Open Problems in Systems Chemistry · • Claudiu Supuran (Univ Firenze, IT) Scope: Open Problems...

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Open Problems in Systems Chemistry Institut Européen des Membranes ■ Montpellier ■ France

Labex Chemisyst ■ Pole Balard Montpellier ■ 23-25 January 2012

Invited Speakers will include

• Gerard Ferey (Inst. Lavoisier Versailles, FR)

• Mihail Barboiu (Inst. Europeen des Memranes, FR)

• Olof Ramström (KTH Stockholm, SE)

• Jean Martinez (Inst. Max Mousseron, Montpellier, FR)

• Thomas Zemb (Inst Chimie Separative, Marcoule, FR)

• Nicolas Giuseppone (Inst Charles Sadron, FR)

• André Vioux (Inst Charles Gerhardt, FR)

• Claudiu Supuran (Univ Firenze, IT)

Scope: Open Problems in Systems Chemistry Symposium is the first Symposium that brings together the scientists representing all research domains of the Systems Chemistry: Chemistry, Life Sciences, Chemical Biology, Biophysics. Participants of Labex Chemisyst (Pole Balard, Montpellier) Labex Systems Chemistry (University of Strasbourg) and European ITN Marie Curie DYNANO will have the opportunity of meeting across the boundaries of different disciplines and opportunity of finding a common language to discuss scientific items from various perspectives.

The aim of the Symposium is to create conditions for exchange and interaction, between different disciplines and between promising younger researchers and the world’s leading scientists. The overall themes of the Symposium will be: complexity and diversity as a driving force for life and evolution; the evolution of physical and chemical complex dynamic structures and the development of novel systems and technologies in the service of society.

SPONSORING ORGANISATIONS

Scientific Organising Committee

� Mihail Barboiu Congress Chair (Inst. Européen des Membranes, FR) � Philippe Miele (Inst. Européen des Membranes, FR) � Thomas Zemb (Inst Chimie Séparative, FR) � Jean Martinez (Inst. Max Mousseron, FR) � François Fajula (Inst. Charles Gerhardt, FR)

Deadline for Registration: 19 January 2012

NAME:

ORGANIZATION: EMAIL:

I WILL ATTEND THE: SESSION ON 23 JANUARY � SESSION ON 24 JANUARY �

MATIN : AMPHI CNRS DR13/AM : IEM IEM Please return simultaneously this information before January 15, 2012 to:

Dr. Mihai BARBOIU : [email protected]

Miss Marion Ritchie : [email protected]

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Open Problems in Systems Chemistry January 23- January 26, 2012

Institut European des Membranes, Montpellier France, Labex Chemisyst, Pole Balard

Montpellier

January 23, 2012 January 24, 2012 January 25, 2012 January 26, 2012

8:30 Welcome addresses

Free time or

1 hour walk in Montpellier Historical

Center 9h30

Chair Olof Ramstrom

Amphitheatre CNRS

DYNANO kick-off meeting - 9:00-16:00 Salle de reunion IEM

9:00 Plenary lecture

Gérard Ferey Social Activities

Excursion Provence

10:00 Coffee break Coffee break

10:30 Invited lecture

Thomas Zemb Open courses On Biomaterials

Conference room IEM 11:15 Invited lecture

Corrine Gérardin

Practical Lecture

André Ayral Inorganic Membranes –

past, present and beyond

12:00 Invited lecture André Vioux

12:45 Lunch IEM

11:30 Lunch IEM

12:30 Lunch

Chair André Vioux Conference room IEM

Stéphane Vincent Conference room IEM

13:45 Plenary lecture

Olof Ramstrom Plenary lecture

Mihail Barboiu Practical Lecture Arie van der Lee

Powder diffraction –

modern tool for the study of materials


Nicolas Giuseppone Invited lecture

François Morvan


Stéphane VINCENT Invited lecture

Calin Deleanu

16:15 Coffee break Coffee break

Chair Eugen Gheorghiu Conference room IEM

Calin Deleanu Conference room IEM


Claudiu Supuran Invited lecture

Eugen Gheorghiu


Dolores Solis Invited lecture

Mihaela Gheorghiu


María Asunción Campanero-Rhodes

Invited lecture

Frédéric Lamaty


Damien Quemener Plenary lecture

Jean Martinez

20:30 Dinner-Clos des Oliviers –St Gely

Dinner- Insense-Montpellier

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Name Affiliation Title of the talk

Gérard Ferey Institut Lavoisier, Université de Versailles-Saint Quentin Bâtiment Lavoisier, 45 avenue des Etats-Unis, 78035 Versailles France, [email protected]

From interesting to useful : the genesis and societal applications of hybrid porous solids.

Olof Ramström Royal Institute of Technology (KTH), Department of Chemistry, Teknikringen 30, S-10044 Stockholm, Sweden. [email protected]

Catalytic Promiscuity and Dynamic Systems

Mihail Barboiu Institut of Macromolecular chemistry Pentru Poni Iasi, Allea Ghica voda no 41 A, Iasi, Romania, [email protected]

Dynamic Interactive Systems-toward natural selection of functions

Jean Martinez Institut des Biomolecules Max Mousseron, Faculté de Pharmacie, 15 av Charles Flahault BP 14491, 34093, Montpellier, Cedex 5, France, [email protected]

Genome as a Source for the Discovery of New Peptide Hormones. Synthesis and Pharmacological Characterization of New Active Peptides.

Thomas Zemb Institut de Chimie Separative Marcoule [email protected]

Collections of dynamic aggregates for selective sorting systems for multivalent cations

André Vioux Chimie Moléculaire et Organisation du Solide, Institut Charles Gerhardt Université Montpellier 2 , CC 1701, 34095 Montpellier cedex 05, France

[email protected]

Nanoscale structures in ionic liquids. Applications in materials chemistry

François Morvan Institut des Biomolecules Max Mousseron, Faculté de Pharmacie, 15 av Charles Flahault BP 14491, 34093, Montpellier, Cedex 5, France. [email protected]

Synthesis of DNA glycomics. Design of a carbohydrate array ans study of Lectin carbohydrate interactions

Dolores Solis Department of Physical Chemistry of Biological Macromolecules at Rocasolano Institute of Physical Chemistry, C/Serrano 119. Madrid. E-28006 (España). [email protected]

Lectins as biosensors: characterization of structural and ligand-binding features.

