Publications by authors named "Starukhin A"

New organic nanostructures were synthesized by introducing 2-methylbenzimidazole (MBI) molecules from a melt, gas phase, or alcoholic solution into nanosized voids of borate porous glasses (PG), nanotubes of chrysotile asbestos (ChA), and mesoporous silica (MS). The incorporation of MBI into borate glasses with different pore sizes is accompanied by the appearance of several phases formed by nanocrystallites which have a MBI crystal structure, but somewhat differ in lattice parameters. The size of some crystallites significantly exceeds the size of nanopores, which indicates the presence of long-scale correlations of the crystal structure.

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Article Synopsis
  • Single crystals of 2-methylbenzimidazolium perchlorate were synthesized for the first time using a slow evaporation method involving 2-methylbenzimidazole and perchloric acid.
  • The crystal structure was analyzed through single crystal X-ray diffraction (XRD), and further confirmed with powder XRD, while complementary techniques like polarized Raman spectroscopy and FTIR assessed molecular vibrations.
  • The study revealed an optical gap of ~3.9 eV and identified two phase transitions above room temperature, indicating changes in permittivity and conductivity similar to ionic liquids during melting.
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Absorption and magnetic circular dichroism (MCD) spectra have been measured and theoretically simulated for a series of palladium octaethylporphyrins substituted at the positions with phenyl groups ( = 0-4). Analysis of the spectra included the perimeter model and time-dependent density functional theory (TDDFT) calculations. With the increasing number of phenyl substituents, the molecule is transformed from a positive hard (ΔHOMO > ΔLUMO) to a soft (ΔHOMO ≈ ΔLUMO) chromophore.

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The steady state fluorescence anisotropy of carbon dot solutions of different viscosities η and its variation with temperature T has been investigated. The dependence of the anisotropy on T/η is shown to be described by the Perrin equation, which implies that Brownian rotational motion of carbon dots in solution is a basic mechanism of fluorescence depolarization. Peculiarities of the Perrin plot testify that the luminous entity ("fluorophore") responsible for carbon dot fluorescence displays noticeable segmental motions, which are independent of the overall rotational diffusion of the dots.

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A method is described for sensitive and selective detection of iodine by using a paper strip modified with silver triangular nanoplates (AgTNPs). It is based on the extraction of iodine from a solution into a flow of air via dynamic gas extraction and transferring it through a reactive paper modified with AgTNPs. The interaction of AgTNPs with iodine results in a color change from blue to white.

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The nonlinear fluorescence properties of colloidal carbon dot solutions in glycerol were investigated at T = 298 K and 77 K. It was first found that the fluorescence intensity depended sublinearly on optical excitation intensity even at moderate excitation levels. With increasing excitation, the fluorescence signal shows a trend toward saturation, the latter being most pronounced at liquid nitrogen temperature.

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Resonance Raman microscopy was used to study the resonance Raman scattering of the diacid (diprotonated form) of free-base porphyrin (21H,23H-porphine) in a crystal powder and KBr pellets. Intensive lines in the spectral range between 100÷1000cm have been detected and assigned as spectral manifestation of out-of-plane modes. The Raman spectra were simulated by means of DFT methods and compared with the experimental data.

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The absorption spectra of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole have been studied in 15 solvents. The formation of deprotonated corrole species was found to account for the dramatic changes in the absorption spectra in several solvents. Careful analysis of the relationship between the formation of deprotonated species and solvent properties results in the conclusion that there is no single solvent parameter correlation, and either multiparameter correlations or specific solute-solvent interactions (preferential solvation of the most acidic NH tautomer or perturbation of intramolecular hydrogen bonding in the macrocycle core) should be considered.

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The fluorescence spectra of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole have been studied in the temperature range from 4.2 to 332 K. For the first time, the individual fluorescence profiles of the two corrole NH tautomers have been assigned over the whole temperature range.

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Protonation of a free-base meso-pyrimidinyl-substituted AB(2)-corrole (H(3)AB(2)) in ethanol solution by stepwise addition of sulfuric acid has been studied in the temperature range from 293 to 333 K. The formation rate of protonated species was found to depend profoundly on the temperature at which the titration was undertaken. Two steps in the titration curve were identified at temperatures around 293-298 K, whereas one-step formation of protonated species was found to occur at temperatures above 308 K.

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