Fine Chemical Technologies

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Vol 8, No 4 (2013)
View or download the full issue PDF (Russian)


3-10 270
The main approaches to the creation of highly sensitive test systems based on polymeric microspheres with immobilized bioligands intended for rapid diagnostics of proteinopathy were considered. The effect of these test systems is based on the latex agglutination reaction between the antigens grafted to the surface of polymeric microspheres and antibodies contained in a biological sample. The issues related to obtaining and optimal properties of polymeric microspheres, which must contain functional groups reactive toward bioligands at their surface were analyzed. Problems associated with immobilization of bioligands on the surface of the polymeric microspheres and the possibility to improve the composition and preparation of test systems were considered. Special attention is given to obtaining test systems for the diagnosis of thyroid disease by means one of its antigens – thyroglobulin.
11-17 274
Some steps were taken to elaborate a method for the preparation of polymeric microspheres using flow microreactors by emulsifying the solution of methacrylic acid esters copolymer in an aqueous PVA solution followed by extraction and evaporation of the solvent. The effect of process parameters on the characteristics of polymeric microspheres with a predetermined set of properties (mean size, polydispersity) potentially suitable for use as carriers in bioligands for diagnostic test systems was investigated. The dependence of the average particle size on the microreactor type, concentration of copolymer solution in methylene chloride and polyvinyl alcohol in water and the ratio of flow rates of organic and aqueous phases was stated, and the optimal process conditions were selected.
18-26 223
Few 5-vinyl substituted 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-[2H]chromenes) (6’-nitro-spiropyrans) were synthesized by a one-step method from 5-formyl precursor – 5-formyl-6’-nitro-1,3,3-trimethylspiro(indolino-2,2’- [2H]chromene) (1). 5-Vinyl-6’-nitro-spiropyran (2) was prepared by the Wittig olefination of 1 with an ylide, which was generated by the action of potassium tert-butylate on methyltriphenylphosphonium bromide in THF. E-6’- Nitro-5-(1’’-nitroethene-2’’-yl)-6’-nitro-spiropyran (3) was obtained by heating 1, nitromethane, ethylenediammonium diacetate at 50°С in absolute methanol and inert atmosphere. Compounds 1’’-[6’-nitro-spiropyran-5- yl]-2’’,2’’-dicyanoethylene (4) and E-1’’-[6’-nitro-spiropyran-5-yl]-2’’-cyano-2’’-methoxycarbonylethylene (5) were prepared from initial 1 by reflux in ammonium acetate / glacial acetic acid / benzene mixture with malonodinitrile or methyl 2-cyanoacetate, respectively. The procedure for synthesizing derivatives 2’’,2’’-dimethyl-5’’-(6’-nitrospiropyran-5-yl)methylidene-1’’,3’’-dioxane-4’’,6’’-dion (6) and 5’’,5’’-dimethyl-2’’-(6’-nitro-spiropyran-5-yl)- methylidenecyclohexane-1’’,3’’-dion (7) includes the interaction of Meldrum's acid or dimedone, accordingly, with 5-formyl precursor 1 by heating in ethanol in the presence of piperidine and molecular sieves (to bind the released water). The structures of the prepared compounds and their purity have been confirmed by physico-chemical analysis. A spectral kinetic study of the photochromic properties of the substituted 5-vinyl spiropyrans was carried out in toluene and ethanol solutions. The 5-vinyl-6’-nitro-spiropyran derivatives 2–7 described in this work are of interest for further synthetic transformations.
27-32 192
Disaccharide nucleosides belong to an important group of natural compounds found in t-RNA and poly(ADPribose). They are also key elements in the structure of antibiotics and other physiologically active compounds. Poly(ADP-ribosylation) is a posttranslational modification of proteins in eukariotic cells catalyzed by poly(ADPribose)-polymerazes. The importance of poly(ADP-ribose) has been established in many cellular processes such as DNA replication, recombination and repair and cellular differentiation. The development of the synthesis of poly(ADP-ribose) and it’s components is still a challenging problem. The synthesis of 2'-O-α-D-ribofuranosyladenosine, a monomeric unit of poly(ADP-ribose) reported earlier has been improved. An important step on this way is the formation of a 2'-O-glycosidic bond between the adenosine and carbohydrate moieties. A new strategy involving glycosylation of 3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)adenosine has been suggested. Varying of the catalyst (SnCl4), nucleoside and carbohydrate relations by the simplex method allowed improving the yields in the glycosylation step from 35 to 64%. As a result, it made possible to reach a higher overall yield of 2'-O-α-D-ribofuranosyladenosine in comparison with the literature data.


