin, Self-organizing Large-scale Extracellular Matrix Protein Networks, Advanced Materials 27 (18), 2838-2845 (2015) - selected as an front cover article

PP62

Poster abstracts

191

Synthesis of phospholipid biosurfactants from vegetable oils and evaluation of

interfacial properties for cosmetic and household products application

S.M. Lee1, J.Y. Lee1, B.J. Kim2, K.Y. Choi2, K.M. Lee2, J.C. Lim1

1Dept. of Chemical and Biochemical Eng., Dongguk Univ., 3-26 Phil-Dong, Seoul 100-715, Korea 2AK ChemTech Central Research Lab, DaeJeon 300-824, Korea

Email address: [email protected]

Recently, Interest in biosurfactants has been steadily increasing due to their diversity, environment friendly nature such as nontoxicity and excellent biodegradability, possibility of large-scale production, selectivity, performance under extreme conditions, and potential applications in environmental protection. In this study, phospholipid biosurfactants were synthesized from renewable vegetable oils such as sunflower oil, rapeseed oil, cottonseed oil, palm oil, and coconut oil for cosmetic and household products applications. The structure of the resulting products was elucidated by FT-IR, 1H NMR, and 13C NMR spectroscopies and environmental compatibility of the surfactants such as biodegradability and acute oral toxicity was also evaluated. The interfacial properties of synthesized surfactant have been examined such as critical micelle concentration (CMC), surface tension, interfacial tension, wetting property, emulsion stability, viscosity, and foam property. Since the newly synthesized biosurfactant is an amphoteric surfactant, it can serve as a dual function surfactant depending on pH variation of the aqueous solution. Zeta potential measurement has indicated that the new phospholipid biosurfactant showed not only detergency but also mildness effect since it showed characteristics of an anionic surfactant in an alkaline condition, while showing characteristics of a cationic surfactant in an acidic condition. Detergency test has shown that the newly synthesized biosurfactant provides moderately good detergency at a pH condition above its isoelectric point. On the other hand, softening effect evaluated by a touch test indicated that the new phospholipid biosurfactant shows relatively good softening effect at a pH condition below its isoelectric point. The prescription test in shampoo formulation prepared with the newly synthesized biosurfactants indicated better sensory feeling and excellent foaming ability compared with silicon. The patch test using the newly synthesized biosurfactants also indicated no irritation during 48 hours, indicating potential applicability in cosmetic and household products.

Figure 1. Synthetic route of phospholipid biosurfactant

Acknowledgement This work was supported by "the Technology Innovation Program“(10050496, Development of environment friendly biocompatible surfactants and their related products derived from natural resources derived) funded by the Ministry of Trade, Industry & Energy, Korea.

PP63

Poster abstracts

192

Corrosion processes of gold modified with phenothiazine based SAMs in aqueous

electrolytes

Julian Rechmann1, Alissa C. Götzinger2, Elena Dirksen2, Maciej Krzywiecki3, Thomas J. J. Müller2, and Andreas Erbe1,4

1Max-Plank-Institut für Eisenforschung GmbH, Max-Planck-Straße 1, 40237 Düsseldorf, Germany

2Heinrich-Heine-Universität Düsseldorf, Universitätsstraße 1, 40225 Düsseldorf, Germany 3Silesian University of Technology, Konarskiego 22B, 44-100 Gliwice, Poland

4NTNU, Norwegian University of Science and Technology, 7491 Trondheim, Norway

E-mail address: [email protected], [email protected]

Bottom-up techniques like self-assembly of organic molecules are highly efficient, economical and fast strategies to synthesize dense and well ordered organic layers. The high degree of surface coverage and its homogenity allows application in electronic appliances, such as organic light-emitting devices (OLEDs) and thin-film organic photovoltaic cells [1-2]. Furthermore, SAMs may assist in corrosion protection of metals [3]. Bare Au(111) surfaces were studied and used as model system to gain deeper insight in the mechanism of electron transfer. Linear sweep voltammetry (LSV) reveals different ongoing corrosion reactions of gold depending on the aqueous environment. Corrosion currents were analyzed and compared with modified gold surfaces with ethynyl phenyl phenothiazine and octadecanethiol. Ethynyl phenyl phenothiazine is a redox-active, fluorescent molecule, exhibiting strong p-type semiconducting character. Due to its large π-electron system, energy levels should couple with bands of metals/semiconductors. Modifying the energy alignment of frontier orbitals HOMO and LUMO, information about the correlation between corrosion current and energy gap can be extracted. Additionally, X-ray photoelectron spectroscopy (XPS) and photoelectron yield spectroscopy (PYS) give access to the band structure of the system metal/organic semiconductor.

Figure 8. Coupling a metal substrate with organic molecules of p-type semiconducting character should result in modification of electron transfer characteristics.

References [1] Vaeth, K. M., Inf. Display 19, 12-17 (2003). [2] Peumans, P.; Uchida, S.; Forrest, S. R., Nature 425, 158-162 (2003). [3] Rechmann, J.; Sarfraz, A.; Götzinger, A. C.; Dirksen, E.; Müller, T. J. J., Erbe, A., Langmuir 31, 7306-7316 (2015).

PP64

Poster abstracts

193

Molecular simulations of n-alkyl-poly(ethylene oxide) micelles

Maisa Vuorte1, Jukka Määttä1, Maria Sammalkorpi1


E-mail address: [email protected]; [email protected]

Non-ionic poly(ethylene oxide) (PEG) based surfactants have received significant attention both because of their relatively simple chemical structure and their biocompatibility. They are used as e.g. drug carriers, in solubilisation, and in molecular coatings. Block copolymer micelles are also considered excellent soft colloidal model systems for studying interparticle interactions and the formation of ordered structures in dilute and semi-dilute concentrations. We have systematically studied a series of amphiphilic n-alkyl-PEG CmEn micelles using coarse-grained molecular simulations. We map the effect of varying the PEG chain length and temperature on the resulting aggregation number and micellar structure. We probe the temperature response of the aggregates both in solutions consisting of molecules of single alkyl-PEG species but also mixtures of surfactants of two different PEG chain lengths. We find indications the alkyl-PEGs of differing PEG chain lengths phase separate at a critical temperature which depends on the PEG chain length mismatch. We compare the findings with existing scattering and other experimental data, as well as, scaling laws and discuss the conclusions that can be drawn from the molecular simulations. The work shows both the applicability but also the limitations of coarse-grained simulations models in representing phase behaviour of molecular aggregates. References [1] Jukka Määttä, Maisa Vuorte, and Maria Sammalkorpi, under preparation (2016).

PP65

Poster abstracts

194

Surface Tension Study of the p-Nitrophenol Monolayer

Parsons M.D.1, Partridge M.2, James S.W.2, and Frey J.G.1

1 Chemistry, University of Southampton, Southampton, SO17 1BJ

2 Engineering Photonics, Cranfield University, Cranfield, MK43 0AL E-mail address: [email protected]

p-Nitrophenol (PNP), has been used for many surface and interface studies. Its properties include lowering the surface tension of aqueous solution [1] and Surface Second Harmonic Generation at the air/water, organic/water and water/solid interfaces [2]. These properties imply the existence of a layer of PNP which forms at the interface by adsorption from solution. This work mechanically confirms the growth of a distinct PNP monolayer on the surface of water. The spontaneous formation from solution is demonstrated in Fig. 1a by the slow increase of surface pressure recorded by Wilhelmy plate in a small container (approximately 10 cm2 surface area) for a 15 mmol solution. The effect of concentration on the formation of the monolayer was investigated over a concentration range of 7.5-60 mmol with the same technique. A detailed study of a 15 mmol solution was also performed in a Nima Langmuir Blodgett trough and compression area isotherms of the monolayer were obtained at three points, T0, just after trough filling, T1, after 2.5 hours, and T3, after 3.5 hours, shown in Fig. 1b. Additionally, elasticity measurements were performed as described in [3] with the layer held at a surface pressure of 5 and 10 mN/m giving elasticity results of 16.39 and 38.06 mN/m respectively.