Eugen Gheorghiu International Centre of Biodynamics, 1B Intrarea Portocalelor, 060101 Bucharest 6 ROMANIA. [email protected]

Analytic platform to assess interfaces based on Magneto Plasmonics (Magnetic SPR)

Mihaela Gheorghiu International Centre of Biodynamics, 1B Intrarea Portocalelor, 060101 Bucharest 6 ROMANIA. [email protected]

Electro-Optical flow-through system to appraise cell dynamics

Nicolas Giuseppone University of Strasbourg , SAMS Research Group – icFRC, Institut Charles Sadron , 23 rue du Loess, BP84047, 67034 Strasbourg Cedex 2 , France [email protected]

Towards Self-fabricating Functional Materials

Stéphane VINCENT FUNDP – Faculté des Sciences , Laboratoire de Chimie Bio-Organique Rue de Bruxelles, 61, B-5000 Namur - Belgique [email protected]

Complex glycan biosynthesis : a case study in systems chemistry ?

María Asunción Campanero-Rhodes

Departamento de Química Física Biológica, Instituto de Química-Física "Rocasolano", CSIC C/ Serrano 119, 28006 Madrid, Espagne. [email protected]

Designer’ microarrays: versatile tools for Glycosciences

Antonio Villalobo Instituto de Investigaciones Biomedicas, CSIC& Universidad Autonoma de Madrid, c/ Arturo Duperier 4, E-28029 Madrid, Spain [email protected]

Protein O-GlcNAcylation: a regulatory mechanism in signal transduction

Claudiu Supuran University of Florence, Laboratorio di Chimica Bioinorganica, Via della Lastruccia, 3, Rm. 188, Polo Scientifico, 50019 - Sesto Fiorentino (Firenze) , Italy. [email protected]

Carbonic Anhydrases as drug targets

Corrine Gérardin Institut Charles Gerhardt, Equipe MACS, ENSCM, 8 rue de l’Ecole Normale, 34296, Montpellier, France. [email protected]

Responsive and switchable micelles for the preparation of functional mesoporous materials

Calin Deleanu Institut of Macromolecular Chemistry Pentru Poni Iasi, Allea Ghica voda no 41 A, Iasi, Romania, [email protected]

NMR spectroscopy from diagnosing metabolic disorders towards personalized medicine

Frédéric Lamaty Institut des Biomolecules Max Mousseron, Faculté de Pharmacie, 15 av Charles Flahault BP 14491, 34093, Montpellier, Cedex 5, France,

Developing the « green tool box » for organic synthesis

Damien Quemener Institut Européen des Membranes, Place Eugene Bataillon, CC 047, 34095, Montpellier, France. [email protected]

Dynamic interactive materials - toward self-instructed membranes with pressure-driven tunable porosity and self-healing ability

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From interesting to useful: the genesis and societal applications of

hybrid porous solids.

Gérard Férey

Académie des Sciences et Institut Lavoisier, Université de Versailles, 45, Avenue des Etats-

Unis, 78035 Versailles (France)

[email protected]

The story of porous solids begins in 1756 in Sweden, but their tremendous

development during the last twenty years make them now strategic materials.

The example of hybrid porous solids – which result from the three-dimensional

association by strong bonds of inorganic and organic moieties – illustrates what the

integrated approach of chemists must be, from pure academic research to industrial

production, for providing solutions to current societal problems in the domains of

energy, energy savings, sustainable development and health.

The mastery of ‘tailor-made’ syntheses implies the knowledge of the mechanisms of

formation of these solids. Once elucidated, it allows, playing on their different

characteristics (framework, pores and specific surface area), to introduce new

properties, to tune the size of the pores, and even predict the structure of new solids

for generating the applications and the industrial development in various domains.

For example, hybrid porous solids are excellent materials for hydrogen storage at

77K, and for greenhouse gases at room temperature. Their separating power for gas

mixtures operates with low energy consumption. Beside, they are excellent catalysts

and, recently, these non-toxic solids appear to be the best nanovectors for the storage

and long-term delivery of anti-tumoral et anti-retroviral drugs. Their easy

production at large scale leads for some of them to an industrial development.

Some references:

1. G. Férey et al. , Science 2005, 309, 2040.

2. G. Férey, Chem. Soc. Rev. 2008, 37, 191.

3. C. Serre, G. Férey, Adv. Mater. 2007, 19,

2246.

4. P. Llewellyn et al. Langmuir 2008, 24, 7245.

5. G. Férey et al., Nature Mater. 2010, 9, 172.

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Collections of water in oil aggregates for selective, controlled and

efficient phase transfer of cations.

Pr Thomas Zemb

Institut de Chimie Separative Marcoule

[email protected]

Water-poor reverse micelles are the

basis of hydrometallurgy, the industry

involved in metal mining, purifying

and recycling, especially in the case of

rare earths and strategic metals.

At nanometre scale, the molecular

systems allowing to control transfer of

cations between widely used are reverse

micelles, in a so-called Winsor equilibria.

Long range interactions control as well as stability of these molecular systems than

the apparent equilibrium « constants » controlling ion extraction and desextraction.

We will first review a few known colloidal and supramolecular properties of these

simple and nevertheless crucially useful chemical systems, and then address a few

open problems in efficient control of ion transfer between phases which are common

to metal recycling via green chemistry, ion transfer through simple model bilayers or

biologic membranes.

