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RUSSIAN ACADEMY OF SCIENCES INSTITUTE OF PHYSICAL CHEMISTRY

RUSSIAN ACADEMY OF SCIENCES INSTITUTE OF PHYSICAL CHEMISTRY. Laboratiry of Physical Chemistry of Supramolecular Systems. FUNCTIONAL SUPRAMOLECULAR SYSTEMS AT INTERFACES. V . V. Arslanov , M.A.Kalinina. Leninskij pr. 31, Moscow, 119991 Russia Tel.: +7 (095) 955-4489 , pcss_lab @ mail .ru.

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RUSSIAN ACADEMY OF SCIENCES INSTITUTE OF PHYSICAL CHEMISTRY

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  1. RUSSIAN ACADEMY OF SCIENCES INSTITUTE OF PHYSICAL CHEMISTRY Laboratiry of Physical Chemistry of Supramolecular Systems FUNCTIONAL SUPRAMOLECULAR SYSTEMS AT INTERFACES V.V.Arslanov, M.A.Kalinina 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.

  2. Dynamics Composition tuning Diffusion-binding Diffusion+Binding Diffusion-Binding+Isolation

  3. “MOLECULAR PUMP” sensing LB membrane for selective calcium determination Immobilization of non-amphiphilic Ca-ionophore in LB film of mixed monolayers with octadecylamine - - - - С О О С О О С О О С О О N N O O + Ca-ionophore (BAPTA) 1,2-Bis(2-aminophenoxy)ethane-N,N,N’N’-tetraacetic acid Octadecylamine (ODA) Fundamental problem of ISE’s membranes: Only a part of binding agent participates in analyte recognition. Diffusion+Binding A2/molec.

  4. QCM responses of a LB film of ODA and Ca-ionophore (BAPTA) to presence of Ca2+ ions in aqueous solution of CaCl2 Effect of interfering ions on the response of 17 layer BAPTA/ODA LB membrane Response time is 10 s pH 7.2 Detection limit is 10-11M CaCl2 CaCl2/0.1 NaCl BaCl2 10-3 M

  5. 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 Surface pressure control of preorganization p = 23 mN/m 5 - 5 min 4 - 1.5 min 3 - 40 s 2 - 10 s p = 32 mN/m 1 - 5 min

  6. Impedance response for 4 layer ODA/BAPTA LB membranes before (original film) and after immersion into solutions of 10-8 M , 10-6 M and 10-4 M of CaCl2 10-4 M 10-6 M 10-8 M free film

  7. Time-dependent reflectance changes measured at a fixed angle of incidence (q = 64°) for 6 layer ODA/BAPTA LB membranes exposed in calcium chloride solutions. Linear calibration of REF signal vs calcium concentration for 10 sec of measurements Where Ca2+-cations are settle? The ratio of number of ionophore molecules to number of Ca2+ ionsin LB (10 seconds) 1:10 1:5 1:3 1:1 Concentration of Ca2+ ions in solution, M 10-1 10-4 10-6 10-8

  8. MECHANIZM OF “MOLECULAR PUMP” OPERATION (LB film of mixed monolayers of Ca-ionophore and ODA) Region of local increase of pH C18H37NH3+ - + - + - + - + + + ++ - + - –COO- pHh - + - + - + - + + ++ + - + - Са2+ Ca(OH)2 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.

  9. a 50 m b 50 m c 1 m Optical microscopy images for 17 layer ODA/BAPTA (a, b) and ODA (c) LB membranes immersed into aqueous solution of 10-2 M CaCl2 ODA/BAPTA 10 s 1.5 min ODA 5 min

  10. Conformational tuning N N N N - powerful method to control the receptor properties of LB membranes Macrocyclic polyamine Conformational flexibility of the ring dicetyl cyclen (DCC) Amphiphilic compound

  11. pH-control Monolayer charge Lc 0 80,4 pH 5.6 N N Surface pressure control Monolayer density pH 3.5 N N pH 8.5 Ld 0 76,2 N N N N LEp 69,5 0 N N N N Control over macrocycle conformation In 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/conformationarrangement