Figure 9.- a - Surface pressure graph showing formation of PNP monolayer from solution over time. b - Compression area isotherms of 15 mmol PNP in water. Isotherms shown for T0, T1 and T2, for times 0, 2.5 and 3.5 hours respectively.

References [1]Paluch M., Filek M, Journal of Colloid and Interface Science, 73, p 282-286 (1980) [2]K.B. Eisenthal,Chem. Rev., 96, 1343-1360 (1996) [3] Partridge M., Davis F., James S.W., Tatam R.P., Higson S.P.J., Fluid Dynamics Research, 46, 055503 (2014)

PP66

Poster abstracts

195

Advanced techniques to prepare a well-defined metal film on top of a self-assembled monolayer

M. Zharnikov



Self-assembled monolayers (SAMs) can be potentially used as ultrathin insulating dielectric layers or intermediate films in future electronic and spintronic devices. Whereas the bottom electrode in such assemblies is represented by the metal substrate, the top electrode should be prepared in controlled fashion at the SAM-ambient interface. Regretfully, the formation of a well-defined metal film on top of the SAMs is a non-trivial task, since the metal atoms deposited onto the SAM-ambient interface do not stay there, but penetrate into the monolayer and diffuse to the metal substrate following a strong thermodynamical drive. Here I discuss three new approaches to suppress the above penetration and diffusion, taken a representative and application-relevant ferromagnetic metal, nickel, as a test adsorbate. The first approach relies on irradiation-induced cross-linking of a thiol-substituted aromatic SAM. Whereas 2D-polymerization of such a SAM prevents penetration of the metal atoms into the monolayer, the thiol groups at the SAM-ambient interface serve as nucleation centers for the growing "top" metal film (see Figure 1a). The second approach, relying on SAMs of perfluoroterphenyl-substituted alkanethiols, utilizes a chemical reaction between the SAM constituents and adsorbate atoms. The primary process is the Ni mediated loss of fluorine atoms followed by extensive cross-linking between the partly defluorinated molecular backbones. The stability of these backbones and the rapid development of the cross-linking are the key components to hinder the metal penetration (see Figure 1b). Finally, the penetration of deposited metal atoms into a SAM can be nearly completely inhibited by preliminary formation of palladium-chloride seeding layer at the SAM-ambience interface. The palladium atoms in the seeding layer serve as nucleation centers for the growing metal film, staying at its bottom during the growth. In contrast, the chlorine atoms are transferred from palladium to the deposited metal, staying on the top of the growing metal film and serving as surfactants (see Figure 1c).

Figure 1. Schematic of the approaches to stabilize metal film at the SAM-ambient interface. (a) physical (irradiation-induced) cross-linking, (b) chemical (adsorbate-induced) cross-linking, and (c) Pd-Cl seeding layer.

PP67


Poster abstracts

196

Phosphonate-anchored molecular layers on Ti02 surfaces

P. Canepa1, I. Solano1, S. Uttyia1, G. Gemme2, R. Rolandi1, M. Canepa1, O. Cavalleri1

1 Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, Genova, Italy 2 INFN, Sezione di Genova, , Via Dodecaneso 33, Genova, Italy

E-mail address:[email protected]

Titanium dioxide films are currently the object of intense investigation because of their wide range of applications, from photocatalysis, to photovoltaics and biomaterial development. In view of biomaterial development a crucial topic to be investigated is the interaction of the TiO2 surface with organic and biological molecules. In particular surface functionalization able to improve the antimicrobial and osteointegration properties of the TiO2 surface is of large interest for the development of orthopedic implants. In this work, we studied the deposition on TiO2 of two kinds of molecules both bearing a phosphonate group as the anchoring head and either a non-fouling oligo-ethylene moiety or a carboxylic group (suitable for further coupling with antibacterial peptides) as the tail. Native oxide-covered polished Ti surfaces were used as substrates for the molecular deposition. Molecular deposition has been monitored by combining atomic force microscopy morphological characterization, X-ray photoemission spectroscopy elemental analysis and differential spectroscopic ellipsometry measurements.

PP68

Poster abstracts

197

Rich Interfacial Films formed from Aggregates in α-Cyclodextrin Solutions

Jorge Hernandez-Pascacio1, Ángel Piñeiro2, Juan M. Ruso2, Natalia Hassan2, José Campos-Terán3, Miguel Costas1 & Richard A. Campbell4

1 Facultad de Química, Universidad Nacional Autónoma de México, 04510 México.

2 Deptartment of Applied Physics, University of Santiago de Compostela, 15782 Spain. 3 Departamento de Procesos y Tecnología, Universidad Autónoma Metropolitana, 05348 México.

4 Institut Laue-Langevin, 71 avenue des Martyrs, Grenoble, 38042 France.


Cyclodextrins (CDs) are cyclic oligosaccharides formed by six (α), seven (β), or eight (γ) 1,4-linked α-D-glucopyranoside units. They are probably the first family of molecules that spring to mind when one looks to encapsulate small hydrophobic species [1]. CDs meet a number of characteristics that are not easy to bring together in a family of compounds, namely low toxicity, biocompatibility, chemical stability, and ease of synthesis and purification [2,3] Additionally, CDs are good targets for chemical modifications, which can enhance further their various attributes [4]. Nevertheless, the fundamental behavior of CDs in aqueous solutions and at interfaces is not fully understood. In the present work [5], the spontaneous aggregation of α-CD molecules in aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K and 298 K using a battery of 7 experimental techniques. We show that molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to form films at the water/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional organized domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface as well as temperature. The resulting film morphology is locked in a kinetically-trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in what might have seemed at first like a rather simple system.

Figure. (left) Dynamic light scattering data for fresh and aged α-CD solutions both at 283 and 298 K; (Right) Ellipsometry data showing the adsorption of aggregates under the same experimental conditions.

References [1] M. Messner, S. V. Kurkov, M. E. Brewster, P. Jansook & T. Loftsson, Int. J. Pharm. 407, 174 (2011). [2] K. Connors, Chem. Rev. 97, 1325 (1997). [3] J. Szejtli, Chem. Rev. 98, 1743 (1998). [4] R. Challa, A. Ahuja, J. Ali & R. K. Khar, AAPS PharmSciTech 6, E329–E357 (2005). [5] J. Hernandez-Pascacio, Á. Piñeiro, J. M. Ruso et al., Langmuir under review (2016).

