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Larissa Valkova, Oskar Koifman

Controlled Formation of 2D- Nanoparticles in Langmuir Layers and 3D- Supermolecules in Langmuir-Blodgett Films of Azaporphyrins. Larissa Valkova, Oskar Koifman Research Institute of Macroheterocyclic Compounds Ivanovo State University of Chemistry and Technology Russia.

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Larissa Valkova, Oskar Koifman

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  1. Controlled Formation of 2D-Nanoparticles in Langmuir Layers and 3D-Supermolecules in Langmuir-Blodgett Films of Azaporphyrins Larissa Valkova, Oskar Koifman Research Institute of Macroheterocyclic Compounds Ivanovo State University of Chemistry and Technology Russia

  2. Controlled Self-Assembly of Azaporphyrins in Langmuir Layers and Langmuir-Blodgett Films gas sensors, optical limitation of laser irradiation, photosensitizes inphotodynamic therapy,… Solutions – Solid Films Aims • Films with controlled structure • NANOSTRUCTURES and SUPERMOLECULES • Methods 2

  3. «Bottom-up» and «top-down» methods of nanoparticles fabrication

  4. Langmuir-Blodgett Technology

  5. Langmuir-Blodgett Films Vertical lift Horizontal lift 5

  6. Methods of films investigation

  7. Classical Model of Langmuir Layer Since 1980… Qualitative data of the layer structure

  8. FUNCTIONAL MATERIALS BASED ON AZAPORPHYRINE FILMS • Application problems Chemical sensors: poor selectivity with respect to volatile organiccompounds Semiconducting devices: low intrinsic conductivity • Fabrication problems General: a) poor reproducibility b) poor homogeneity

  9. Experiments to be explained…

  10. Langmuir layers of CuPctBu4Brewster-Angle Microscopy π=1.2 mN/mπ=16 mN/m 100 mm 100 mm Classical analysis MONOLAYER tillπ=24 mN/m 10

  11. New approach…Two-dimensional aggregation Classical monolayer Different n n=1 Nanostructured monolayer Colloid Journal2008, 70, 6-11 (Fulleren C60) 11

  12. Model and Method of Determination of the Layer Structure π(Atotal– NaggrAaggr) = NaggrkT π(A – Amol) = n-1kT xj = fj (с), were xj– parameters of the model с Xj : Saggr=Amoln; ci-face = 100%·Sproj-face/Ai ci-edge = 100%·Sproj-edge/Ai; ψmin=arcsin(Apack-edge/Amol);win-M=Amol–Aprojи winter-M-i=Аi–Amol; wfree-o=100%·(А0–Ai)/А0;ρaggr=Aproj-face/Amol; B=(Аi –Аf )/(f– πi)Ai;сi-aggr = 100%·Amol/Ai; сf-aggr = 100%·Amol/Af; nH2O (H2O/Pc)=(win-M/0.1)/n. di = df= xj = fj (с) 12

  13. Quantitative data of the layer structure 100 mm 100 mm π= 0 π=1.2 mN/m Stable monolayer π=16 mN/m Monolayer - Polylayer (Classical analysis - Monolayer) BAM, CuPctBu4, 400х300µm 13 100 mm

  14. Diagram of the layer statesPrognosis of the resultsPassport of the floating layers CuPctBu4 14

  15. Floating polylayers of CuPaz 4 CuPaz 15

  16. Supermolecules in LB-films ofCuPaz • black - initial • red - 3 h. old Tetralayer Bilayer Monolayer structure Multi-stacked supermolecules are experimentally registered 16 22

  17. Different structures of CuPaz LB-films Monolayers Bilayer Tetralayers Stable

  18. Nanostructures of CuPaztBu4 CuPaztBu4 18

  19. Formation of 3D-nanostructures of CuPctBu4in heterostructures CuPctBu4/Сdstearate-d35 1 layer Pc χ-form BilayerPc 2 layers Сd- stearate CuPctBu4 β-form LB-film of A1B2stearbefore (left) and after heating till 120C

  20. Imprint of CuPctBu4Langmuir layer in Сdstearate matrics On the water In LB-film A1B2ст Small-angle neutron diffraction pattern

  21. Reversible temperature transition in oriented supermolecular LB-films ofCuPaz oligomer 21

  22. Hierarchy of azaporphyrin assembly CuPaztBu4 CuPctBu4 Floating monolayers 100 mm 100 mm 2D- nanoaggregates near 5 nm microaggregates 3-5 µmor 100-300 µm are groped in Floating polylayers and LB-films CuPc(tBu,NO2)4 3D- nanoaggregates near 5 nm aggregates 50-200 nmand near5 µm are groped in LB-film 22

  23. WE WOULD LIKE 23

  24. But usually the films look like…

  25. 2D- or 3D-nanoparticles arethe units of structure in floating layers of macroheterocycles QUNTITATIVE MODEL and METHOD LB-technology is an instrument for formation of nanostructures of organic compounds Main problems are the problems of NANOARCHITECTONICS 25

  26. 2012 The work is supported by : Russian Foundation for Basic Research Education and Science Ministry of the Russian Federation Russian Academy of Sciences 26

  27. Main publications • Thin Solid Films2000, v. 379, pp. 279-286 • Langmuir2001, v. 17 (12), pp. 3639-3642 • Thin Solid Films2001, v. 401 (1-2), pp. 267-272 • Mater. Sci. and Eng. C, Biomimetic and Supramolecular Systems 2002, v. 22, pp. 167-170 • Colloids and Surfaces A, Physicochemical and Engineering Aspects,2002, v.198 - 200, pp. 891 - 896 • Journal of Applied Crystallography2003, v. 36, pp. 758-762 • Biosensors and Bioelectronics2004, v. 48, pp. 642-647 • Proceedings of the International Schools on Advanced Material Science and Technology, Jesi, Italy 2002,2003,2005 • Applied Surface Science2005, 245, P. 369-375 • Colloid Journal2008, 70, 6-11 • Langmuir 2008, V. 24, No 9. P. 4857-4864 • Journal of Porphyrins and Phthalocyanines2010,14,513-522 • Macroheterocycles2011, V. 4, N 3, P. 222-226 • Journal of Porphyrins and Phthalocyanines2011,15,1044-1051

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