33-37 224
The flow of two thin films of mutually insoluble liquids was studied taking into account the impact of the oncoming gas flow. A method of calculating the films thickness was developed. Software was built for calculation based on that method.
38-42 224
In this paper we considered the granules formation process using the "fattening" technology in a granulation bowl. Development of rolling overgranulation technology primarily due to the need to obtain granules of larger size with much better quality indicators than those that can be attained in granular towers. Also, this technology gives granules with a complex chemical composition. Fattening is the process of overgranulation of an initial pellet by powder (with or without binding) by rolling in different devices, including bowls. The mathematical description of various embodiments of the process: with or without the birth of pellets. Besides, the process of fragmentation of the granules is considered separately. Fragmentation is usually an undesirable process, but sometimes it is not possible to get rid of it. The calculation results obtained by the models are represented as a series of graphic dependencies. We also develop algorithms that allow for the effect of fragmentation and agglomeration in arbitrary ratios. A block diagram of the implementation of the algorithm is also presented in the paper.
43-50 219
The analysis of the published composition – scalar property diagrams of ternary mixtures containing an ionic liquid was performed. Insufficiency of composition – property data for ternary mixtures, especially for different conditions, and the absence of results of the statistical analysis of measurements in the original papers was noted. The main problems that arise when building diagrams of isolines of properties according to the data of the calculation experiment were found. It is shown that in some cases it is fundamentally impossible to simulate the scalar quantities of ternary mixtures using data on binary components, because the boundary contour of the concentration triangle characterized by a certain number and the location of the binary critical points may correspond to different topological structure diagrams of isolines of the ternary mixture. Recommendations were made for testing topological structures of the diagrams of isolines of scalar properties of ternary mixtures built on the results of field measurements and precision calculations with the use of model equations.
51-56 207
The article deals with the configuration of the concentration simplexes of multicomponent mixtures and its different representations. The analysis of the phase diagram of a five-component mixture was made.