PP69

Poster abstracts

198

Formation of extracellular matrix protein coated giant unilamellar vesicles and their physical properties

Sojeong Nam1, K. Y. Lee1,2, Serin Lee1, Hyojin Ko1, Chang–Ju Kim3, Kwanwoo Shin1*

1 Department of Chemistry and Institute of Biological Interfaces, Sogang University, 35, Baekbeom-ro, Mapo-gu, Seoul 04107, Korea

2 Department of Energy Science, Sungkyunkwan University, 2066, Seobu-ro, Jangan-gu, Suwon-si, Gyeonggi-do 16419, Korea

3 Department of Physiology, College of Medicine, Kyung Hee University, 26, Kyungheedae-ro, Dongdaemun-gu, Seoul 02447, Korea


Mimicking structural and functional “artificial cells” can open a new horizon in biophysics, since a cell is also considered to be the basic unit in many pathological processes. Current achievements of researches in mimicking cellular structures are including 1) assembling cellular membranes, composed of mainly phospholipids, and 2) determining the cytoplasmic skeletons, and it will provide a key information to produce, at least, physically (visoelastically controlled) and chemically (lipid based) controlled cellular vesicles when those structures are combined into a single structure. In this presentation, we will introduce a way to produce bio-mimetic lipid vesicle structures, aiming to create a complex cell-like boundary, reinforced by single or more protein fibrils from extracellular matrix proteins (collagen, fibronectin and laminin) to lipid unilamellar membranes in a single structure. We controlled the surface charge density of unilamellar lipid vesicles, and monitored the surface adsorption and network-formation of ECM proteins which are known to provide cellular functions and structures. Improved mechanical strength against osmotic pressures was carefully measured. In addition, we will detail how we can build up a simple lipid membranes to functionalized complex membrane, and by addition of extra-, intracellular proteins, we could build an artificial cellular structures, mimicking a living cellular structures, physically and functionally.

Figure 1. (left) Schematic of ECM-fibril combined lipid vesicles, (right) Confocal microscopic view of ECM-combined giant unilamellar vesicle

PP70

Poster abstracts

199

Vertical alignment of Au nanorods using DNA brush

Satoshi Nakamura1, Hideyuki Mitomo2, Yasutaka Matsuo2, Kenichi Niikura2, and Kuniharu Ijiro2

1Grad. Sch. of Chem. Sci. and Eng., Hokkaido Univ, Kita 13, Nishi 8, Kita-ku, Sapporo 060-8628, Japan 2RIES., Hokkaido Univ. 2, Kita 20, Nishi 10, Kita-ku, Sapporo 001-0020, Japan


<Introduction> Orientation control of anisotropic nanoparticles such as Au nanorod (AuNR) is an important topic for both fundamental and practical researches. In this study, we aim to demonstrate that DNA brush can be used for orientation control of anisotropic nanoparticles as template. DNA brush is a layer of DNA attached with one end to a surface. DNA chains stretch away from the substrate due to a steric repulsion and osmotic pressure. Therefore, DNA brush is anisotropic material. Owing to their anisotropy, it is expected that DNA brushes enable AuNR to align on a substrate (Figure 1). <Experiment> Linear double stranded (ds) DNA of 148 bp were synthesized by a standard PCR procedure using λDNA as a template and a pair of 5’ modified primers, one attached to biotin and the other to a fluorescent marker (Alexa Fluor 647). Linear dsDNA modified with biotin was immobilized on a glass curvette coated with streptavidin. DNA inter-chain distance was evaluated from fluorescent intensity of the DNA brush. AuNR (34 nm×10 nm) were synthesized following the previous report and modified with two kinds of alkanethiol, one has primary amine and the other has hydroxyl group as a terminal functional group (described as NH2E6C11 and E6C11). To investigate the orientation of AuNR on the DNA brush, extinction spectra of AuNR on the DNA brush were measured. <Results and discussions> AuNR has two modes of locarlized surface plasmon resonance (LSPR) corresponding to a transverse LSPR (TLSPR) and a longitudinal LSPR (LLSPR). These LSPR can be used for the evaluation of orientaion of AuNR. First, we investegated the effect of the intensity of electrostatic interaction between AuNR and the DNA brush, the inter-chain distance of which was 34 nm, on the orientaion of AuNR. Figure 2 shows the normalized extinction spectra of AuNR immobilized on the DNA brush when the mixed ratios of NH2E6C11 and E6C11 were changed. As the intensity of electrostatic interaction decreased, the intensity of TLSPR, which is located around 520 nm, increased slightly and the intensity of LLSPR, which is located around 800 nm, decreased drastically. These results suggest that AuNR gradually stands against to the substrate as electrostatic interaction becomes weaker. Secondly, the effect of the DNA inter-chain distance was investigated. The normalized extinction spectra of AuNRs immobilized on the DNA brush, DNA inter-chain distance of which varied from 34 nm to 113 nm, were totally different. As the DNA inter-chain distance became narrow, the intensity of TLSPR increased slightly and that of LLSPR decreased drastically. This result suggests that AuNRs gradually stand against to a substrate as the density of the DNA brush increase. Thus we concluded that DNA brush can be applied for orientaion control of AuNR as a useful template.

PP71

Poster abstracts

200

1,2-Epoxyalkane: Another precursor molecules for self-assembled

monolayers on hydrogen terminated Si(111)

T. Utsunomiya, A. I. A. Soliman, S. Kokufu, T. Ichii, H. Sugimura

Department of Materials Science and Engineering, Graduate School of Engineering, Kyoto University, Yoshida-hommachi, Sakyo-ku, Kyoto 606-8501, Japan


Nowadays, self-assembled monolayers (SAMs) that covalently bonded to silicon (Si) substrates formed through a chemical reaction of hydrogen-terminated Si (H-Si) with organic molecules have attracted a great attention, since these SAMs are thermally, chemically and mechanically stable. Several reports have discussed the immobilization of different precursors on the H-Si substrate, such as 1-alkene, and 1-alkanol. Recently, the monolayer formation through the reaction of the scribed (bare) Si surface with alkyl epoxides were reported [1]. However, the reactivity of alkyl epoxides with the passivated H-Si surface has not been reported. SAM formation through a reaction between the reactive oxirane moieties on the well-defined H-Si could offer a new way to design the silicon semiconductor devices. In this report, we have immobilized 1,2-epoxydodecane (EDD) on hydrogen terminated silicon (H-Si) substrates by UV photochemical grafting [2]. Figure 1a shows the schematic illustration of the SAM formation and water contact angle results of each sample. The water contact angle, 106.3°, shows the highly-dense methyl-termination at the surface. As revealed by X-ray photoelectron spectroscopy, the atomic composition of carbon shows the grafting of alkyl chain on the surface. The thickness of the film is ca. 2 nm, which is comparable to the length of the precursor molecule. Figure 1c shows the AFM topography of the EDD treated sample after UV photochemical grafting. The step-terrace structure, which is in good agreement with the HSi(111) surface (Figure 1b), indicates that the molecular film is homogeneously formed on H-Si terraces with atomically scale precision. These precise SAM formation shows that the epoxy-moieties react with the H-Si(111) surface through UV photochemical grafting. Therefore, alkyl epoxides can be another precursor molecules for functionalizing the H-Si surface.

Figure 1. (a) Schematic illustration of the SAM formation, and water contact angles of the samples. AFM topographic images of (b) H-Si substrate, and (c) EDD treated sample after UV irradiation.

References [1] Y. Lua, M. V. Lee, W. J. J. Fillmore, R. Matheson, A. Sathyapalan, M. C. Asplund, S. A. Fleming, M. R. Linford, Angew. Chem. Int. Ed., Amine-Reactive Monolayers on Scribed Silicon with Controlled Levels of Functionality: Reaction of a Bare Silicon Surface with Mono- and Diepoxides, 42, 4046 (2003). [2] A. I. A. Soliman, S. Kokufu, T. Utsunomiya, T. Ichii, H. Sugimura, Chem. Lett., Photochemical Preparation of Alkoxy Self-Assembled Monolayers on Si from 1,2-Epoxyalkane Molecules, in press (2016).