Reference: R G French, V A Parsegian et al, Rev Mod. Phys. 2010 , 82, 1887 : Long range

interactions in nanoscale science

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Responsive and switchable micelles for the preparation of functional

mesoporous materials

Corrine Gérardin

Institut Charles Gerhardt Montpellier, CNRS ENSCM UM2 UM1 Montpellier, France

[email protected]

Nanostructured hybrid materials with a long range organization at the meso-scale

are usually prepared by using micelles of surfactants or amphiphilic polymers as

structuring agents of the inorganic phase, typically silica. Most commonly used

structuring agents are micelles of cationic or neutral surfactants and

polyethyleneoxide-based block copolymers. They are used as porogens and they also

ensure the formation of ordered homogeneous hybrid mesophases, precursors for

mesoporous materials. Here we present a method for the preparation of functional

mesoporous materials, which relies on the use of different structuring agents: they

are functional PolyIon Complex (PIC) micelles, and their role is double: (1) they

direct the structure of the inorganic porous framework and (2) they are able to confer

functionalities to the final mesoporous material. Such micelles are different from the

permament surfactant assemblies that result from hydrophobic interactions, since

PIC micelles are induced assemblies of hydrosoluble polymers that result from

electrostatic interactions between two polyions of opposite charge, one of the

polyions belonging to a double-hydrophilic block copolymer (DHBC). We will

describe several preparation routes of functional hybrid silica-based mesoporous

materials using such stimuli-responsive and switchable polyion complex micelles.

We will mention the material potential applications as catalysts, drug delivery

systems, sensors or metal ion sequestering agents.

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Nanostructures in ionic liquids.

Application to the synthesis of materials.

André Vioux

Chimie Moléculaire et Organisation du Solide, Institut Charles Gerhardt

Université Montpellier 2 , CC 1701, 34095 Montpellier cedex 05, France

[email protected]

Salts (generally salts of organic cations) which have melting points lower than

100°C are called ionic liquids (ILs). Interestingly, a large family of them are air and

water stable, as well as thermally stable at temperatures higher than 300°C. Most

attractiveness of ILs relies on the possibility to tune their properties by the choice of

the anion-cation combination.

ILs, which are able to solubilise both organic and inorganic species, have been

widely used as reaction media for catalysis and biocatalysis, being claimed as

“green” solvents, in relation to their negligible vapour pressure and non

flammability, combined with their ability to be recycled in liquid-liquid processes.

Nevertheless, the use of ILs in material chemistry is just emerging, particularly in

metal electrodeposition, “ionothermal” syntheses and sol-gel.

A great deal of works involving material chemistry in ILs was performed in

imidazolium salts, the properties of which can be adjusted by the nature of side-

chains at the 1- and 3-positions on the ring. Many of their typical features arise from

the acidic character of the ring proton in C2 position, located between two

electronegative nitrogen atoms. Thus, the interactions between C2H and anions that

are disclosed in crystalline structures play a key role in the structure of liquid phases

through extended hydrogen bonded networks resulting in supramolecular ions

aggregates.

Long carbon-chains direct the crystal packing to layered structures, which may

be maintained in liquid state as smectic phases. However even “isotropic” ILs are

structured on a nanoscale. Computer simulation on 1-alkyl-3-methylimidazolium ILs

predicts a nano-segregation into polar and nonpolar domains. It was observed that

the polar domain forms a tridimensional network of ionic channels, while the

structure of non-polar domains changes from isolated islands to a second continuous

nano-domain as the length of the alkyl-side chain increases. Moreover, in a manner

analogous to aqueous solutions, solvatophobic interactions have been observed with

the hydrocarbon moieties of some surfactants, which entail amphiphile self-assembly,

in relation to the high cohesive energy density of ILs. Nevertheless surface tensions

of most ILs are lower than that of water, which results in high nucleation rates.

Finally, the high ionic atmosphere in ILs makes the electrostatic repulsion

inefficient to stabilize charged nanoparticles, owing to charge screening. Accordingly,

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it has been proposed that IL-based steric forces and IL-based solvation forces account

for the experimental evidence of unusual colloidal stabilization in ILs without any

stabilizers.

In conclusion imidazolium ILs may be regarded both as structured and

structuring media, their nanoscale organization driving to well defined

nanostructures. Several examples arising from works of different teams of CheMISyst

will be presented to illustrate the potential of IL media in the synthesis of

nanoparticles (metal, metal sulfides, coordination polymers etc.), or in sol-gel

chemistry (templating and catalyst effects). Other examples will illustrate how the

use of building blocks inspired from ILs or the immobilization of ILs in ionogels

open new routes for designing functional membranes (for separation, electrolyte,

sensing, catalysis applications) and drug release systems.

CMOS, Université Montpellier 2, case courrier 1701

Place E Bataillon, 34095 Montpellier

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Catalytic Promiscuity and Dynamic Systems

Olof Ramström

Royal Institute of Technology (KTH), Department of Chemistry, Teknikringen 30, S-10044

Stockholm, Sweden. [email protected]

Dynamic systems based on reversible reactions can be applied to both selective

synthesis and discovery processes. These systems can be resolved to provide optimal

constituents for a wide range of applications. In this presentation, examples of such

resolution processes will be given, with special emphasis on kinetic approaches. For

example, biocatalysis have been employed for asymmetric transformation processes,

generating a range of chiral ester and amide structures. By use of such biocatalysts,

optimal constituents were selectively chosen and amplified from the dynamic

systems in one-pot processes. Additional examples involve self-transformation and

crystallization-induced diastereomeric resolution, where optimal diastereomeric

structures were efficiently selected from dynamic systems, as well as fragment-based

inhibitor identification for selected protein targets.

Sakulsombat, M., Zhang, Y., Ramström, O. Top. Curr. Chem. 2011, DOI: 10.1007/128_2011_203

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Towards Self-constructing Functional Materials

Professor Nicolas Giuseppone

University of Strasbourg, SAMS Research Group, icFRC, Institut Charles Sadron, 23

rue du Loess, BP 84047, 67034 Strasbourg Cédex 2, France

[email protected]

The confluence of dynamic and constitutional features related to supramolecular

self-assemblies[1,2] – when they occur within mixtures of competing molecular

architectures – has recently opened a very intriguing branch of chemical science, the

so-called dynamic combinatorial chemistry (DCC). Within this framework, emerging

lines of investigations have been directed towards the development of dynamic

combinatorial materials and devices.[3,4] These ones can be defined as multi-

component chemical systems which, thanks to the reversibility of their

interconnections within networks of competing reactions, and thanks to their

sensitivity to environmental parameters, aim at performing modular functional tasks

by responding to external stimuli. The behaviour of such dynamic materials is by

essence more complex than the one produced by their static or single-component

counterparts and as such, they hold higher potentialities in terms of information

processing and functionality tuning.

