Fine Chemical Technologies

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Vol 9, No 1 (2014)
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3-17 115
The present review is devoted to the 70th element of the Periodic system and its complexes with natural and synthetic porphyrins. The ytterbium combination with porphyrin compounds, which are able to accumulate selectively in malignant tumors, led to the creation of a new class of diagnostic compounds fluorescing in the NIRregion in a "window of tissues transparency". Syntheses of Yb-complexes of various porphyrins with the use of Yb(acac)3 in several solvents and microwave radiation are considered. Electronic absorption spectra, fluorescence spectra and luminescence decay curves are given, the lifetimes of excited Yb-complexes state are measured, and the influence of chromophore aromatic fragments in macrocycle meso-positions on quantum exits values is considered. The carried out screening of more than 20 compounds allowed to choose the most perspective substance for early luminescent diagnostics – dipotassium salt of Yb(acac)-dimethoxyhematoporphyrin IX. Biological tests on tumor-carrier mice are carried out, and primary preparation accumulation in malignant tumors is shown. This compound was used also for the functionalization of composite nanoparticles consisting of gold-silver nanocages covered with mesoporous silicon dioxide. Syntheses of bis-porphyrins with different elements, application of ytterbium compounds in biomedicine, technics, chemical reactions and etc. are considered.
18-21 83
The goal of the present study was the development of composition analysis method for vision pigments chromophore groups of different animals with the use of high performance liquid chromatography as well as the development of synthetic method for all-E-3,4-didehydroretinal – one of standard compounds. The all-E-3,4- didehydroretinal synthetic route developed earlier has been polished, and the product structure has been confirmed by physical-chemical analysis methods. The chromatographic separation process of Z-isomers of natural retinal and 3,4-didehydroretinal has been studied under isocratic flow conditions with the use of one and two sequentially connected normal phase columns. Optimal chromatographic conditions have been proposed for the separation and analysis of both retinoid model mixtures and animal eye extracts.


22-31 91
The charged particles motion in graphene under the influence of an external electric field in the frame on the nonlocal quantum hydrodynamic description is considered. With the help of the numerical solution of a system of nonlocal hydrodynamic equations the dependence of the soliton structures on the external electric field is investigated
32-37 96
Ternary vapor-liquid equilibrium (VLE) diagrams provide a graphical tool to predict qualitatively the feasible separations for multicomponent azeotropic mixtures before detailed simulation or experimental study of their distillation. The various graphical representations of the VLE (residue curve and distillation line maps, isotherm map, equilibrium vector field) are closely related and are equally capable of characterizing the mixture. The total information about the ternary system α,γ-dichlorohydrin – hydrogen chloride – water (azeotropy, the boiling temperature of individual substances and singular points) is not available in literature. That is why identification of the distillation line map is a difficult task. Improvement of the distillation line map was made on the base of thermodynamic and topological analyses, simulation of vapor-liquid equilibrium on the base of UNIFAC method and experimental work. Isothermal-isobaric manifold was obtained on the base of experimental work. The boiling points of ternary systems (α,γ-dichlorohydrin – hydrogen chloride – water) were measured accurately at constant pressure using an ebulliometer
38-42 99
Analysis of heat cost for rectification was performed taking into account the phase state of the original mixture. It was proved theoretically that increasing feed vapor fraction leads to decreasing energy consumption in conventional distillation process. With a low excess factor of reflux, total energy consumption by the reboiler and feed heater is greater than for a distillation column without a feed heater. For high excess factor of reflux values the cost of energy consumed by the reboiler can increase even for rising feed vapor fraction. The most economical condition for full condensation of the vapor-liquid feed before entering the distillation column was found
47-52 79
Analysis of classifications of planar quadrangular diagrams published in the literature was carried out. These classifications deal with projections of chemical equilibrium surfaces in a quarternary system, with ternary intermutual systems containing liquid and solid solutions between constituent salts and also with graphical representation of response surfaces. The synthesis of the complete set of topological types of planar quadrangular diagrams was carried out. The complete set includes 98 types, which differ in boundary and inner simple singular points (elliptic and hyperbolic); the total amount of subtypes is 120. The subtypes of the diagrams may differ in the mutual arrangement of either boundary or both boundary and inner singular points. In previously published classifications, repeating diagram structures and unstable structures were revealed. The most accurate results are achieved by a formalized procedure of synthesis of a topologically possible set of planar quadrangular diagrams. By “formalized procedure” we mean the use of a specific program for variants enumeration of possible mutual arrangement of singular points in planar quadrangular diagrams. This procedure in the most correct way allows to take into account diagrams differing in the mutual arrangement of not only boundary, but also inner singular points.