  12. Intensity, Intensity, Intensity, imp imp imp NiKa 250 NiKa CuKa 150 CuKa CuKa 200 NiKb NiKb 40 100 150 CuKb N N N N N N N N N 100 20 CuKb 50 N N N N N N CuKb N N N Cu N N N N N N N N NiKb NiKa 50 N Cu N Cu N Cu N Ni N Cu N Ni N N Ni 0 0 7 8 9 10 0 7 8 9 10 7 8 9 10 Energy, keV Energy, keV Energy, keV Ni ) ) 4.2 4.8 pH 4.6 INVERSION OF MACROCYCLE SELECTIVITY IN LANGMUIR MONOLAYER Ni(II) Ni(II) Ni(II) Cu(II) Ni(II) Cu(II) Cu(II) Ni(II) Cu(II) Ni(II) Ni(II) Cu(II) Ni(II) Cu(II) Cu(II) Ni(II) Cu(II) Ni(II) Cu(II) Ni(II) Ni(II) Cu(II) Ni(II) Ni

  13. PLANAR ELEMENT OF CHEMICAL SENSOR Cu(II) Zn(II) Ni(II) Selectivity of DCC in ultra thin films Cast film of DCC LB film of DCC Cu(II) Zn(II) Ni(II) SENSING UNIT TRANSDUCING PLATFORM PLANAR SENSOR Quartz crystal microbalance LB film of DCC + 10 mmol CuCl2 Testing measurements (2 weeks later) calibration -8 0.01 mol CuCl2

  14. N H O N O H H N N + 2 Z n N N H H The interactionsof Zn(II)-DCC complex with imide group of the uracil in SAM-supported LB monolayer Interaction of Zn-DCC with deprotonated imide moiety 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 “Switch on” and “switch off” the binding of uracil Zn(II)-DCC complexes preformed in Langmuir monolayer Zn(II)-DCC complexes formed in LB film (LB of pure DCC + solution of ZnCl2) SPR- sensograms uracil uracil, 10-3 M, pH 7.3 adenine

  15. - O R O P - O O H H N N 2 + Z n N N H H The interactions of Zn(II)-DCC complex with dianionic phosphate monoester Zn-DCC as monotopic receptor for dianionic phosphate monoester HPO42- H2PO4- 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

  16. Monolayers of polymeric compounds (linear, branched, comb-like) Polymerization of monomers in monolayers • PROBLEMS • Demand of amphiphility • Restrictions on reaction conditions(temperature, water surface) • Common system – photopolymerization of olefins • PROBLEMS OF POLYMER APPLICATION • Functionalization • Formation of true monolayer on the water surface • Low level of organization The Enhancement of Nanodevice Stability Low-molecular weight compounds TYPES OF INSTABILITY STRUCTURALTHERMALMECHANICAL CHEMICAL Reorganization ToC Tip Solvent Reorganization ToC Tip Solvent

  17. R N N R H N H N Functionalized surfaces and ultrathin films of 2D networked polymer matrix for immobilization of molecules and nanoparticles Reactive surface or 2D block of cross-linked polymer formed by use of monolayer technique Functional groups of the network Reactive oligomer(s) Functional molecules or nanoprticles interlocked in polymer network Interlocking of molecules or nanoparticles in matrix of networked polymer Dicetylcyclen 2D hybrid blocks of networked polymer containing molecules or nanoparticles Gold nanoparticle 3D multilayer structure assembled of 2D blocks by LB technique

  18. Epoxy-novolac oligomer (GY-1180) 24 hours H3[PW12O40] 4 hours n 10 min water NH -CH CH -NH-CH CH -NH-CH CH NH 2 2 2 2 2 2 2 2 M A T E R I A L S Compression isotherms of epoxy oligomer monolayers on the surface of water and aqueous H3[PW12O40]solutions at various exposure times 24 hours H3[PW12O40] CURING AGENTS 4 hours Triethylenetetramine (TETA) 10 min Polyoxometalates:H3[PW12O40] water Epoxy oligomer H3[PW12O40] ECOF2004