PP72

Poster abstracts

201

Mesoporous silica hollow capsules embedded with magnetic nanoparticles

S. Yoshikawa, N. Kato,* G. Obara

Graduate School of Science and Technology, Meiji University, Kawasaki 214-8571, Japan E-mail address: [email protected]

Mesoporous silica hollow capsules (MSHCs) are one of the candidates of drug carriers in a drug delivery system (DDS), and we had proposed the synthesis methods to obtained monodispersed MSHCs with uniform shell thickness [1,2]. Recently, the functionalized MSHCs such as magnetic MSHCs (MMSHCs) [3-5] are of interest to develop advanced DDSs. Here, we aim to obtain MMSHCs, whose shells contain magnetic nanoparticles (NPs), using our synthesis method. The PEGylation of the capsule surface was also performed. The magnetite NPs were prepared based on the reported method [6]. Their diameters were ranged from 5 to 15 nm, the magnetite structure was confirmed by XRD, and their magnetization saturation value was 62.55 emu/g. The preparation process is illustrated in Figure 1(a). The polystyrene (PS) particle (202 nm in diameter) as the core template was coated by polyethyleneimine (PEI) and the citrate-stabilized magnetite NPs were adsorbed on the PEI-coated PS particles. The co-condensation of cetyltrimethylammonium bromide (CTAB) and tetraethoxysiliane (TEOS) were then made on the coated PS particles by the sol-gel reaction, followed by calcination to remove the PS core and CTAB molecules. The surfaces of the obtained MMSHCs were made hydrophobic (Figure 1(b)) using hexamethyldisilazane (HMDS) and the MMSHCs were then redispersed in the aqueous solution of the amphiphilic triblock copolymer (Pluronic, F127). Because F127 consists of two PEG blocks and one polypropylene oxide block between the two PEG blocks, F127 adsorbed on the hydrophobic surfaces of MMSHCs the via hydrophobic interaction, resulting in the PEGylated surfaces. Figure 1(c) shows a photograph of the PEGylated MMSHCs trapped by a magnet.

Figure 1. (a)Preparation process of mesoporous silica hollow capsules embedded with magnetite nanopaericles. (b) Transmission electron microscope image of hydrophobic MMSHC. (c) Photograph of the PEGylated MMSHCs trapped by a magnet.

References [1] N. Kato, T. Ishii, S. Koumoto, Langmuir 26, 14334 (2010). [2] N. Kato, N. Kato, Micropor. Mesopor. Mat. 219, 230 (2016). [3] J. Liu, Y. Deng , C. Liu, Z. Sun, D. Zhao, J. Colloid Interf. Sci. 333, 329 (2009). [4]Z. Huang, F. Tang, J. Colloid Interf. Sci. 281, 432 (2005). [5] F. Wang, Y. Tang, B. Zhang, B. Chen, Y. Wang, J. Colloid Interf. Sci. 386, 129 (2012). [6] Y. Deng, W. Yang, C. Wang, S. Fu, Adv. Mater. 15, 1729 (2003).

PP73

Poster abstracts

202

Single molecule force spectroscopy study on polymer-nanoparticle interactions

Zhandong Li, Wenke Zhang*

State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130012 E-mail address: [email protected]

The study of polymer-nanoparticle interactions is very important for both material and biological sciences.

Polymer nanocomposites, widely known for their enhanced mechanical property, have taken essential

parts in numerous fields and become indispensable in the development of material science[1]. In addition,

the investigation of polymer-nanoparticle interactions will also facilitate the design of quantum dots for

efficient biolabelling[2]. Atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS)

has been proved to be an useful method for the study of intra- and intermolecular interactions at single

molecule level[3],[4]. In this study, an AFM-based method has been established for quantifying the

interactions between a positively charged polymer, poly-l-lysine (PLL), and negatively charged

polyoxometalates (POMs), as shown in Figure 1. By comparing the change of force spectra of PLL in the

absence and presence of POMs, both the binding mode and strength have been obtained. The effects of

particle sizes, charge numbers as well as the shapes of POMs on the PLL-POMs interactions were studied

systematically. Our results show that the particle shape has greatly influenced the binding strength

between PLL and POMs particles. However, charge numbers are not crucial for the binding strength

indicated. In addition, the dynamic assembly and disassembly process of POMs on the PLL chain have been

investigated in situ.

Figure 1. The study of PLL-POMs interactions using AFM-based single molecule force spectroscopy

References [1] Manias, E.; Touny, A.; Wu, L.; Strawhecker, K.; Lu, B.; Chung, T. C. Chemistry of Materials 13, 3516(2001). [2] Selvan, S. T.; Patra, P. K.; Ang, C. Y.; Ying, J. Y. Angewandte Chemie-International Edition, 46, 2448(2007). [3] Liu, K.; Song, Y.; Feng, W.; Liu, N.; Zhang, W.; Zhang, X. Journal of the American Chemical Society 133, 3226(2011). [4] Xue, Y.; Li, X.; Li, H.; Zhang, W. Nature Communications 5(2014).

PP74


Author list

203

Author list

Author list

204

Author list

205

Surname Initials University / Institution Country Presentation

Abdelkader H. Åbo Akademi University Finland PP26

Abdel-Rahman N. University of Helsinki Finland PP55

Agabekov V.E. National Academy of Sciences of Belarus

Belarus OP32, PP19, PP22, PP45

Ahn S. Sogang University Korea PP62

Al-Alwani Ammar J.K. Babylon University / National Research Saratov State University

Iraq/Russia PP3, PP48

Alessio P. Univ Estadual Paulista Brazil PP29, PP41

Allain C. PPSM France OP9

Ang J.C. Australian National University Australia PP18

Antila H.S. Aalto University Finland OP30

Araghi H.Y. University of Saskatchewan Canada OP13

Araki K. Osaka University Japan OP17

Arita T. Tohoku University Japan PP42

Aslan S. Yale University USA OP67

Assis D.R. UNESP Brazil PP13

Aubert N. Synchrotron SOLEIL France PP17

Badia A. Université de Montréal Canada IL4

Baglioni P. University of Florence Italy OP44

Banchelli M. CNR Italy OP71

Barattin M. University of Padova Italy PP25

Bardin L. Synchrotron SOLEIL/Université Pierre et Marie Curie

France OP15

Barile G. Sirio Panel SpA Italy PP60

Batys P. Aalto University/Polish Academy of Sciences

Finland/Poland PP27, PP30

Becker J.-M. University Jean Monnet France PP15

Belkacem Y. Houari Boumediene University

Algeria PP51

Benvenuti E. CNR-ISMN Italy PP60

Berthelot K. University of Bordeaux France OP6

Berthod L. University Jean Monnet France OP1

Bettini S. University of Salento Italy OP45, OP60

Bilewicz R. University of Warsaw Poland IL3, OP18

Bisso S. University of Helsinki/University of Padova

Finland/Italy PP34

Blanco Y. Universidad de Valladolid Spain PP28

Blobner F. Technische Universität München

Germany OP64

Author list

206

Blum L. Université Lyon 1 France PP54

Bolte M. University of Frankfurt Germany OP64

Bonatout N. LICORNE/UMR France OP25, OP68, PP12

Bonfils F. University of Montpellier 2 France OP6

Bonfrate V. University of Salento Italy OP45

Bottier C. Kasetsart University Thailand OP6

Boucheham A. University of Frères Mentouri/Centre de Recherche en Technologie des Semi-conducteurs pour l’Energetique