53-58 97
The influence of preliminary modifying treatment of brown coal on the properties and yield of resulting brown coal waxes was investigated. The efficiency of coal demineralization by hydrochloric, oxalic and citric acid solutions was studied. A scheme for complex processing of brown coal to obtain waxes was proposed.
59-63 101
In this work the kinetics of liquid-phase oxidation of n-alkanes C<sub>10</sub>–C<sub>13</sub> on the titanium silicalite-shaped heterogeneous catalyst DP-1 with aqueous hydrogen peroxide in methanol at a temperature of 40–60°C was studied in a continuous reactor. It is shown that the rate of n-alkanes oxidation to alcohols and ketones increases with increasing reaction temperature and the initial concentration of the n-alkanes and hydrogen peroxide. For the kinetics of oxidation of n-alkanes C<sub>10</sub>–C<sub>13</sub> on the heterogeneous catalyst DP-1 with aqueous hydrogen peroxide in methanol the exponential equation was used. The parameters of the kinetic equations of the main and side reactions were determined. These data can be used when calculating the integrated plants producing the higher fatty alcohols C<sub>10</sub>–C<sub>13</sub> fraction


64-67 90
The quantitative definition method of N-vinylpyrrolidone and 2-methyl-5-vinylpyridine ratio units in the copolymers using UV-spectrophotometry was developed. Copolymers were prepared by radical copolymerization using azo-bisisobutiric dinitrile as the initiator. On the basе of experimental results and simple mathematical transformations the simplified formula of calculation of the maintenance of 2-methyl-5-vinylpyridine units in the copolymer, including extinction coefficients of poly-2-methyl-5-vinylpyridine and a copolymer sample is concluded. The validity of the method as compared to 13С NMR was shown. According to results obtained by that method the synthesized copolymers are characterized by reproduceable characteristics, in particular the content of 2-methyl-5- vinylpyridine units was found 30-40 mol.%.
68-72 115
Diane epoxy oligomers (EO) are the most widespread among epoxies, their production makes more than 70% from the general release. To improve the impregnation of fibrous filler to create a polymer composite material (PCM) to reduce the viscosity of the binder and to that end the low viscosity diluents. This article presents the results of investigation of the influence of the various nature diluents on kinetics and value of the ED-20 brand and the EHD chlorine-containing brand epoxy oligomers final volume shrinkage is surveyed at solidification with the different types of low-viscosity liquid curing agents. Kinetic dependences of volume shrinkage of epoxy oligomer for different types of diluents are received at various concentration and dependence of shrinkage to answering point of jellification and shrinkage to answering point of the beginning of jellification from concentration of diluents. It is established that using active diluents to 20% mass decreases viscosity of the epoxy oligomers, but the kinetics of shrinkage and final shrinkage practically don't change. Introduction of active low-viscid diluents in EHD brand EO to 20 wt.% practically doesn't change kinetics of shrinkage and value of final shrinkage and allows to reduce by 2-4 times viscosity binding that leads to the referred adjustment of technical characteristics polymeric binding and conditions of processing of systems on the basis of EHD. Final heat treatment of samples at an increased temperature practically has no impact on shrinkage, however its carrying out is expedient as it leads the glass transition temperature increase.
73-75 89
The article is devoted to questions of accumulated data usage to find out regularities by means of pattern recognition methods that allow predicting formation of not synthesized substances and estimating its properties. The formal task of computer-aided inorganic compounds design is stated. An approach to reproduce of missing data in learning samples for computer-aided inorganic compounds design is proposed. It is based on combination of linear regression and interpolation taking into consideration the problem domain – inorganic chemistry. The approach is more powerful than methods of missed data reproduction used currently in information-analytical system for inorganic compounds design running at IMET RAS.
76-80 95
A method of conjugate harmonic functions in solving boundary value problems for Laplace’s equation in two dimensions was developed. A series of illustrative problems was considered.
81-86 97
The role of inertial effects in the problem of heat stroke with a massive body having an internal spherical crack as an example was studied. An interrelationship for the calculation of the maximum dynamic stress, which is of great practical importance, is suggested.
87-92 93
An approach to the systematization of coupled problems of different science areas is suggested. A unified methodology for solving such problems is described. The usage of this methodology is illustrated by examples of solving the contact problem and the problem of chemical machine-building.

ISSN 2410-6593 (Print)
ISSN 2686-7575 (Online)