V.V. Arslanov, M.A.Kalinina

FUNCTIONAL SUPRAMOLECULAR SYSTEMS

AT INTERFACES

Leninskij pr. 31, Moscow, 119991 Russia

Tel.: +7 (095) 955-4489, pcss_lab@mail.ru

1. Dynamic properties of organized ultra thin films at liquid and solid surfaces.

2. 2D polymer networks for immobilization of functional molecules and nanoparticles and improvement stability of supramolecular devices.

DD yy nn aa mm ii cc ss

Diffusion-binding Diffusion+Binding Diffusion-Binding+Isolation

Composition tuning

Compression isotherms of ODA monolayer and mixed monolayer of ODA+Ionophore

0

10

20

30

40

50

60

0 20 40 60 80

Surface area,

, mN/m

Е2/molec.

π

octadecylamine+ionophore

octadecylamine

Ca-ionophore (BAPTA)1,2-Bis(2-aminophenoxy)ethane-

N,N,N’N’-tetraacetic acid

“MOLECULAR PUMP” sensing LB membrane for selective calcium determination

Immobilization of non-amphiphilic Ca-ionophore in LB film of mixed monolayers with octadecylamine

Octadecylamine

(ODA)

A2/molec.

Fundamental problem of ISE’s membranes:Only a part of binding agent participates in analyte recognition.

NN

O O

СОО-

СОО- СОО- СОО-

Diffusion+Binding

+

Effect of interfering ions

on the response of 17 layer

BAPTA/ODA LB membrane

QCM responses of a LB film of ODA and Ca-ionophore (BAPTA) to presence of Ca2+ ions in aqueous solution of CaCl2

BaCl2

10-3 M0

300

600

900

1200

-8 -7 -6 -5 -4 -3 -2 -1lg[Ca2+]

ma

ss u

pta

ke

, n

g

1

2

CaCl2/0.1 NaCl

CaCl2

[metal salt],

1.0010-3 M

Mass uptake (m) (ng)

CaCl2 827

BaCl2 58

MgCl2 72

NaCl 24

KCl 8

Response time is Response time is 10 s10 s

pH 7.2pH 7.2

Detection limit is Detection limit is 1010-11-11MM

= 23 mN/m

5 - 5 min

4 - 1.5 min

3 - 40 s

2 - 10 s

= 32 mN/m

1 - 5 min0

200

400

600

800

1000

1200

-8 -6 -4 -2lg [Ca

2+]

Mas

s u

pta

ke,

ng

1

5

43

2

Surface pressure control of

preorganization

Influence exposure time and of deposition surface pressure on a work of sensor.

Mass uptake vs calcium concentration dependencies obtained with 17-layer ODA/BAPTA LB membranes deposited on quartz crystals at surface pressure 32 mN m-1 and 23 mN m-1 and

exposed to CaCl2 solutions

Impedance response for Impedance response for 4 layer4 layer ODA/BAPTA LB ODA/BAPTA LB

membranes before (original film) and after immersion membranes before (original film) and after immersion

into solutions of 10into solutions of 10-8-8 M , 10 M , 10-6-6 M and 10 M and 10-4-4 M of CaCl M of CaCl22

0

10

20

30

40

50

60

70

80

0 50 100 150 200 250

ZRe, kOhm

ZIm

, kO

hm

10-4 M

10-6 M

10-8 M

free film

Time-dependent reflectance changes measured at a fixed angle

of incidence ( = 64°) for 6 layer ODA/BAPTA LB membranes

exposed in calcium chloride solutions.

0 25 50 75 100 125 150 175 200 225 250 275 3004200

4400

4600

4800

10-8 M

10-6 M

10-4 M

10-2 M

Ca2+

refle

cta

nce

, a

rb.

un

its

time, sec

44

44,2

44,4

44,6

44,8

-8 -6 -4 -2lg [Ca2+]

refl

ecta

nce

, a

rb.

un

its

Linear calibration of REF signal vs calcium concentration for 10

sec of measurements

10-810-610-410-1Concentration of Ca2+ ions in solution, M

1:11:31:51:10

The ratio of number of ionophore molecules to number of Ca2+ ions in LB (10 seconds)

Where Ca2+-cations are

settle?