Algeria PP57

Boumaour M. Houari Boumediene University

Algeria PP51

Bowers C.M. Harvard University USA OP54

Brazzale C. University of Padova Italy PP34

Breiten B. Harvard University USA OP54

Brezesinski G. Max Planck Institute of Colloids and Interfaces

Germany OP4, OP12, OP23, OP46, PP10

Briand E. INSP France PP21

Bruchiel-Spanier N. The Hebrew University of Jerusalem

Israel IL2

Buck M. University of St Andrews UK IL12

Bunker A. University of Helsinki Finland OP41, PP55

Butcher S. University of Helsinki Finland PP55

Butt H.-J. Max Planck Institute for Polymer Research

Germany OP5

Buzin A.I. Russian Academy of Sciences Russia OP12, PP24

Bykov A.G. St. Petersburg State University Russia PP56

Camacho L. University of Cordoba Spain OP26

Caminati G. University of Florence Italy OP44, OP71, PP60

Campbell R.A. Institut Laue-Langevin France OP29, PP18, PP69

Campos-Terán J. Universidad Autónoma Metropolitana

México PP69

Canepa M. Università di Genova Italy OP58, PP68

Canepa P. Università di Genova Italy PP68

Casalis L. Sincrotrone Trieste SCpA Italy OP58

Caseli L. Federal University of São Paulo

Brazil IL1

Castano S. University of Bordeaux France OP6

Author list

207

Castronovo M. Sincrotrone Trieste SCpA Italy OP58

Cavalleri O. Università di Genova Italy OP58, PP68

Cebim M.A. Universidade Estadual Paulista Brazil OP7

Chadli M. Université Lyon 1 France OP49

Charrière R. University Jean Monnet France PP15

Che D.-C. Osaka University Japan OP17, OP66, PP31, PP58

Cheng A. Kyoto University Japan OP53

Cheng F. Åbo Akademi University Finland PP26

Choi K.Y. AK ChemTech Central Research Lab

Korea PP63

Chumakov A.S. National Research Saratov State University named after N.G. Chernyshevsky

Russia OP26, PP3, PP48

Chvalun S.N. Russian Academy of Sciences/National Research Centre “Kurchatov Institute”

Russia OP12

Ciatto G. Synchrotron SOLEIL France PP17

Cohen-Bouhacina T. Univ. de Bordeaux France OP47

Corn R. University of California-Irvine USA PP38

Cortes S. Synthelis France OP49

Costas M. University of Santiago de Compostela

Spain PP69

Cyganik P. Jagiellonian University Poland OP52, OP54, OP64

da Silva Martin B. Univ Estadual Paulista Brazil PP41

Davis F. University of Chichester UK OP70

Davolos M.R. Universidade Estadual Paulista Brazil OP7, PP4, PP13

de Ruiter G. The Weizmann Institute of Science

Israel PP61

Dellea O. French Alternative Energies and Atomic Energy Commission (CEA)/LITEN

France OP1, OP73, PP15

Deravi L.F. University of New Hampshire USA OP33

DeWolf C. Concordia University Canada OP24

Diamond D. Université Lyon 1 France PP54

Dionne E.R. Université de Montréal Canada IL4

Dirksen E. Heinrich-Heine-Universität Düsseldorf

Germany PP64

Dubatouka K.I. NAS of Belarus Belarus PP19

Author list

208

Ducros C. French Alternative Energies and Atomic Energy Commission (CEA)

France OP1

Dunderdale G.J. National Institute of Advanced Industrial Science and Technology

Japan OP43

Dutton S. Sheffield Hallam University UK OP70

Eklund O. Åbo Akademi University Finland PP50

England M.W. National Institute of Advanced Industrial Science and Technology

Japan OP43

Erbe A. Max-Plank-Institut für Eisenforschung GmbH/Norwegian University of Science and Technology

Germany/Norway PP64

Eriksson J. Åbo Akademi University Finland PP26

Etoh R. Osaka University Japan OP66

Fan C. Chinese Academy of Sciences China PL3

Fauré M.-C. Université Pierre et Marie Curie/Université Paris Descartes

France OP9. OP15, OP57

Feulner P. Technische Universität München

Germany OP64

Filipe E. Universidade Tecnica de Lisboa

Portugal PO15, OP25

Fontaine P. Synchrotron SOLEIL France OP15, OP25, OP57, OP68, PP12, PP17

Fragneto G. Institut Laue – Langevin France OP48

Francius G. Université de Lorraine France OP51

Freudenthal O. Université de Lorraine France OP51

Frey J.G. University of Southampton UK PP66

Fugier P. French Alternative Energies and Atomic Energy Commission (CEA)/LITEN

France OP1, OP73

Fujimori A. Saitama University Japan OP3

Fung M. University of California-Irvine USA PP38

Galewski Z. University of Wroclaw Poland OP8

Gammoudi I. Univ. de Bordeaux France OP47

García Pérez A. University of Helsinki Finland IL8

García-Cabezón C. Universidad de Valladolid Spain PP28

García-Hernandez C. Universidad de Valladolid Spain PP28

Gascon I. Universidad de Zaragoza Spain PP12

Author list

209

Gemme G. INFN Italy PP68

Gerelli Y. Institut Laue – Langevin France OP48

Giancane G. University of Salento Italy OP45, OP60

Giménez R. Universidad de Zaragoza Spain PP12

Giner-Casares J.J. University of Cordoba Spain OP26

Girard Egrot A. Université Lyon 1 France OP49, PP54

Glukhovskoy E.G. National Research Saratov State University named after N.G. Chernyshevsky

Russia OP4, OP26, PP3, PP48

Gnatek D. Jagiellonian University Poland OP64

Gofman I.V. Institute of Macromolecular Compounds

Russia PP53

Goldmann M. Université Pierre et Marie Curie/Université Paris Descartes/Synchrotron SOLEIL

France OP9, OP15, OP25, OP57, OP68, PP12, PP17

Goloudina S.I. St. Petersburg State Electrotechnical University

Russia PP53

Gorbachev I. National Research Saratov State University

Russia OP4

Gorbatsevitch O.B. Russian Academy of Sciences Russia PP24

Gorczyca M. Jagiellonian University Poland OP51, PP1

Granjon T. Université Lyon 1 France PP54

Granqvist N. BioNavis Ltd Finland OP61

Grauby-Heywang C. Univ. de Bordeaux France OP47

Grundström K. Kimmy Photonics Finland IL8

Guenoun P. LIONS/CEA-CNRS France IL5

Götzinger A.C. Heinrich-Heine-Universität Düsseldorf

Germany PP64

Hæggström E. University of Helsinki Finland IL8

Hakola H. Tampere University of Technology

Finland PP35

Haley D.A. University of Calgary Canada PP33

Han C. China University of Petroleum China OP56

Hanzliková M. University of Helsinki Finland PP44

Hasegawa H. Hokkaido University Japan OP11

Hassan N. University of Santiago de Compostela

Spain PP69

He W.-L. Fudan University China PP59

Hébert M. University Jean Monnet France PP15

Hernandez-Pascacio J. Universidad Nacional Autónoma de México

México PP69

Author list

210

Hertmanowski R.A. Poznan University of Technology

Poland OP10

Herzog A. Freie Universität Berlin Germany PP40

Higson S.P.I. University of Chichester UK OP70

Hileuskaya K.S. National Academy of Sciences of Belarus

Belarus PP22, PP45

Hirai Y. Chitose Institute of Science and Technology

Japan PP37, PP39, PP42, PP46, PP47

Hiroyuki K. Osaka University Japan OP17

Hitrik M. The Hebrew University of Jerusalem

Israel IL2

Holopainen J.M. University of Helsinki and Helsinki University Hospital

Finland OP38

Horie K. Hokkaido University Japan OP59

Hozumi A. National Institute of Advanced Industrial Science and Technology

Japan OP43

Huang J. Northwestern University/Donghua University

USA/China OP2, PP7

Ichii T. Kyoto University Japan OP53, OP69, PP72

Ihalainen P. Åbo Akademi University Finland PP26, PP50

Ijiro K. Hokkaido University Japan OP37, OP59, PP71

Imahori H. Kyoto University Japan PL2

Imura Y. Tokyo University of Science Japan OP7

Iwamoto M. Tokyo Institute of Technology Japan IL7

Ivanov G.R. University of Architecture, Civil Engineering and Geodesy

Bulgaria OP16

Iyo N. Hokkaido University Japan OP37

Izawa H. Tottori University Japan OP36

Jablonowska E. University of Warsaw Poland IL3

Jafelicci Jr M. UNESP Brazil PP13

James S.W. Cranfield University UK PP66

Jang J. Seoul National University Korea OP33

Janikowska M. Jagiellonian University Poland PP9, PP20

Jarva H. University of Helsinki Finland PP25

Javanainen M. University of Helsinki Finland OP38

Jokinen A. BioNavis Ltd Finland OP61

Jourlin Y. University Jean Monnet France OP1, OP73

Juhaniewicz J. University of Warsaw Poland OP20

Author list

211

Jungwirth P. Academy of Sciences of the Czech Republic/Tampere University of Technology

