Synthesis of o- and m-Carborane-substituted Porphyrins of the Natural Type

Basing on protoporphyrin IX, its monobenzyl ester, deuteroporphyrin IX, 9-hydroxymethyl-m- and 9-hydroxymethyl-p-carboranes, mono- and dicarborane-containing porphyrins were prepared.     

Formation of porous matrices from lactide and ε-caprolactone copolymers in supercritical carbon dioxide medium

A series of lactide and ε-caprolactone copolymers containing 4–24 mol % of ε-caprolactone with 20- to 30-kDa molecular weights are synthesized. Based on them, porous materials are produced by foaming in supercritical carbon dioxide. The pore size was shown to decrease with increasing ε-caprolactone content in copolymer, while the porosity of the entire sample was not altered. The resulting pore size also decreases if 7 wt % polyethylene glycol is added to the initial monomer mixture. The Young’s modulus of the porous samples decreases with increasing ε-caprolactone content and when polyethylene glycol is added.     

Nuclear-chemical processes under the conditions of laser ablation of metals in aqueous media (problems of “cold fusion”)

A brief review of results on initiation of nuclear transformations under conditions of the laser ablation of metals in aqueous media upon exposure to picosecond laser impulses with peak intensity J _E ～ 10¹⁰–10¹³ W/cm², which is orders of magnitude less than required for the direct initiation of nuclear processes, J _E ～ 10¹⁸–10¹⁹ W/cm², is presented. It is shown that the decay rate of radioactive nuclei (using the example of uranium 238) increases significantly (by orders of magnitude), nucleus transmutation processes are initiated (using the example of the transmutation of mercury 196 nuclei into gold 197), and the nuclear fusion of light elements occurs (using the example of tritium nuclei) under such conditions. Concepts regarding the processes of inelastic (with the generation of neutrino-antineutrino pair) interactions between electrons of high (on the chemical scale) energies (～5–10 eV) and nuclei are developed in order to understand the totality of the current experimental data on the initiation of such processes under conditions of the laser ablation of metals in solutions of ordinary and heavy water. This is reflected in the definition of such processes as nuclear-chemical. It is suggested that the state of nuclear matter in nuclei formed during such interactions is in an unbalanced in-shake-up state, and cannot be pictured in the standard manner, as an ensemble of a certain number of nucleons. Such states are reactive for a wide class of nuclear transformations.     

Anomalous diffusion in the dynamics of complex processes

It is shown that complex signals represented in the form of time series of measured dynamic variables can contain chaotic components whose time changes can be described as anomalous diffusion processes. To determine the parameters of such processes, procedures for the extraction of low-frequency and highest-frequency flicker-noise components, which are flicker-noise spectroscopy characteristics, should be developed. The methodology of the corresponding analysis is demonstrated for the example of magnetoencephalogram signals recorded as responses to the external action of a flickering color stimulus.     

Combined laser and photodynamic treatment in extensive purulent wounds

Recently, photodynamic therapy (PDT) has been used for the treatment of festering wounds and trophic ulcers. An important advantage of PDT is its ability to affect bacterial cultures that are resistant to antibiotics. However the use of PDT alone does not usually guarantee a stable antiseptic effect and cannot prevent an external infection of wounds and burns. In this work attention is focused on the healing of the extensive soft tissues wounds with combined laser therapy (LT) and PDT treatment. At the first stage of this process festering tissues (for example spacious purulent wounds with area more than 100 cm²) were illuminated with high-energy laser beam (with power 20 W) in continues routine. The second stage involves “softer” PDT affect, which along with the completion stages of destruction pathological cells, stimulating the process of wound granulation and epithelization. Also, according to our previous results, photosensitizer (photoditazin) is introduced inside the wound with different amphiphilic polymers for increasing the PDT efficacy.     

Conductive composites based on chitosan and polyvinylpyrrolidone-stabilized graphene

Highly concentrated dispersions of polyvinylpyrrolidone-stabilized graphene were prepared. Using transmission electron microscopy, it was found that the graphene particles consisted, on average, of one to four layers, with the lateral size of 50–400 nm. From these dispersions, new film composites of chitosan with the filler content up to 4 wt % characteristic of electrical conductivity as high as 1.9 × 10^–2 S/cm were formed.     

The effect of porphyrin supramolecular structure on singlet oxygen photogeneration

This work is to show that activity of porphyrins in singlet oxygen generation (SOG) is determined not only by their molecular structure but also by supramolecular structure of porphyrin containing systems. This is demonstrated by results of studies of SOG in the gas phase by vacuum deposited tetraphenylporphyrin (TPP) layers under photoexcitation conditions. The structure of the layers was studied by atomic force microscopy (AFM), TEM in diffraction regime (TED) and by the flicker-noise spectroscopy (FNS) method. It was shown that substrates affect the deposited layers structure only at earlier stages of the layer formation. AFM and TED data, together with FNS quantitative parameters of TPP layers, show directly that the chemical activity of solid-phase systems can be determined not only by their chemical nature but also by their supramolecular structure.     

Substituted benzotriazoles as inhibitors of copper corrosion in borate buffer solutions

The adsorption of substituted 1,2,3-benzotriazoles (R-BTAs) onto copper is measured via ellipsometry in a pure borate buffer (pH 7.4) and satisfactorily described by Temkin’s isotherm. The adsorption free energy (?ΔG _a ⁰ ) values of these azoles are determined. The (?ΔG _a ⁰ ) values are found to rise as their hydrophobicity, characterized by the logarithm of the partition coefficient of a substituted BTA in a model octanol–water system (logP), grows. The minimum concentration sufficient for the spontaneous passivation of copper (C _min) and a shift in the potential of local copper depassivation with chlorides (E _pt) after an azole is added to the solution (i.e., ΔE = E _pt ⁱⁿ ? E _pt ^backgr characterizing the ability of its adsorption to stabilize passivation) are determined in the same solution containing a corrosion additive (0.01М NaCl) for each azole under study. Both criteria of the passivating properties of azoles (logC _min and ΔE) are shown to correlate linearly with logP, testifying to the role played by surface activity of this family of organic inhibitors in protecting copper in an aqueous solution.     

Photocatalytic properties and structure of chitosan-based porphyrin-containing systems

The photocatalytic activity of the disodium salt of substituted hematoporphyrin in a model reaction of tryptophan oxidation in the presence of chitosan with different molecular masses and a block copolymer of ethylene and propylene oxides (Pluronic F-127) is studied. It is shown that, in the presence of the Pluronic, the catalytic activity of the chitosan-porphyrin system increases. The structure of chitosan-Pluronic systems, depending on the molecular mass of chitosan and the presence of porphyrin, is examined by AFM. A pleasible mechanism of the influence of the Pluronic on the photocatalytic activity of chitosan-por-phyrin systems is proposed.     

Preparation and optical properties of composite materials based on polybenzimidazole and silver nanoparticles

Rigid-chain heat resistant polymers (with poly-2,2'-p-oxydiphenylene-5,5′-bisbenzimidazole as example) were impregnated for the first time with a silver-containing precursor in formic acid and in supercritical carbon dioxide. A procedure allowing the precursor reduction to silver nanoparticles both throughout the volume by thermal annealing of the films in the temperature interval 100–150°С and in the targeted mode using lasers operating at 405 and 532 nm was developed. It opens prospects for developing a process for production of heatresistant optical gratings and light guides. The reduces nanoparticles and their agglomerates have the size in the interval 50–200 nm and give a plasmon band in the range 450–460 nm.