Publications on the project |
043 Synthesis of calixarene-based ketocyanine fluorophores |
Authors: | Y. Matvieiev, I. Karpenko, A. Kulinich, A. Ryabitskii, V. Pivovarenko, S. Shishkina, O. Shishkin, V. Kalchenko | |
Summary: | Cup-shaped calix[4]arenes bearing one or two ketocyanine fluorophore fragments at the wide rim of the macrocycle are synthesized by condensation of formyl calix[4]arenes with arylmethylene(hetarylmethylene)cyclopentanones in the presence of the ionic liquid, dimethylammonium dimethylcarbamate (DIMCARB) and characterized using UV–vis and fluorescence spectroscopy. Strong positive solvatofluorochromism for the calixarene ketocyanines is observed. | |
Keywords: | calix[4]arenes, ketocyanines, chemosensors, solvatofluorochromism | |
Edition: | Tetrahedron Letters | | | 2011,
3922-3925,English |
043 A method of synthesis of 5-formyl-17-{(E)-[(3E)-3(4-methoxybenzylidene)-2-oxocyclopentylidene]methyl}-25,27-dipropyloxy-26,28-dihydroxycalix[4]arene |
Authors: | Y. Matvieiev, I. Karpenko, A. Kulinich, V. Pivovarenko, V. Kalchenko | |
Summary: | A method of synthesis of 5-formyl-17-{(E)-[(3E)-3(4-methoxybenzylidene)-2-oxocyclopentylidene]methyl}-25,27-dipropyloxy-26,28-dihydroxycalix[4]arene, which is characterized by condensation of 5,17-diformyl-25,27-dipropyloxy-26,28-dihydroxycalix[4]arene with (2E)-2-(4-methoxybenzylidene)cyclopentanone in the presence dimethylammonium dimethlcarbamate (DIMCARB) in chloroform at 45-50 °C. | |
Keywords: | calix[4]arene, ketocyanine | |
Edition: | Ukraine Patent № 57677 (Bul. #5, 10.03.2011) | | | 2011,
1-4,Ukrainian |
043 Formation of mixed J-aggregates of cyanine dyes under the influence of Eu3+ cations |
Authors: | B.I. Shapiro, L.V. Chirkova, A.I. Tolmachev, Yu.L. Slominskii, V.A. Kuzmin | |
Summary: | For the first time the "modular mechanism" of formation of J-aggregates from dimers of various dyes in aqueous solution under the influence of a multiply charged cation Eu+3 was considered. It is revealed that the structure and position of the absorption maximum of mixed J-aggregates is determined by the chromophore length. In conclusion, the mixed J-aggregates are shown to be of particular interest as nanoscale optical elements with variable optical and electronic properties depending on the structure of the cyanines used. | |
Keywords: | J-aggregates, polymethine dyes | |
Edition: | High energy chemistry | | | 2010,
450-454 [418-422 (en)],Russian |
043 Structure and physico-chemical properties of cationic polymethine dyes in Langmuir-Blodgett films |
Authors: | N.Kh. Ibrayev, E.V. Seliverstova, A.R. Tenchurina, A.A. Ishchenko, A.Yu. Shargaeva | |
Summary: | The physicochemical properties of monomolecular layers of amphiphilic cation polymethine dyes (i.e., thia_ and oxacarbocyanines) on the surface of a water subphase are studied along with the conditions of Langmuir–Blodgett (LB) film preparation. The area occupied by one dye molecule in the liquid_stretched and liquid_condensed states of a monolayer is determined. Based on a comparison of experimental and theoretically calculated areas, the nature of dye packing in monolayers is studied by means of molecular mechanics using data from conformation analysis. The spectral and luminescent properties of cationic polymethine dyes in various media are investigated. Excimer fluorescence is observed in LB films. The excimers in LB films are found to arise not from monomers but from dye dimers. A possible mechanism of their formation is considered. | |
Keywords: | polymethine dyes, Langmuir-Blodgett films, excimer fluorescence | |
Edition: | Russian Journal of physical chemistry | | | 2013,
2125-2132 [2082-2088 (en)],Russian |
043 Effect of meso-alkyl substituents in the polymethine chain of thiacarbocyanines on the morphology of dye aggregates |
Authors: | B.I. Shapiro, L.S. Sokolova, V.A. Kuz'min, A.I. Tolmachev, Yu.L. Slominskii, Yu.L. Briks | |