Besides materials science, another recent approach in DCC consists in coupling

networks of reversible reactions with autocatalytic loops, in order to combine their

constitutional “plasticity” with a self-replicating process as an amplification tool.[5-7]

We will discuss some of our works concerning such responsive systems along these

two different lines and, more particularly, we will focus on their merging to access

self-constructing materials with advanced functional properties for electronic conduction.[8-9]

We will also outline the potential of such systems to act as vectors of information.[10]

[1] Moulin, E., Giuseppone, N. – Encyclopedia of Supramolecular Chemistry – From molecules to

nanomaterials - Reactions in Dynamic Assemblies, John Wiley & Sons, Ltd., 2012.

[2] Giuseppone, N., Lutz, J.-F., Nature, 2011, 473, 40.

[3] Moulin, E., Cormos, G., Giuseppone, N., Chem. Soc. Rev., 2012, published online DOI:

10.1039/C1CS15185A.

[4] Tauk, L., Schröder, A., Decher, G., Giuseppone, N., Nat. Chem., 2009, 1, 649.

[5] Xu, S., Giuseppone, N., J. Am. Chem. Soc. 2008, 130, 1826-1828.

[6] Nguyen, R., Allouche, L., Buhler, E., Giuseppone, N. Angew. Chem. Int. Ed. 2009, 48, 1093-1096.

[7] Moulin, E., Giuseppone, N., Top. Curr. Chem., 2012, published online DOI: 10.1007/128_2011_198.

[8] Moulin, E., Niess, F., Maaloum, M., Buhler, E., Nyrkova, I., Giuseppone, N., Angew. Chem. Int. Ed.

2010, 49, 6974-6978.

[9] Faramarzi, V., Niess, F., Moulin, E., Maaloum, M., Dayen, J.-F., Beaufrand, S. Zanettini, J.-B.,

Doudin, B., Giuseppone, N., submitted.

[10] Giuseppone, N., Acc. Chem. Res. 2012, Accepted.

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The glycochemistry and biochemistry of Complex Systems –

The biosynthesis of Mycobacterium tuberculosis cell wall as a case

study

Stéphane P. VINCENT

University of Namur (FUNDP), Département de Chimie, Laboratoire de Chimie Bio-

Organique, rue de Bruxelles 61, 5000 Namur, Belgium

E-mail: [email protected]

Our laboratory is interested in the mechanistic and inhibition studies of

essential enzymes involved in the bacterial cell wall biosynthesis of important human

pathogens such as Mycobacterium tuberculosis. The virulence of this bacterium is

directly linked to the structure of its cell wall depicted below. Its extraordinary

complexity has led to considerable efforts to understand its biosynthesis but also to

synthesize some of the main fragments.

This research field is probably a typical case where systems glycobiology and

organic synthesis have to meet. We will thus review this topic from the “systems

chemistry” viewpoint.

D-MurNAcO

OH

HO

O

O

O

OH

HO

HOO

O

OH

HO

O

OH

O

OOH

ONHAc

PeptidoglycanO

OP

O

OHO

CO2H

OH

HO

AcHNO

OO HO

OH

O

HO OH

O

OH

HO

HO

OH

O

OH

HO

HOO

O

OH

HO

O

OH

OO OH

OH

OO OH

OH

OOH

OH

O

OOH

OH

b-1,6

b-1,5

D-GlcNAcL-Rha

b-1,6

b-1,5 n > 10

n

D-GalfD-Araf

Galactan

Arabinan

D-Galf

D-Araf

D-MurNAc

O

O

O

OHD-Araf

O

O

O

OO OH

OH

O

O

O

OO OH

OMe

O

O

O

OO OH

OH

O

O

OO OH

OMe

HOHO

HOOH

Mycolic acids(heterogeneous structures)

n

n

The mycobacterial cell wall main glycoconjugate

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Carbonic anhydrases as drug targets

Claudiu T. Supuran and Andrea Scozzafava

Laboratorio di Chimica Bioinorganica, Università degli Studi di Firenze, Rm 188,

Via della Lastruccia 3, I-50019 Sesto Fiorentino, Firenze, Italy.

[email protected]

Carbonic anhydrases (CAs), a group of ubiquitously expressed metalloenzymes,

are involved in numerous physiological and pathological processes, including

gluconeogenesis, lipogenesis, ureagenesis, tumorigenicity and the growth and

virulence of various pathogens. In addition to the established role of CA inhibitors

(CAIs) as diuretics and antiglaucoma drugs, it has recently emerged that CAIs could

have potential as novel anti-obesity, anticancer and anti-infective drugs.

Furthermore, recent studies suggest that CA activation may provide a novel therapy

for Alzheimer's disease. The presentation discusses the biological rationale for the

novel uses of inhibitors or activators of CA activity in multiple diseases

(predominantly cancer), and highlights progress in the development of specific

modulators of the relevant CA isoforms, some of which are now being evaluated in

clinical trials.1-4

1. Supuran, C.T. Nature Rev. Drug. Discov. 2008, 7, 168-181.

2. Alterio, V.; Hilvo, M.; Di Fiore, A.; Supuran, C.T.; Pan, P.; Parkkila, S.;

Scaloni, A.; Pastorek, J.; Pastorekova, S.; Pedone, C.; Scozzafava, A.; Monti,

S.M.; De Simone, G. Proc. Natl. Acad. Sci. USA, 2009, 106, 16233-16238.

3. Supuran, C.T. Bioorg. Med. Chem. Lett. 2010, 20, 3467-3474.

4. Neri, D.; Supuran, C.T. Nature Rev. Drug. Discov. 2011, 10, 767-777.

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Designer’ microarrays: versatile tools for glycosciences

M. A. Campanero-Rhodes

Departamento de Química Física Biológica, Instituto de Química-Física "Rocasolano", CSIC

C/ Serrano 119, 28006 Madrid, Espagne.