MECHANIZM OF “MOLECULAR PUMP” OPERATION

(LB film of mixed monolayers of Ca-ionophore and ODA)

Са2+

Ca(OH)2

–COO-

C18H37NH3+

- + - + - + - + + + ++ - + - pHh

- + - + - + - + + + + + - + -

Са2+ + 2OH- = Ca(OH)2

1. Specific molecular organization of the film providing both a weak bonding of ions with ionophore and rapid transfer of Ca-ions.

2. Local increase of pH in sites of film with increased content of protonated amine groups. The precipitation of Ca hydroxide is observed in this sites.

Region of local increase

of pH

Optical microscopy images for 17 layer ODA/BAPTA (a, b) and ODA (c) LB Optical microscopy images for 17 layer ODA/BAPTA (a, b) and ODA (c) LB membranes immersed into aqueous solution of 10membranes immersed into aqueous solution of 10-2-2 M CaCl M CaCl

22

50 ma 50 mb

1 mc

1.5 1.5 minmin

10 s10 s

5 min5 minODAODA

ODA/BAPTAODA/BAPTA

N

N N

N

Macrocyclicpolyamine

Conformationalflexibility of the ring

Amphiphiliccompound

dicetyl cyclen(DCC)

Conformational tuning

- powerful method to control the receptor properties of LB membranes

0

10

20

30

40

50

60

50 70 90 110 130 150

Аrea per molecule, square angstroms

,mN/m

Condensedstates

Expanded state NN NN

69,5 0LEp

N

NNN

76,2 0

Ld

80,40

N

NN

N

Lc

0

10

20

30

40

50

60

40 70 100 130 160

Area per molecule (square angstroms)

,mN/ m

pH 3.5pH 5.6

pH 8.5

Surface pressure control Monolayer density

pH-controlMonolayer charge

Control over macrocycle conformationIn Langmuir monolayer

Monolayer is a precursor of solid state ultra thin film (LB film).

Evaluation of functional efficiency as well as adjustment of the molecular composition/conformation arrangement

4.2

pH4.6 4.8

Cu(II)Cu(II)Ni(II)

Ni(II)

Ni(II)

Cu(II)

Cu(II)

Cu(II)

Cu(II)

Cu(II)

Cu(II)Ni(II)

Ni(II)Ni(II)

Ni(II)

Ni(II)

Ni(II)

Ni(II)

Ni(II)

Ni(II)Cu(II)

Cu(II)

Ni(II)

INVERSION OF MACROCYCLE SELECTIVITY IN LANGMUIR MONOLAYER

7 8 9 100

50

100

150

200

250CuK

NiK

NiK

CuK

Intensity,

imp

Energy, keV

NN CuN

NNN N Cu

NNN N Cu

7 8 9 100

20

40

NiK

NiK

CuK

CuK

Intensity,

imp

Energy, keV

NNN Cu

NNN N Cu

NNN N Ni

Intensity,

imp

Energy, keV7 8 9 10

0

50

100

150NiK

CuK

NiK

CuK

)) NiN

NN N Ni

NNN N Ni

NNN N

PLANAR ELEMENT OF CHEMICAL SENSORPLANAR ELEMENT OF CHEMICAL SENSOR

50

100

150

200

250

300

350

400

-8 -7 -6 -5 -4 -3 -2lg [Cu(II)]

f, Hz

DCC LB-film ( 11 layers)

0

80

160

240

320

400

0 2 4n, number of cycles

f, Hz

SENSING UNIT TRANSDUCING PLATFORM PLANAR SENSOR+LB film of DCCQuartz crystal microbalance

calibration

Testing measurements(2 weeks later)

-8

10 mmol CuCl2

0.01 mol CuCl2

0

50

100

150

200

f, Hz

Zn(II)Ni(II)

Cu(II)

Cu(II) Zn(II) Ni(II)

0

50

100

150

200

f, Hz

Cast film of DCC LB film of DCC

Selectivity of DCC in ultra thin films

The interactions of Zn(II)-DCC complex with imide group of the uracil in SAM-supported LB monolayer

Time-dependent changes of resonance angle measured for SAM-supported LB monolayer of Zn(II)-DCC complex exposed to the uracil

or adenine solution.