  19. Н2О Н2О Preparation of cross-linked monolayer by use of mixture of oligomer and curing agent Formation of mixed monolayer 2D cross-linking Epoxy oligomer in monolayer Curing agent in mixed monolayer (TETA) 24 hours Compression isotherms of mixed monolayers of epoxy oligomer and triethylenetetramine on the surface of water at various exposure times 4 hours 1 hour

  20. Н2О Н2О TRANSMISSION ELECTRON MICROSCOPY IMADGES OF TWO-DIMENSIONAL EPOXYAMINE POLYMER NETWORKS TEM image of one monolayer of epoxyamine cross-linked polymer deposited onto the TEM grid Au nanoparticles immobilized in 2D epoxyamine polymer network One monolayer One monolayer Immobilization of gold nanoparticles

  21. 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 Interaction of Cu2+ cations with DCC immobilized into cross-linked polymer matrix “Complexation-Regeneration” cycles pH 5.6 Phase of amphiphilic cyclen pH 2.0

  22. R N Zn(II) N R H N H N O N– O N H Zn(II)/ DCC/URACIL COMPLEXES IMMOBILIZED IN 2D NETWORKED EPOXYAMINE MATRIX TEM - image Zn(II)-DCC complex/Uracil One monolayer 50 nm

  23. Design active biomimitic surfaces for programmed self-assembling of nucleotides P P P P N H 2 X N N O H O P N O N O O H S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S H O O H X O O O H O P O P P O O H O H O H O O O N H N H O O O H H pH 8.5 adenosine-5’-phosphate (AMP) Zn(II)-BC Langmuir monolayer uridine-5’-triphosphate (UTP) pH 7.0-7.5 LB monolayer transferred on SAM Active matrices of Zn(II)-BC in nucleotide solution

  24. S S S S S S S S Molecular recognition in Zn(II)-BC monolayers – water/solid interface 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. Zn(II)-BC monolayer binds both imide and phosphate groups and can be used as a sensing unit of chemical sensors 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. 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.

  25. P P P P P P P P P P P P P P P P P P P P P P P P X X S S S S S S S S S S S S S S S S S S S S S S S S X X X X X 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 via base pairing and the coordination of the terminal phosphate group of complementary nucleotide to the other head of Zn(II)-BC • 3)The binding of the terminal phosphate and decomposition of the couple • 4)The binding of the second complementary nucleotide via specific base pairing 4 2 3 1 X

  26. P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P X X X X S S S S S S S S S S S S S S S S S S S S S S S S S S S S S S X X X P P P X 1st step UTP 2nd step ATP X X ONE- AND MULTI-STEP HIERARCHICAL SELF-ASSEMBLING OF FUNCTIONALIZED SUPRAMOLECULAR SYSTEMS MULTI-STEP ONE-STEP 3d step UTP X

  27. 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 P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P X S S S S S S S S S S S S S S S S S S S S S S S S X X X X X X P P P P 1st step UMP X X 2nd step ATP 1st step ATP 1st step 2nd step UMP 2nd step 3d step X X X X X X X ?

  28. OUTLOOKS P P P P P P P P P P P P P P P P P P P P P P P S S S S S S S S S S S S S S S S S X B A A G C X X X X X X X X X X X Different 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 new biocompatible and non-toxic materials through polymerization of complementary matrices organized arrays of artificial codons

  29. AgJ LB patterning via gel stamping agarose stamp H2O + KJ Ag+ +J-= AgJ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ LB film of Ag(I)-DCC complex Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ Ag+ A B A B A Ag+ Ag+ Ag+ Ag+ Ag+ UV treatment: LB decomposition + Ag reduction A B A B A arrays of silver nanoparticles patterned surface A B A B A

  30. Optical microscopy images for 17 layer arrays of silver nanoparticles silicon surface (stamp’s “photo”) 50m

  31. arrays of silver nanoparticles silicon surface (stamp’s “photo”) 50 m

  32. Laboratiry of Physical Chemistry of Supramolecular Systems

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