[email protected]

Application of the microarray technology to the glycobiology field is impelling the study of

protein-carbohydrate interactions, enabling the high-throughput analysis of biologically

relevant systems. Several microarray platforms involving different carbohydrate

immobilisation strategies are being developed by the glycoscientists. A neoglycolipid-based

carbohydrate microarray platform was set up at the Glycosciences Laboratory (Imperial

College London) leaded by Professor Ten Feizi. Arraying, binding and quality control

protocols were established and dedicated software and database created for the analysis,

scrutiny and storage of results. The system has been validated with plant lectins and is being

applied to biomedically important systems that operate through oligosaccharide recognition,

in particular, receptors of the immune system, parasites and viruses. In this talk, some

applications of this microarray system to the elucidation of pathogen–receptor interactions at

the early stages of host cell invasion will be described.

A versatile microarray platform incorporating and exploring a variety of microarray

technologies and dedicated to the study of carbohydrate-mediated interactions is currently

being established at Dr. Dolores Solís’ group (Institute of Physical Chemistry “Rocasolano”,

CSIC).

14

Dynamic interactive materials - toward self-instructed membranes

with pressure-driven tunable porosity and self-healing ability

Prashant Tyagi1, André Deratani1, Denis Bouyer1, Didier Cot1, Mihai Barboiu1, Trang NT

Phan2, Denis Bertin2, Didier Gigmes2 and Damien Quémener1*

1 Institut Européen des Membranes,Université Montpellier 2, Case 047,Place E. Bataillon,

34095 Montpellier Cedex 05, France. 2 Laboratoire Chimie Provence, Chimie Radicalaire,

Organique et Polymères de Spécialité, Université d’Aix Marseille I, II et III, Campus Saint

Jérôme, Case 542, 13397 Marseille Cedex 20, France.


Constitutional adaptive self-assembly of nanometric objects gives the possibility to extend

and to engineer interactions of complex matter across extended scale towards systems

expressing the adaptive behaviors. Within this context constitutional self-instructed

membranes were developed to allow the fine tuning of their virtual morphological structure

in response to operating applied pressure, leading to a range of accessible porosities and

effective autonomous healing. These systems express a synergistic adaptive behaviour: the

applied pressure drives a constitutional evolution toward the selection of the specific

membrane nanostructures regulating and thereby controlling water filtration performances.

The present efforts involve the investigation of nanoporous adaptive self-regenerating

membrane films obtained via one pot hierarchical assembly of block copolymers. They

generate flower-like block copolymer micelles composed of a soft corona of polyethylene

oxide-PEO, enabling slight deformation under compression and a relatively hard core of

poly(styrene-co-acrylonitrile)-PSAN, maintaining the micelle’s structural integrity. The

spherical micelles self-assemble in the material in such a fashion that PEO external

hypersurfaces might be able to maximize of all structure/energy combinations in order to

form stable membrane films exhibiting porosity modulation and an intrinsic self-healing

capability. It is demonstrated that a selective compression of the micelle corona leads to a

controlled change of the porosity by decreasing the free space while reversibly transforming

spheres into spheroids. Beyond a critical pressure, the compression leads to an irreversible

change of the morphology from spheres to wormlike network leading to another accessible

porosity range. Moreover, this material was able to repair autonomously a perforation. A

mechanism is proposed, based on the combination between a compression gradient in the

film and a concerted movement of the micelles. These results should initiate new

interdisciplinary discussions about interactive constitutional systems and may confer to

membrane materials the capacity to self-regulate their performances upon operating

conditions. Moreover these systems confer to membrane materials the capacity to mend

themselves and to undergo self-healing, self-repairing processes as found in biomolecular

materials.

15

Dynamic interactive systems-toward natural selection of functions

Mihail D. Barboiu

Institut Européen des Membranes, Adaptative Supramolecular Nanosystems Group,

IEM/UMII, Place Eugene Bataillon, CC047, F-34095 Montpellier, France.


Numerous artificial transport systems utilizing carriers, channel-forming or self-organized

polymeric superstructures able to orient, to select and to pump the ionic transport across

membranes have been developed in the last decades. Of special interest is the structure-

directed function of hybrid membrane materials and control of their build-up from suitable

units by self-organisation. The main interest focus on functional hybrid membranes in which

the recognition-driven transport properties could be ensured by a well-defined incorporation

of receptors of specific molecular recognition and self-organization functions, incorporated

in a hybrid dense materials. We are therefore proposing to review the membrane transport

properties of such supramolecular membrane materials with potential in renewable energy

applications as fuell-cells technology, biomimetic water and ion channels, etc.

[1] M. Barboiu, C. Luca, C. Guizard, N. Hovnanian, L. Cot, G. Popescu, J. Membrane Sci., 1997, 129,

197-207.

[2] M. Barboiu, C. Guizard, J. Palmeri, C. Reibel, C. Luca, L. Cot, J. Membrane Sci. 2000, 172, 91-103.

[3] M. Barboiu, S. Cerneaux, G. Vaughan, A. van der Lee, J. Am. Chem. Soc. 2004, 126 3545-3550.

[4] A. Cazacu, C. Tong, A. van der Lee, T.M. Fyles, M. Barboiu, J. Am. Chem. Soc. 2006, 128(29), 9541-

9548.

[5] C. Arnal-Herault, A. Pasc-Banu, M. Barboiu A. van der Lee, Angew. Chem. Int. Ed. 2007, 46, 4268-

4272.

[6] C. Arnal-Herault, A. Pasc-Banu, M. Michau, M. Barboiu, Angew. Chem. Int. Ed. 2007, 46, 8409-

8413.

[7] C. Arnal-Hérault, M. Barboiu, A. Pasc, M. Michau, P. Perriat, A. van der Lee, Chem. Eur. J. 2007,

13, 6792

[8] M. Michau, M. Barboiu, R. Caraballo, C. Arnal-Hérault, A. van der Lee, Chem. Eur. J. 2008, 14,

1776-1783.