(inset); the linear calibration of maximal SPR signal on a logarithm of uracil concentration

Zn(II)-DCC complexes preformed in Langmuir monolayer

Zn(II)-DCC complexes formed in LB film(LB of pure DCC + solution of ZnCl2)

adenine

uracil

NN

N NZn+2

H

HH

H

N

NH

O O

Interaction of Zn-DCC with deprotonated imide

moiety

SPR-sensogram

suracil, 10-3 M, pH

7.3

“Switch on” and “switch off” the binding of uracil

The interactions of Zn(II)-DCC complex with dianionic phosphate monoester

SPR kinetic curves of phosphate recognition by SAM-supported LB monolayer of Zn(II)-DCC formed after monolayer transferring on SAM support:

the binding of HPO42- in 10-4 M of Na2HPO4 at pH 7.5

and the curve obtained for 10-4 M NaH2PO4 at pH 6.5

O-PRO

O-

O

Zn2+NN

N N

HH

H H

Zn-DCC as monotopic

receptor for dianionic

phosphate monoester HPO4

2-

H2PO4-

SolventTipToCReorganization

TYPES OF INSTABILITY

STRUCTURAL THERMAL MECHANICAL CHEMICAL

The Enhancement of Nanodevice Stability

Low- molecular weight compounds

ReorganizationToC Tip Solvent

Monolayers of polymeric compounds

(linear, branched, comb-like)

PROBLEMS OF POLYMER APPLICATION• Functionalization• Formation of true monolayer on the water surface• Low level of organization

Polymerization of monomers in monolayers

PROBLEMS Demand of amphiphility Restrictions on reaction conditions

(temperature, water surface) Common system –

photopolymerization of olefins

Functionalized surfaces and ultrathin films of 2D networked polymer Functionalized surfaces and ultrathin films of 2D networked polymer

matrix for immobilization of molecules and nanoparticlesmatrix for immobilization of molecules and nanoparticles

2D hybrid blocks of networked polymer containing molecules or nanoparticles

3D multilayer structure assembled of 2D blocks by LB technique

Reactive surface or 2D block of cross-linked polymer formed by use of monolayer technique

Interlocking of molecules or nanoparticles in matrix of networked polymer

Functional groups of the network

Functional molecules or nanoprticles interlocked in polymer network

Reactive oligomer(s)

Gold nanoparticle

NH

NNN

R

R HDicetylcyclen

M A T E R I A L SM A T E R I A L SM A T E R I A L SM A T E R I A L S

Triethylenetetramine (TETA)

Polyoxometalates: H3[PW12O40]

Epoxy-novolac oligomer (GY-1180)

O

CH2

HC

H2C

O

CH2

O

CH2

HC

H2C

O

CH2

O

CH2

HC

H2C

O

n

NH2-CH2 2 2 2NH2CH 2CH -NH-CH 2-NH-CHCH

CURING AGENTS

Compression isotherms of epoxy

oligomer monolayers on the surface of

water and aqueous H3[PW12O40] solutions

at various exposure times

water

10 min

4 hours

24 hours

H3[PW12O40]

water

10 min

4 hours

24 hours

H3[PW12O40]

H3[PW12O40]

Epoxy oligomer

ECOF2004

Formation of mixed monolayer 2D cross-linking

Н2О

Н2О

Preparation of cross-linked monolayer by use of mixture of oligomer and curing agent

0

5

10

15

20

25

30

0 50 100 150 200 250 300

A, A2/molec.