Czech Republic/Finland OP41

Kaddouri N. CRTSE Algeria PP52

Kamimura Y. Meiji University Japan PP32

Kang C. Sookmyung Women’s University

Korea OP33

Kankaanpää P. Åbo Akademi University Finland PP26

Kappl M. Max Planck Institute for Polymer Research

Germany OP5

Karaali A. University of Frères Mentouri Algeria PP57

Kari O.K. University of Helsinki Finland PP25

Karppinen M. Aalto University Finland PL4

Kartal-Hodzic A. University of Helsinki Finland PP34

Karthaus O. Chitose Institute of Science and Technology

Japan PP40

Kassamakov I. University of Helsinki Finland IL8

Kato R. Nagasaki International University

Japan OP14

Kato N. Meiji University Japan PP14, PP32, PP43, PP73

Kauppila J. Åbo Akademi University Finland PP49, PP50

Kawai T. Tokyo University of Science Japan OP72, PP5

Kazakova V.V. Russian Academy of Sciences Russia PP24

Kechouane M. Houari Boumediene University

Algeria PP51, PP52

Keffous A. Houari Boumediene University

Algeria PP51

Keisar H. The Weizmann Institute of Science

Israel OP28, PP61

Keresztes Zs. Hungarian Academy of Sciences

Hungary OP22

Kermadi S. Houari Boumediene University

Algeria PP51, PP57

Kezzoula F. Houari Boumediene University

Algeria PP52

Khan M. Heidelberg University Germany OP27

Khatri O.P. Indian Institute of Petroleum India OP69

Kholodkov D.N. Russian Academy of Sciences Russia PP24

Kim Y.Y. Pohang University of Science & Technology

Korea OP62

Kim H. Dongguk University College of Medicine

Korea PP36

Author list

212

Kim C. Pohang University of Science and Technology

Korea PP36

Kim Y. Sogang University Korea PP62

Kim C.-J. Kyung Hee University Korea PP62, PP70

Kim B.J. AK ChemTech Central Research Lab

Korea PP63

Kind M. University of Frankfurt Germany OP64

Kirilenko D.A. Ioffe Institut Russia PP53

Kishida K. Meiji University Japan PP14

Kishimoto H. Osaka University Japan PP58

Ko H. Sogang University Korea OP33, PP62, PP70

Kokufu S. Kyoto University Japan OP69, PP72

Kolesnikova A.S. National Research Saratov State University

Russia PP3

Konarzewska D. University of Warsaw Poland PP2

Kondo R. Meiji University Japan PP43

Konovalov O. ESRF France PP12

Korchowiec J. Jagiellonian University Poland OP40, PP1, PP9, PP20

Korchowiec B Jagiellonian University Poland OP40, PP1, PP9, PP20

Krafft M.P. Université de Strasbourg France PP16

Kraskouski A.N. NAS of Belarus Belarus PP22, PP45

Kraus S. The Hebrew University of Jerusalem

Israel IL2

Krawiec M. Marie Curie Sklodowska University

Poland OP52

Krzykawska A. Jagiellonian University Poland OP54

Krzywiecki M. Silesian University of Technology

Poland PP64

Kudryavtsev V.V. Institute of Macromolecular Compounds

Russia PP53

Kulikouskaya V.I. National Academy of Sciences of Belarus

Belarus PP22, PP45

Kulkarni C.V. University of Central Lancashire

UK OP57

Kwiecińska K. Jagiellonian University Poland PP9

Kwon K. Pohang University of Science & Technology

Korea OP62, PP36

Lahav M. The Weizmann Institute of Science

Israel OP28, PP61

Lajunen T. University of Helsinki Finland OP41

Langlet M. University Grenoble Alpes France OP73

Lecomte S. University of Bordeaux France OP6

Author list

213

Lee Y.-S. Seoul National University Korea OP32

Lee T. Seoul National University Korea OP33

Lee J. Sookmyung Women’s University

Korea OP33

Lee J. Pohang University of Science & Technology

Korea OP62, PP36

Lee S. Sogang University Korea PP62, PP70

Lee S.M. Dongguk University Korea PP63

Lee K.M. AK ChemTech Central Research Lab

Korea PP63

Lee K.Y. Sogang University/Sungkyunkwan University

Korea PP70

Lee J.Y. Dongguk University Korea PP63

Leitner A. ETH Zurich Switzerland OP50

Lendlein A. University of Potsdam/Helmholtz-Zentrum Geesthacht

Germany OP21

Li J. CAS Institute of Chemistry China PP54

Li Z. Jilin University China PP74

Liang H. Tampere University of Technology

Finland PP35

Liengprayoon S. University of Montpellier 2 France OP6

Lim J.C. Dongguk University Korea PP63

Linder M. Technical Research Centre of Finland/Aalto University

Finland PP55

Lindfors T. Åbo Akademi University Finland PP50

Lindhorst T.K. University of Kiel Germany OP35

Liu D. Tsinghua University China OP55

Luchinin V.V. St. Petersburg State Electrotechnical University

Russia PP53

Lukyanova V.O. National Research Saratov State University

Russia PP3

Lund S. Åbo Akademi University Finland PP49, PP50

Lutkenhaus J. Texas A&M University USA OP30

Mach M. Jagiellonian University Poland PP8, PP11

Machida R. University of Tsukuba Japan PP39

Maciazek D. Jagiellonian University Poland OP52

Maehira A. Osaka University Japan PP31

Magarkar A. Academy of Sciences of the Czech Republic/Univdrsity of Helsinki

Czech Republic/Finland OP41, PP55

Makowiecki J. Poznan University of Technology

Poland OP8, OP10

Author list

214

Malakhova Y.N. Moscow Technological University/Russian Academy of Sciences

Russia PP24

Maley A. University of California-Irvine USA PP38

Manaka T. Tokyo Institute of Technology Japan IL7

Mandler D. The Hebrew University of Jerusalem

Israel IL2

Maniti O. Université Lyon 1 France OP49, PP54

Manseri A. Centre de Recherche en Technologie des Semi-conducteurs pour l’Energetique

Algeria PP57

Marchand G. M. French Alternative Energies and Atomic Energy Commission (CEA)

France OP1

Marcillat O. Université Lyon 1 France PP54

Marie H. French Alternative Energies and Atomic Energy Commission (CEA)