[9] M. Barboiu, P. Aimar, J.M. Lehn, From simple molecules to complex membrane systems, Editorial,

Special issue of J. Memb. Sci., 2008, 321, 1-2.

[10] M. Michau, M. Barboiu, J. Mater. Chem., 2009, 19, 6124-6131.

[11] A. Cazacu, Y.M. Legrand, A. Pasc, G. Nasr, A. van der Lee, E. Mahon, M. Barboiu, Proc. Natl.

Acad. Sci., 2009, 106(20), 8117-8122.

[12] S. Mihai, A. Cazacu, C.Arnal-Herault, G. Nasr, A. Meffre, A. van der Lee, M. Barboiu, New. J.

Chem, 2009, 33, 2335-2343.

[13] M. Barboiu, Chem. Commun. 2010, 46, 7466-7476.

[14] Y. Le Duc, M. Michau, A. Gilles, Valerie Gence, Y.-M. Legrand, A. van der Lee, S. Tingry, M.

Barboiu,; Angew. Chem. Int. Ed. 2011, DOI : 10.1002.anie.201103312

16

Synthesis of DNA Glycomimetics, Design of a carbohydrate array and

study of Lectin carbohydrate interactions

François Morvana, Albert Meyera, Sébastien Vidalb, Yann Chevolotc, Eliane Souteyrandc and Jean-

Jacques Vasseura

aInstitut des Biomolécules Max Mousseron UMR 5247 CNRS Université de Montpellier 1 Université

de Montpellier 2, CC1704, Place Eugène Bataillon 34095 Montpellier cedex 5, France.

[b]Institut de Chimie et Biochimie Moléculaires et Supramoléculaires UMR 5246 CNRS Université

Lyon 1, cInstitut des Nanotechnologies de Lyon, UMR 5270 CNRS Ecole Centrale de Lyon.

Glycoarrays are powerful tools for the understanding of protein/carbohydrate interactions

and should find applications for the diagnosis of diseases involving these interactions. They

are two key issues for obtaining a high performance device. The first one relates to the

difficulty in obtaining a large variety of carbohydrates probes and the second one to their

immobilisation on the solid support. Herein, we demonstrate that DNA Glycomimetics can

be synthesized using nucleic acid chemistry. The synthesis is based on a combination of

oligonucleotide phosphoramidite or H phosphonate chemistries on solid support and

microwave assisted click chemistry[1-8]. These glycomimetics are immobilised by DNA-

directed immobilisation (DDI) onto a DNA chip. The performance of the resulting device is

compared to direct covalent immobilisation. The IC50 values are measured for different

glycomimetics towards their lectins. Furthermore, DDI permits to perform first the

interaction between these glycomimetics and the lectin and then to address the resulting

complex thanks to the specificity of DNA hybridization.

Next, affinities of different glycomimetics were tested towards Ricinus communis agglutinin

120 and Pseudomonas aeruginosa 1 Lectin.[7, 9-11]

[1] C. Bouillon, A. Meyer, S. Vidal, A. Jochum, Y. Chevolot, J. P. Cloarec, J. P. Praly, J. J.

Vasseur, F. Morvan, J. Org. Chem. 2006, 71, 4700-4702, [2] F. Morvan, A. Meyer, A. Jochum, C.

Sabin, Y. Chevolot, A. Imberty, J.-P. Praly, J.-J. Vasseur, E. Souteyrand, S. Vidal, Bioconjugate

Chem. 2007, 18, 1637, [3] G. Pourceau, A. Meyer, J. J. Vasseur, F. Morvan, J. Org. Chem. 2008,

73, 6014-6017, [4] G. Pourceau, A. Meyer, J. J. Vasseur, F. Morvan, J. Org. Chem. 2009, 74,

6837-6842, [5] G. Pourceau, A. Meyer, J. J. Vasseur, F. Morvan, J. Org. Chem. 2009, 74, 1218-

1222, [6] G. Pourceau, A. Meyer, J.-J. Vasseur, F. Morvan, J. Org. Chem. 2008, 73, 6014–6017,

[7] L. Moni, G. Pourceau, J. Zhang, A. Meyer, S. Vidal, E. Souteyrand, A. Dondoni, F. Morvan,

Y. Chevolot, J.-J. Vasseur, A. Marra, ChemBioChem 2009, 10, 1369-1378, [8] G. Pourceau, A.

Meyer, Y. Chevolot, E. Souteyrand, J. J. Vasseur, F. Morvan, Bioconjugate Chem. 2010, 21,

1520-1529, [9] J. Zhang, G. Pourceau, A. Meyer, S. Vidal, J.-P. Praly, E. Souteyrand, J.-J.

Vasseur, F. Morvan, Y. Chevolot, Biosensor Bioelectronics 2009, 24, 2515–2521, [10] Y. Chevolot,

C. Bouillon, S. Vidal, F. Morvan, A. Meyer, J.-P. Cloarec, A. Jochum, J.-P. Praly, J.-J. Vasseur,

E. Souteyrand, Angewandte Chem. Intl Ed. 2007, 46, 2398-2402, [11] J. Zhang, G. Pourceau, A.

Meyer, S. Vidal, J. P. Praly, E. Souteyrand, J. J. Vasseur, F. Morvan, Y. Chevolot, Chem.

Commun. 2009, 6795-6797.

17

“NMR spectroscopy from diagnosing metabolic disorders towards

personalized medicine”

Calin Deleanu

“Petru Poni” Institute of Macromolecular Chemistry, Iasi

&

“Costin D. Nenitescu” Centre of Organic Chemistry, Bucharest

During its rather brief history, NMR spectroscopy was initially used by

physicists. It was only in the 1960’s when the chemical shift was discovered that the

chemical community started to use it and the field took off. NMR became an

indispensable tool in structure elucidation of pure compounds and until late 1980’s

this remained the most important type of application. Once the high field NMR

spectrometers entered the chemical community the method started to be used also

for complex mixture analysis, penetrating also fields like medicine or food sciences.

Today we see a rather balanced use of the NMR spectroscopy between the structure

elucidation of pure compounds and analysis of complex mixtures.