, mN/m

1 час

4 часа

24 часа

II

I

1 hour

24 hours

4 hours

Compression isotherms of mixed monolayers of

epoxy oligomer and triethylenetetramine on the

surface of water at various exposure times

Curing agent in mixed monolayer (TETA)

Epoxy oligomer in monolayer

TRANSMISSION ELECTRON MICROSCOPY IMADGES OF TWO-DIMENSIONAL EPOXYAMINE POLYMER NETWORKS

Au nanoparticles immobilized in 2D epoxyamine polymer network

One monolayer

Immobilization of gold nanoparticles

Н2О

Н2О

TEM image of one monolayer of epoxyamine cross-linked polymer

deposited onto the TEM grid

One monolayer

AFM-IMAGE OF MIXED MONOLAYER OF TERNARY SYSTEM - EPOXY OLIGOMER/TRIETHYLENETETRAMINE (CURING AGENT)/DICETYLCYCLEN - ON THE

SURFACE OF SILICON

Matrix of cross-linked epoxy-amine

polymer

Phase of amphiphilic

cyclen

Interaction of Cu2+ cations with DCC immobilized into cross-linked polymer matrix

“Complexation-Regeneration” cycles

pH 5.6

pH 2.0

Zn(II)/ DCC/URACIL COMPLEXES IMMOBILIZED IN 2D NETWORKED EPOXYAMINE MATRIX

Zn(II)NH

N

NN

R

R H

N –

NH

OO

Zn(II)-DCC complex/UracilTEM - image

50 nm

One monolayer

X PPP

X P

PO

OH

PO

O

OH

OH

OH

O

O

POO

OHOH NH

NH

O

O

OH

OH

O

POO

OHOH

N

N

N

N

NH2

NN

N NH H

N N

NNN

N NH

H

H

NH

H

CH38

Zn2+Zn2+

4 ClO4-

Zn(II)-BC

Langmuir monolayer

adenosine-5’-phosphate (AMP)

uridine-5’-triphosphate (UTP)

pH 8.5

S S S SSS SS

LB monolayertransferred on SAM

S S S SSS SSS SSS SS S S S S SS SSS S

Active matrices of Zn(II)-BC in nucleotide solution

pH 7.0-7.5

Design active biomimitic surfaces for programmed self-assembling of nucleotides

Molecular recognition in Zn(II)-BC monolayers – water/solid interface

S S S SSS SS

0

30

60

90

120

0 1000 2000 3000 4000 5000F, Hz

Z R

e, O

m

thiol-Zn(II)-BC

thiol-Zn(II)-BC-adenine

thiol-Zn(II)-BC-adenine-uracil

0 50 100 150 200 250 300

3796

3797

3798

3799

3800

3801

3802

0.1 g/l

H2O

min

uracil

Zn(II)-BC

time, min

The dependence of resonance angle of SPR spectra on time for Zn(II)-BC monolayer exposed to uracil solution with concentration of base 0.1gL-1 at pH 7.3; 20˚C.

Bode diagram for Zn(II)-BC monolayer exposed in adenine solution (0.05 gL-1) and in mixed solution of adenine/uracil with concentration of each base 0.05 gL-1. Red/Ox [FeCN6]3-/4-/KCl (0.1N), pH 7.35.

The dependence of resonance angle of SPR spectra on time for Zn(II)-BC monolayer exposed to Na3PO4 solution (10-4M of salt) at pH 7.5; 20˚C.

0 50 100 150 200 2503796

3797

3798

3799

3800

3801

3802

3803

Na3PO

4

Zn(II)-BC

min

time, min

Zn(II)-BC monolayer binds both imide and phosphate groups and can be usedas a sensing unitof chemical sensors

THE BINDING OF COMPLEMENTARY NUCLEOTIDES IS A MULTISTEP PROCESS CONTROLLED BY THE GEOMETRY OF THE ACTIVE MATRIX!!!(the hierarchical self-assembling of functionalized supramolecular systems)