France OP1

Marquette C. Université Lyon 1 France OP49

Martin C.S. Univ Estadual Paulista Brazil PP29

Martina M.R. University of Florence Italy OP44

Martín-Pedrosa F. Universidad de Valladolid Spain PP28

Martynski T. Poznan University of Technology

Poland OP8, OP10

Mathelié-Guinlet M. Univ. de Bordeaux/ICMCB, UPR CNRS

France OP47

Matsumoto T. Osaka University Japan OP17, OP65, OP66, PP31, PP58

Matsuo Y. Hokkaido University Japan OP37, OP59, PP42, PP46, PP71

Matsuzawa A. Oyama College Japan PP5

Matteini P. CNR Italy OP71

Matyszewska D. University of Warsaw Poland IL3, OP18

Maximino M.D. Univ Estadual Paulista Brazil PP29

McNamee C.E. Shinshu University Japan OP5

Medina-García C. Universidad de Valladolid Spain PP28

Mele N. University of Helsinki Finland PP55

Menari H. CRTSE Algeria PP52

Meri S. University of Helsinki Finland PP25

Author list

215

Miclette Lamarche R.A. Concordia University Canada OP24

Mitomo H. Hokkaido University Japan OP37, OP59, OP71

Miura Y.F. Toin University of Yokohama Japan OP11

Modlinska A. Poznan University of Technology

Poland OP8

Mohamadi S. University of Leeds UK OP39

Mori H. Chitose Institute of Science and Technology

Japan PP37

Moroté F. Univ. de Bordeaux France OP47

Mukherjee S. Université Pierre et Marie Curie

France OP57

Muller F. LICORNE France OP25, OP68, PP12

Mungse H.P. Indian Institute of Petroleum India OP69

Murray B.S. University of Leeds UK OP19

Murtomäki L. Aalto University Finland PP38

Muzafarov A.M. Russian Academy of Sciences Russia PP24

Müller T.J.J. Heinrich-Heine-Universität Düsseldorf

Germany PP64

Määttä J. Aalto University Finland OP67, PP65

Määttänen A. Åbo Akademi University Finland PP26

Nabok A. Sheffield Hallam University UK OP70

Nakagawa M. Tokyo University of Science Japan OP72

Nakahara H. Nagasaki International University

Japan OP14, PP16

Nakamura I. Yamagichi University Japan PP58

Nakamura S. Hokkaido University Japan PP71

Nam S. Sogang University Korea PP62, PP70

Natalich A.V. National Research Saratov State University named after N.G. Chernyshevsky

Russia OP26

Nazaruk E. University of Warsaw Poland IL3

Nelson L.A. University of Leeds UK OP19, OP39

Nicolas H. University of Muenster Germany PP23

Nie H. Northwestern University / Donghua University

USA/China OP2, PP7

Niemelä E. Åbo Akademi University Finland PP26

Niikura K. Hokkaido University Japan OP37, OP59, PP71

Nishijima S. Osaka University Japan OP65

Nishimura T. Tokyo University of Science Japan OP72

Nolvi A. Åbo Akademi/University of Helsinki

Finland IL8

Author list

216

Nosek M. Polish Academy of Sciences Poland PP30

Noskov B.A. St. Petersburg State University Russia OP29, PP56

Noworolska A. Jagiellonian University Poland OP54, OP64

Obara G. Meiji University Japan PP73

Ôhara M. The Hokkaido University Museum

Japan PP39

Ohoyama H. Osaka University Japan PP58

Ohyama H. Osaka University Japan OP66

Ohzono T. Nanosystem Research Institute

Japan PP46

Okamatu T. The Yokohama Rubber Co. Ltd.

Japan PP42

Okuda N. Chitose Institute of Science and Technology

Japan PP39

Oliveira J.S.L. Max-Planck-Institut für Kolloid- und Grenzflächenforschung

Germany OP23

Oliveira H.H.S. University Estadual Paulista / Instituto Federal de Educação, Ciência e Tecnologia de São Paulo

Brazil OP7, PP4, PP13

Orczyk M. Warsaw University of Technology

Poland OP46

Ossowski J. Jagiellonian University Poland OP52, OP54, OP64

Otsuka Y. Osaka University Japan OP65, OP66

Paananen R.O. University of Helsinki and Helsinki University Hospital

Finland OP38

Paananen A. Technical Research Centre of Finland

Finland PP55

Pagano R. University of Salento Italy OP45, OP60

Paige M.F. University of Saskatchewan Canada OP13

Palosaari J. Åbo Akademi University Finland PP49

Panda A.K. Vidyasagar University India PP56

Panov M.F. St. Petersburg State Electrotechnical University

Russia PP53

Papakonstantinou I. University College London UK OP42

Papkov V.S. Russian Academy of Sciences Russia OP12

Paribok I.A. NAS of Belarus Belarus OP32

Parisse P. Sincrotrone Trieste SCpA Italy OP58

Park S.J. Harvard University USA OP33

Parker K.K. Harvard University USA OP33

Parkin I.P. University College London UK OP42

Author list

217

Parsons M.D. University of Southampton UK PP66

Partridge M. Cranfield University UK PP66

Pasyuta V.M. St. Petersburg State Electrotechnical University

Russia PP53

Patterson M.J. University of Calgary Canada PP33

Paul P.K. Osaka University/Jadavpur University

Japan/India OP17

Paulovich F.V. University of São Paulo Brazil PP29

Peltonen J. Åbo Akademi University Finland PP26, PP50

Perez-Salas U. University of Illinois USA OP48

Peruch F.C. University of Bordeaux France OP6

Pinchuk S.V. National Academy of Sciences of Belarus

Belarus PP45

Piñeiro Á. University of Santiago de Compostela

Spain PP69

Piosik E. Poznan University of Technology

Poland OP8, OP10

Pisman Y. The Hebrew University of Jerusalem

Israel IL2

Porcar L. Institut Laue – Langevin France OP48

Postawa Z. Jagiellonian University Poland OP52

Pozharov M.V. National Research Saratov State University named after N.G. Chernyshevsky