When it comes to applications of NMR to complex systems, like biological

ones, one should carefully balance between the excitement of the “potential” of the

technique and claims of “ultimate diagnosis tool capabilities”. Thus, one should be

always aware which techniques and protocols are valuable to medical research and

which ones can be extended to clinical practice.

The present paper starts with examples of structure elucidation of isolated

compounds, and moves to spectra of complex body fluids, discussing some

experimental factors, reproducibility, and data interpretation via either biomarker

identification approach or blind statistical classifier approach. The core of this paper

focuses on successful applications of NMR spectroscopy to clinical tests for metabolic

disorders. Finally, perspectives of using NMR in predictive and personalized

medicine are discussed.

1.01.21.41.61.82.02.22.42.62.8 ppm

CitCit

DMA

GABAPyr

Lac

Ala

Val

Val

Figure 1. Water-suppression whole 1H-NMR spectrum (400 MHz) of a urine sample

(left),

with examples of metabolite signal assignments in the region 1.0-2.8 ppm (right).

18

High sensitive analytic platform to assess interfaces based on Magneto

Plasmonics (Magnetic SPR)

Eugen Gheorghiu, Sorin David, Cristina Polonschii, Dumitru Bratu and Mihaela Gheorghiu

International Centre of Biodynamics, Bucharest www.biodyn.ro

[email protected]

Recent developments within the International Centre of Biodynamics concerning

chip preparation as well as accomplishment of a measuring set-up allowing

magneto-optic surface-plasmon-resonance (MOSPR1,2) assays are presented.

The platform comprises the magneto-plasmonic sensor, the fast surface plasmon

resonance detection module, the electromagnet providing the oscillating magnetic

field (with controlled field strength and frequency) with actuation role for MOSPR

and the flow-through chamber with integrated microfluidics.

The physical transduction principle is based on the combination of the magneto-

optic activity of magnetic materials and plasmonic properties of selected metallic

layers. The actual structure of layers was optimized using a Transfer Matrix

approach3-5 based on the magneto-optical activity of the trilayers as a function of the

thickness and position of the Cr, Co and Au layers, and has been constructed in

house via physical vapor deposition of thin layers of Cr, Au and Co.

Such combination can produce a significant enhancement of the SPR effects that

strongly depends on the optical properties of the surrounding medium, allowing its

use for biosensing applications2. Calibration curves based on solutions with different

refractive indices show a steeper slope in the case of the magneto-optical sensor

proving an increased sensitivity.

The sensing avenues emphasizing analytical capabilities of the platform e.g. to

assess biomolecular reactions will be highlighted. Acknowledgment: This work is supported by the NANOMAGMA FP7-214107-2

and National Project RoNanomagma.

Selected References

[1] B. Sepúlveda, A. Calle, L. M. Lechuga, and G. Armelles, Optics Letters, 31, 8 (2006) 1085-1087

[2] D. Regatos, D. Fariña, A. Calle, A. Cebollada, B. Sepúlveda, G. Armelles, and L. M. Lechuga, J.

Appl. Phys. 108, 054502 (2010); doi:10.1063/1.3475711

[3] M. Born, E. Wolf, Principles of optics: electromagnetic theory of propagation, interference and

diffraction of light, 6th ed.; Pergamon Press: Oxford; New York, 1980.

[4] M. Gheorghiu, A. Olaru, A. Tar, C. Polonschii, E. Gheorghiu, “Sensing based on assessment of

non-monotonous effect determined by target analyte: case study on pore forming compounds”,

Biosensors and Bioelectronics, 24 (2009) 3517–3523

[5] A. Olaru, M. Gheorghiu, S. David, T. Wohland, E. Gheorghiu, “Assessment of the multiphase

interaction between a membrane disrupting protein and a lipid membrane”, J. Phys. Chem. B, 113

(2009), 14369–14380

19

Electro-Optic flow through system to appraise cell dynamics

Mihaela Gheorghiu, Sorin David, Cristina Polonschii, Szilveszter Gaspar, Dumitru Bratu

and Eugen Gheorghiu

International Centre of Biodynamics, Bucharest www.biodyn.ro

[email protected]

Noninvasive, long term appraisal of cell dynamics holds the promise for

development of effective sensitive cellular platforms suitable to assess the

interactions between noxious compounds (including unknown agents) and living

cells1,2 to be implemented in medical and environmental applications.

Taking up this challenge, recent developments within the International Centre of

Biodynamics concerning electro-optic evaluation of model cell cultures as well as

accomplishment of a measuring flow through electro-optical set-up allowing

impedimetric, imaging or Surface Plasmon Resonance (SPR) assays are presented.

Beyond combining impedance and optics (light microscopy) as implemented in

ECIS3 chips, we advance novel measurement configurations supported by modeling

tools4,5 pertaining to electrochemical impedance and SPR to reveal cell dynamics of

cells in relation to cell attachment to functionalized substrates, growth conditions6

and pore formation4,5,7. Acknowledgment: This work is supported by the NANOMAGMA FP7-214107-2

and National Projects 71-073 & 41-013.

Selected References

[1] S. Andreescu, M. Gheorghiu, R. E. Ozel, K. Wallace, Methodologies for Toxicity Monitoring and

Nanotechnology Risk Assessment Biotechnology and Nanotechnology Risk Assessment: Minding and Managing the

Potential Threats around Us, Chapter 7, pp 141–180, Chapter DOI: 10.1021/bk-2011-1079.ch007, ACS Symposium

Series, Vol. 1079, ISBN13: 9780841226609 eISBN: 9780841226616, Publication Date (Web): October 18, 2011

[2] E. Gheorghiu, M Gheorghiu, S David, C Polonschii, "Biodynsensing: sensing through dynamics of hybrid

affinity / cellular platforms; towards appraisal of Environmental and Biological Risks of Nanobiotechnology" in

NATO Science for Peace and Security Series B: Physics and Biophysics , Magarshak, Yuri; Kozyrev, Sergey;