Summary: | Using the example of meso-alkylsubstituted thiacarbocyanine dyes, it has been demonstrated that an ethyl substituent, as a rule, promotes the formation of long-wave J-aggreagtes in aqueous solutions and a methyl substituent favors the formation of short-wave H*-aggregates. The formation of dye aggregates proceeds through dimers by the block mechanism. The formation of three bands in the absorption region of dimers, which plausibly relate to three different forms of dimers and can be attributed to dimers consisting of the cis-, cis-/trans-, and trans-conformations of the dyes, has been recorded for the first time in meso-CH3-substituted thiacarbocyanines. The formation of three different types of H*-aggregates from the three appropriate dimeric forms has also been shown for the first time. It has been established that introducing a multicharged Eu+3 cation into aqueous solutions of dyes shifts the equilibrium, nD-aggregate, towards aggregates; meso-CH3-substituted dyes in this case shift towards H*-aggregates and meso-C2H5-substituted dyes shift towards J-aggregates. Hence it has been shown that an alkyl group in the meso-position to the polymethine chain of thiacarbocyanines plays the role of a regulating agent in the aggregation process due to stereochemical effects and, by this means, predetermines the morphology and spectral properties of the formed aggregate. | |
Keywords: | thiacarbocyanines, dimers, J-aggregates, H-aggregates, meso-substituents | |
Edition: | Nanotechnologies in Russia | | | 2012,
28-33 (випуск 5-6) [205-2012 (en)],Russian |
043 Effect of organic polyelectrolytes on H*-aggregation of meso-methyl-substituted thiacarbocyanine dyes |
Authors: | A.D. Nekrasov, B.I. Shapiro, A.I. Tolmachev, Yu.L. Slonimskii, V.A. Kuzmin | |
Summary: | H*-Aggregation of anionic meso-methyl-substituted thiacarbocyanines of different structures has been studied in dilute aqueous solutions and in the presence of cationic organic polyelectrolytes. The thermodynamic parameters of the H*-aggregation from the trans-dimers have been determined. The thermodynamic equilibrium between two forms of the H*-aggregates in the presence of poly-N,N-dimethyl-N,N-diallylammonium chloride has been observed for the first time, and these forms have been assigned to H* cis and H* trans forms. | |
Keywords: | thiacarbocyanines, organic polyelectrolytes, H-aggregates | |
Edition: | High energy chemistry | | | 2011,
563-569 [525-531 (en)],Russian |
043 Interaction between gold nanoparticle plasmons and aggregates of polymethine dyes: “Invisible” nanoparticles |
Authors: | B.I. Shapiro, E.S. Kol’tsova, A.G. Vitukhnovskii, D.A. Chubich, A.I. Tolmachev, Yu.L. Slominskii | |
Summary: | Composite nanoparticles consisting of rodlike gold particles coated by an organic layer and polymethine (cyanine) dyes of J-aggregates of different structures absorbing light in red and infrared spectrum ranges have been synthesized. It has been demonstrated that, for dyes with J-band absorption maxima in the gold plasmon-band range, one observes an absorption dip as a result of the interference of the photoexcited states of nanoparticles and J-aggregates. The latter results in the decoloration of the gold colloid solution. The effect of the emergence of new intensive absorption bands of dye aggregates, which is assumed to be related to the perturbance of dye aggregate electron levels by gold plasmons and, consequently, lifting the ban on electron transitions to perturbed levels of aggregates, has been found. | |
Keywords: | polymethine dyes, J-aggregates, gold nanoparticles, plasmonic effects | |
Edition: | Nanotechnologies in Russia | | | 2011,
83-87 (вип. 7-8) [456-462 (en)],Russian |
The events in the framework of the project |
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043 2.1. Physics and chemistry of nanomaterials and nanostructures Purpose:Molecular design, synthesis and spectral investigations of polymethine dyes and calixarenes capable of forming nanoparticles – J aggregates, size and properties of which are determined by the molecular structure of dyes and calixarenes. Exploring the possibilities of creating the "hybrid" materials based on J-aggregates and inorganic materials (semiconductors, nanoparticles of gold, silver, titanium dioxide thin films of gold, etc.). Expected results:Issue of new types of products: methods, theories Stage 1:Aggregation of dyes with one or two chromophores in polymer and liquid mediums. Stage 2:Investigation of the properties of J-aggregates of dyes and calixarenes on inorganic substrates. Stage 3:Conjugated systems based on calixarenes. Association of dyes in the presence of one- and polyvalent cations. Stage 4:Quantum-chemical simulation of J-aggregation. Study of dye and calixarene nanoparticle formation in aqueous and non-aqueous mediums. Stage 5:Methods of tailoring of size, structure, shape, morphology of nanoparticles as well as of the distance between the J-aggregates in nanostructures. Definition of the general regularities of creation of J-aggregates based on dyes and calixarenes.
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