1)The binding of the first nucleotide on one head of Zn(II)-BC

2)The coupling of complementary

nucleotide with a first one nucleotide with a first one

via base pairing and the via base pairing and the

coordination of the terminal coordination of the terminal

phosphate group of phosphate group of

complementary nucleotide complementary nucleotide

to the other head of Zn(II)-to the other head of Zn(II)-

BCBC

3)The binding of the terminal 3)The binding of the terminal

phosphate and phosphate and

decomposition of the coupledecomposition of the couple

4)The binding of the second 4)The binding of the second

complementary nucleotide complementary nucleotide

via specific base pairing via specific base pairing

XP

PP

S S S SSS SSS SSS SS S S S S S

XP

PP

XP

PP

XP

PP

XP

PP

XP

PP

X

PP

PXP

PP

S SSS S

21 34

XP

PP

P P P

S S S SSS SSS SSS SS S S S S S S

XP

PP

XP

PP

XP

PP

3d step UTP2nd step ATP1st step UTP

S

XP

PP

XP

PP

X

XP

PP

SS S S S S S S

XP

PP

S

XP

PP

XP

PP

0 100 200 300 400

3792

3794

3796

3798

3800

3802

UTP

ATP

ATP+UTP

Zn(II)-BC

min

time, min

ONE- AND MULTI-STEP HIERARCHICAL SELF-ASSEMBLING OF FUNCTIONALIZED SUPRAMOLECULAR SYSTEMS

0 50 100 150 200 250 300 3503774

3775

3776

3777

3778

3779

3780

3781

3782

ATP

UTP

UTP

H2O

Zn(II)-BC

min

time, min

ONE-STEPMULTI-STEP

S S S SSS SS

XP

XP

PP

XP

XP

PP

XP

XP2nd step

UMP

1st step ATP

S S S SSS SS

XP

PP

XP

PP

XP

PP

XP

PP X

PP

XP

PP

XP

P3d step2nd step1st step

S S S SSS SS

XP

PP

X P X P

2nd step ATP1st step UMP

Formation of self-organized matrices of non-uniform chemistry and topography by use of complementary

nucleotides with different number of phosphate residues and ”switch off” the process by UMP

0 50 100 150 200 250 300 3503790

3791

3792

3793

3794

3795

3796

min

H2O

UMP

ATP

Zn(II)-BC

time, min

0 100 200 300 400 500

3792

3795

3798

3801

3804

3807

3810

3813

UDP

UTPATP+ADP

H2O

Zn(II)-BC

min

time, min 0 50 100 150 200 250 3003790

3792

3794

3796

3798

H2O

min

ATPUMP

Zn(II)-BC

time, min

?

XP

PP

OUTLOOKSDifferent systems of controllable composition and structure can be produced using two types of complementary nucleotides and only type of matrix by means of complementary self-assembling of nucleotides at physiological pH

different chemical and biosensors and functionalized surfaces for cyclic preparative synthesis ( i.e. regioisomers) and catalysis

S S S S S S S

P

S

PX X

A B

new biocompatible and non-toxic materials through polymerization of complementary matrices

XP

P

XP

PP

XP

PP

XP

PP

XP

P

XP

P

organized arrays of artificial codons

S S S S S S S S

PX

PX

PXG C

A

S

LB patterning via gel stamping

agarose stamp

H2O + KJ

Ag+

Ag+

Ag+

Ag+ Ag+Ag+

Ag+

AA A

Ag+

Ag+

Ag+

Ag+

Ag+

Ag+

Ag+

B B

Ag+ +J-= AgJ

Ag+

AA A

Ag+

Ag+

Ag+

Ag+

Ag+

Ag+

Ag+

B B

AgJ

UV treatment:LB decomposition +Ag reduction

AA AB B

arrays of silver nanoparticlespatterned surface

LB film of Ag(I)-DCC complex

50 m

arrays of silver nanoparticles

silicon surface(stamp’s “photo”)

Optical microscopy images for 17 layerOptical microscopy images for 17 layer

50 m

silicon surface(stamp’s “photo”)

arrays of silver nanoparticles