Vaseashta, Ashok K. (Eds.) 2009, ISBN: 978-90-481-2522-7

[3] www.biophysics.com

[4] M. Gheorghiu, A. Olaru, A. Tar, C. Polonschii, E. Gheorghiu, “Sensing based on assessment of non-

monotonous effect determined by target analyte: case study on pore forming compounds”, Biosensors and

Bioelectronics, 24 (2009) 3517–3523

[5] A. Olaru, M. Gheorghiu, S. David, T. Wohland, E. Gheorghiu, “Assessment of the multiphase interaction

between a membrane disrupting protein and a lipid membrane”, J. Phys. Chem. B, 113 (2009), 14369–14380

[6] Gaspar, S., David, S., Polonschii, C., Marcu I., Gheorghiu, M., Gheorghiu E. Simultaneous impedimetric and

amperometric interrogation of renal cells exposed to a calculus-forming salt, Anal Chim Acta 713, (2012), 115–120

[7] M. Gheorghiu*, C. Polonschii, S. David, A. Olaru, E. Gheorghiu, SPR Bioanalytical platform to appraise the

interaction between antimicrobial peptides and lipid membranes, In Optical Nano- and Microsystems for

Bioanalytics, Series Chemo and Biosensors, Springer (2012) in press

20

Institut des Biomolécules Max Mousseron (IBMM)

UMR 5247

CNRS-Universités Montpellier 1et 2

Developing the « green tool box » for organic synthesis

Dr Frédéric Lamaty

Directeur de Recherche CNRS

Team Green chemistry and Enabling Technology

Institut des Biomolécules Max Mousseron (IBMM)-UMR 5247 CNRS-UM1-UM2,

Université Montpellier 2, cc1703, Place Eugène Bataillon, 34095 Montpellier Cedex 05,

France

Organic synthesis, including the preparation of biomolecules and bioactive

compounds, needs to comply with the environmental and societal needs for

sustainable synthetic methods. Based on the 12 principles of Green Chemistry, we

propose to pursue research in the field of biomolecules that will contribute to the

sustainable development of chemistry. Examples of our research activity for the

development of eco-friendly methods (“green tool box”) with applications in the

synthesis of value added molecules such as peptides, amino acids, heterocycles will

be presented.

Results in the following areas will be presented :

· Solvent-free reactions (mechanochemistry)1

· PEG as alternative solvents and polymeric support2

· Microwave activation3

References : 1. Declerck, V.; Nun, P.; Martinez, J.; Lamaty, F. Angew. Chem. Int. Ed. 2009, 48, 9318. Baron, A.;

Martinez, J.; Lamaty, F.Tetrahedron Lett. 2010, 51, 6246. Nun, P.; Martin, C.; Martinez, J.; Lamaty, F.

Tetrahedron 2011, 67, 8187.

2. Ribière, P.; Declerck, V.; Nédellec, Y.; Yadav-Bhatnagar, N.; Martinez, J.; Lamaty, F. Tetrahedron 2006,

62, 10456. Colacino, E.; Villebrun, L.; Martinez, J.; Lamaty, F.Tetrahedron 2010, 66, 3730

3. Declerck, V.; Ribière, P.; Nédellec,Y.; Allouchi, H.; Martinez, J.; Lamaty, F. Eur. J. Org. Chem. 2007,

201. Petiot, P.; Charnay, C.; Martinez, J.; Puttergill, L.; Galindo, F.; Lamaty, F.; Colacino, E. Chem.

Commun. 2010, 8842. Baron, A.; Verdié, P. ; Martinez, J.; Lamaty, F. J. Org. Chem. 2011, 76, 766-772.

21

Genome as a Source for the Discovery of New Peptide Hormones.

Synthesis and Pharmacological Characterization of New Active

Peptides.

Puget Karine, Carnazzi Eric, Le Gallic Lionel, Valeau Stéphanie, Clavier Karine,

Subra Gilles, Gaudry Hervé, Ripoll Jean-Philippe, Bergé Gilbert, and Martinez Jean

Institut des Biomolécules Max Mousseron (IBMM) UMR5247, Université Montpellier 1,

Université Montpellier 2, Faculté de Pharmacie, 15 Av Charles Flahault, 34093 Montpellier

Cedex 5, France, e-mail: [email protected]

We have designed a program for generating active peptides from protein and

genomic sequence data. This program is able to search in the available data

concerning protein structures and nucleotidic sequences to provide putative natural

active peptide sequences ending by a C-terminal amide.

Among the peptide sequences that were generated, quite an important number have

been synthesized, either in 96-well plates on classical solid supports using an ACT

instrument, by the Multipin technology, or using classical peptide synthesis for the

longer peptides. So far, more than 3500 peptides of variable lenght were obtained.

As a general screening, these peptides were tested for their affinity to Guinea Pig

brain membranes and for their activity on a second messenger system (cAMP, IP,

Ca++) on transfected cells. Among the tested peptides, two of them showed high and

specific affinity for the brain membranes (in the nanomolar range) and a significant

activity in stimulating cAMP accumulation in various cells.

The details of the mining program will be presented, as well as the automated

synthesis on solid support of libraries of amidated peptides and their general

screening. The pharmacology of active peptides that were identified will be

presented in more details.

References "Oligonucléotides permettant l'identification de précurseurs d'hormones peptidiques amidées", J. MARTINEZ &

C. GOZE, Brevet n° 9710643 déposé le 26 août 1997, PCT WO 99/10361 March 1999.

"Rational selection of putative peptides from identified nucleotide, or peptide sequences, of unknown function", J.

A. CAMARA y FERRER, C. A.THURIEAU, J. MARTINEZ, G. BERGE & C. GOZE, PCT WO 00/50636 August 2000.

"Nouveau polynucléotide utilisable pour moduler la prolifération des cellules cancéreuses", E. FERRANDIS, J.

CAMARA, J. MARTINEZ & C. THURIEAU, French Patent 01/02801 March 2001, PCT/FR02/070700 September

2002. E. FERRANDIS, J. CAMARA, J. MARTINEZ & C. THURIEAU, cDNAs encoding BAA91361.1 protein

associated with modulating cancer cell proliferation and their use in therapy, PCT Int. Appl.(2002), WO

2002070700.

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