Russia PP48

Prenner E.J. University of Calgary Canada PP33

Qian D.-J. Fudan University China PP59

Quilès F. Université de Lorraine France OP51

Rappolt M. University of Leeds UK OP19

Rashid A. University of Leeds UK OP39

Ratanaporn K. Kasetsart University Thailand OP6

Raunio S. Åbo Akademi University Finland PP49

Rebaud S. Université Lyon 1 France OP49, PP54

Rechmann J. Max-Plank-Institut für Eisenforschung GmbH

Germany PP64

Ree M. Pohang University of Science & Technology

Korea OP62

Regnouf-de- Vains J.-B. Université de Lorraine France PP1

Rehman J. University of Saskatchewan Canada OP13

Rodríguez S. Universidad de Valladolid Spain PP28

Rodríguez-Méndez M.L. Universidad de Valladolid Spain PP28

Rogalska E. Université de Lorraine France OP51, PP1

Rojalin T. University of Helsinki/BioNavis Ltd

Finland OP61, PP25

Rojas O.J. Aalto University Finland OP36

Author list

218

Rolandi R. Università di Genova Italy PP68

Románszki L. Hungarian Academy of Sciences

Hungary OP22

Rosenholm J.R. Åbo Akademi University Finland PP44

Rosqvist E. Åbo Akademi University Finland PP26

Ruso J.M. University of Santiago de Compostela

Spain PP69

Rysz J. Jagiellonian University Poland OP52, OP64

Sadeghpour A. University of Leeds UK OP19

Sadowski J.W. BioNavis Ltd Finland OP61, PP25

Safonov R.A. National Research Saratov State University

Russia PP3

Sakai H. Oyama College Japan PP5

Sakeye M. ETH Zurich Switzerland OP50

Salamianski A.E. NAS of Belarus Belarus PP19

Sali S. CRTSE/Houari Boumediene University

Algeria PP51

Salmaso S. University of Padova Italy PP25, PP34

Sammalkorpi M. Aalto University Finland OP30, OP67, PP27, PP65

Sandler N. Åbo Akademi Finland IL8

Santos F.C. University Estadual Paulista Brazil PP4

Santos Pereira M. Univ Estadual Paulista Brazil PP41

Sanver D. University of Leeds UK OP19, OP39

Sato T. National Institute of Advanced Industrial Science and Technology

Japan OP43

Sawano M. Saitama Medical University Japan PP31

Schonhoff M. University of Muenster Germany PP23

Schott M. INSP France OP9, PP21

Schulz B: University of Potsdam/Helmholtz-Zentrum Geesthacht

Germany OP21

Schöne A.-C. University of Potsdam/Helmholtz-Zentrum Geesthacht

Germany OP21

Sebastiani F. Institut Laue-Langevin France PP18

Segawa Y. Chitose Institute of Science and Technology

Japan PP47

Sek S. University of Warsaw Poland OP20, PP2

Semenova T.F. St. Petersburg State University Russia PP53

Sen Karaman D. Åbo Akademi University Finland PP44

Serimaa R. University of Helsinki Finland PP55

Author list

219

Shavdina O. French Alternative Energies and Atomic Energy Commission (CEA)/LITEN

France OP1, OP73

Shibata O. Nagasaki International University

Japan OP14, PP16

Shimomura M. Chitose Institute of Science and Technology

Japan PP37, PP39, PP42, PP46, PP47

Shimouchi A. NCVC Japan PP31

Shin K. Sogang University Korea OP33, PP62, PP70

Shin H.-K. Pohang University of Science and Technology

Korea PP6

Shinkarenko O. National Research Saratov State University named after N.G. Chernyshevsky

Russia PP48

Shtykov S.N. National Research Saratov State University

Russia OP4

Shûhei N. National Museum of Nature and Science

Japan PP39

Silén T. University of Helsinki Finland PP44

Silies L. University of Frankfurt Germany OP64, PP35

Sklizkova V.P. Institute of Macromolecular Compounds

Russia PP53

Skoczek M. Polish Academy of Sciences Poland PP30

Skottman H. University of Tampere Finland PP35

Smirnov A.N. Ioffe Institut Russia PP53

Smått J.-H. Åbo Akademi University Finland OP50

Solano I. Università di Genova Italy OP58, PP68

Soliman A.I.A. Kyoto University Japan PP72

Sorkio A. University of Tampere Finland PP35

Sowah-Kumah D. University of Saskatchewan Canada OP13

Spagnoli S. LIPhy France OP9, PP21

Stachowicz-Kuśnierz A. Jagiellonian University Poland OP40, PP20

Streltsov D.R. Russian Academy of Sciences Russia PP24

Sturm M. Ernst Moritz Arndt University/Max Planck Institute of Colloids and Interfaces

Germany PP10

Sugimura H. Kyoto University Japan OP53, OP69, PP72

Sumida S. Osaka University Japan OP66

Suutari T. University of Helsinki Finland PP44

Svetlychnyi V.M. Institute of Macromolecular Compounds

Russia PP53

Author list

220

Synak A. University of Gdansk Poland OP10

Szlezak M. University of Warsaw Poland IL3

Tamura R. Chitose Institute of Science and Technology

Japan PP42

Taylor A. University College London UK OP42

Telegdi J. Óbuda University Hungary OP22

Terfort A. University of Frankfurt Germany OP35, OP52, OP64

Tillier B. Synthelis France OP49

Tiribilli B. CNR Italy OP71

Torizuka K. University of Tokyo Japan OP11

Torkkeli M. University of Helsinki Finland PP55

Torsi L. Università degli Studi di Bari Italy IL10

Trojan S. Jagiellonian University Poland OP40, PP9, PP20

Tsunashima R. Yamagichi University Japan PP58

Tummino A. Institut Laue-Langevin/Eötvös Loránd University

France/Hungary OP29, PP18

Turchanin A. Friedrich Schiller University Jena

Germany IL11

Uchiya K. Chitose Institute of Science and Technology

Japan PP40

Ujula T. Aalto University Finland PP35

Ulman A. NYU Tandon School of Engineering

USA PL1

Urata C. National Institute of Advanced Industrial Science and Technology

Japan OP43

Urtti A. University of Helsinki Finland OP41, PP25

Utsunomiya T. Kyoto University Japan OP53, OP69, PP72

Uttyia S. Università di Genova Italy PP68

Uwatoko Y. University of Tokyo Japan OP11

Wadeesirisak K. Kasetsart University Thailand OP6

Vakurov A. University of Leeds UK OP39

Walch N.J. Cranfield University UK OP70

Valle-Delgado J.J. Aalto University Finland PP35

Valli L. University of Salento Italy OP45, OP60

van der Boom M.E. The Weizmann Institute of Science

Israel OP28, OP61

Van Tassel P.R. Yale University USA OP67

Wang J. Fudan University China PP59

Varga I. Eötvös Loránd University Hungary OP29

Author list

221

Vasilevich I.B. National Academy of Sciences of Belarus

Belarus PP45

Vattulainen I. University of Helsinki Finland OP38

Vaysse L. Kasetsart University Thailand OP6

Węder K. Jagiellonian University Poland PP8, PP11

Wei H. Hokkaido University Japan OP37

Wenda J. Université de Genève Switzerland OP20

Venu A.P. Åbo Akademi University Finland PP26

Weroński P. Polish Academy of Sciences Poland PP30

Verrier I. University Jean Monnet France OP73

White J.W. Australian National University Australia PP18

Whitesides G.M. Harvard University USA OP54

Vickridge I. INSP France PP21

Vierros S. Aalto University Finland OP67

Vignoud S. French Alternative Energies and Atomic Energy Commission (CEA)

France OP1

Viitala T. University of Helsinki Finland IL8, OP41, PP25, PP34, PP44

Viitala L. Aalto University Finland PP38

Vocanson F. University Jean Monnet France OP73

Vogel H.J. University of Calgary Canada PP33

Wojciechowski K. Warsaw University of Technology

Poland OP46

Wojszko K. Jagiellonian University/Université de Lorraine

Poland/France OP51

Volotovski I.D. National Academy of Sciences of Belarus

Belarus PP45

Vuorimaa-Laukkanen

E. Tampere University of Technology

Finland PP35

Vuorte M. Aalto University Finland PP65

Wydro P. Jagiellonian University Poland PP8, PP11

Wächter T. Universität Heidelberg Germany OP64

Xu J.F. Tsinghua University China PP23

Yamaguchi H. Osaka University Japan OP66, PP58

Yamamoto T. Nagoya University Japan IL6

Yang H. Tsinghua University China OP31

Yang C.H. Maple semiconductor Inc. Korea PP6

Yildirim E. Aalto University Finland OP30

Yliperttula M. University of Helsinki Finland PP25, PP35, PP44

Yoshikawa S. Meiji University Japan PP73

Author list

222

Yoshitake S. Meiji University Japan PP43

Yuan B. Tsinghua University China OP31, PP23

Yun H. Pohang University of Science & Technology

Korea OP62

Zaba T. Jagiellonian University Poland OP54

Zegtouf H. Houari Boumediene University

Algeria PP52

Zhang W. Jilin University China IL9, PP74

Zhang R. Aalto University/Chinese Academy of Sciences

Finland OP30, PP27

Zhang Y. Texas A&M University USA OP30

Zhang X. Tsinghua University China OP31, PP23

Zharnikov M. Heidelberg University Germany OP27, OP34, OP64, PP67

Zimmerli C.E. Åbo Akademi University Finland OP50

Zougar L. Houari Boumediene University

Algeria PP51

Österberg M. Aalto University Finland OP63, PP35

Author list

223

Author list

224

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