57-63 294
We present the synthesis of new complexes of praseodymium and holmium bromides and biuret (NH2CONHCONH<sub>2</sub> - BU), PrBr<sub>3</sub>2BU4H<sub>2</sub>O (I) и HoBr<sub>3</sub>2BU4H<sub>2</sub>O (II) and the results of IR spectroscopy and X-ray diffraction analysis. In the crystals of I and II we find complex cations [Ln(H<sub>2</sub>O)4(BU)<sub>2</sub>] <sup>3+</sup> (Ln = Pr, Ho) and uncoordinated bromide ions existing in the external sphere. Biuret molecules serve as bidentate ligands (through the oxygen atoms) and are transformed from the original cis- to trans-configuration. Four molecules of water are coordinated in the internal sphere through the oxygen atoms too. The coordination polyhedron is a two-capped trigonal prism. The oxygen atoms of two BU molecules and the first and second oxygens of the water ligands form a trigonal prism. The third and fourth oxygens of the water ligand form two caps of the coordination polyhedron. The coordinated BU molecules are joined with the bromide ions and water molecules of the neighbour complex cations by hydrogen bonds. We discuss the conversion of trans-BU to cis-BU in the complexes of this type for the lanthanide chlorides and bromides.
64-72 215
For the first time the composition and microstructure of large (more than 2 cm) urinary stones, including staghorn stones, were studied according to their volume by a set of techniques (X-ray, X-ray microanalysis, scanning electron microscopy, infrared spectroscopy, spectrophotometry, gas chromatography with a flame ionization detector), as well as the composition of the urine, in which their formation and growth occurred. The results and analysis combined with the published data have allowed to clarify and expand the theories of formation and suggest the process of urinary stones growth.
73-76 230
Strained InGaAs/AlGaAs quantum wells based on GaAs substrates are successfully used in wide optoelectronic applications. In this paper the advantages of these strained wells and their manufacturing difficulties in MOCVD have been described. In order to estimate the quality of InGaAs/AlGaAs quantum wells with and without GaAsP compensation layer the photoluminescence method at room temperature was used. It is shown that optimal thickness and content of InGaAs layers lies in the small metastable region, which was accurately calculated. The effective critical stress, which leads to misfit dislocations formation, was found and equals to 0.014mGaAs (where mGaAs is rigidity modulus in GaAs). The GaAsP compensation layers close to highly strained quantum wells for better reproducibility of the growth method were proposed. Finally, the best position of the GaAsP layer for higher photoluminescence signal has been chosen and discussed.
77-79 206
Recently carbon-doped epitaxial layers become more attractive in most practical applications. In this paper we have considered the mechanisms of etching of CCl<sub>4</sub>-doped GaAs grown by MOCVD in the temperature range of 600–800°C. It has been shown that, as temperature increases, the etching of solid GaAs with the formation of volatile GaCl3 becomes the leading contribution to the growth rate reduction.
80-84 256
The main ways of formation of palladium particles in the water-alcohol solution were studied. The basic factors governing this process were established, and the electrokinetic characteristics of dispersions of nanoparticles were determined.
85-91 206
A three-dimensional (3D) detailed heat, mass and momentum transfer model was constructed to describe the thermal behavior, fluid dynamics and the diffusion in a horizontal metal-organic vapor-phase epitaxy (MOVPE) reactor with a rectangular section and a rotated substrate keeper with inductive heating used for numerical studying to obtain optimum conditions for the growth process and to calculate the growth rate and the composition of In<sub>x</sub>Ga<sub>1-x</sub>As nanolayers.
92-95 204
The results of a study on the rate of galvanic corrosion of thin ferromagnetic iron films in an external uniform magnetic field are presented. It is shown that the direction of the external magnetic field has different influence on the corrosion rate in the presence of a magnetic field. The shape of the micro-relief surface iron film subjected to a short-term treatment with a solution of acetic acid was studied. The relief is formed on the surface due to the heterogeneity of the corrosion rate on the surface of the film. Areas of high corrosion rates correspond to areas of the domain boundaries of the ferromagnetic film. When the orientation of the external magnetic field is changed, the domain structure changes, which is reflected in the change of the average rate of corrosion.
96-98 281
Regularities of changes in the electrical conductivity of solid NiO – ZnO solutions in the temperature range of 20– 700°C were studied. It was found that all the compositions of solid solutions have a negative temperature coefficient of resistance. The change in electrical resistance is 3-4 orders of magnitude. Solid solutions of NiO(ZnO) are stable under thermal treatment up to 700°C, and changes in electrical resistance upon the heat treatment do not occur. Solid solutions of ZnO(NiO) decompose at temperatures above 350°C. Decomposition occurs by the diffusion mechanism with the formation of two new phases of solid solutions. Solid solutions of NiO – ZnO have the values of coefficients of temperature sensitivity 4000–11000 K. Solid solutions of NiO(ZnO) are perspective for use in temperature sensors and thermistors.


99-102 241
Reokinetic properties of multifunctional epoxy resin at diffrent temperatures with low-viscosity reactive diluents containing glycidyl ether, and the glass transition temperature and the degradation temperature of heat-resistant polymer matrix was investigated. The reactive diluents increases the glass transition temperature at 37°C, reduces the viscosity of 4 times, and the curing time is not changed. It was developed technological polymer binder based on epoxy resin and reactive diluents with low viscosity, and high glass transition temperature (~ 280о С) and degradation temperature ~ 335°С.
103-108 236
The process of co-condensation of 3-aminopropylmethyldimethoxysilane with α,ω-dihydroxyoligo-dimethylsiloxanes is studied. It is shown that the method proposed allows obtaining aminosiloxanes with a definite structure in quantitative yield. The methoxy group in aminopropylmethoxysiloxane oligomers can be quantitatively replaced by trimethylsiloxy group by transesterification with trimethylsilanol, leading to aminosiloxanes with the same chain length. The hydrolysis of the methoxy groups in aminopropylmethoxysiloxane oligomers causes the increase of the polymer chain length due to partial co-condensation of silanol groups leading to aminosiloxanes with a strictly alternating dimethylsiloxane block of the fixed length and a pair of aminopropylmethylsiloxane units. The reaction of N,N’-bis(trimethylsilyl)carbodiimide or hexamethyldisilazane with residual silanol groups leads to trimethylsiloxy-substituted polyaminopolysiloxanes. The trimethylsililation of the residual silanol groups with hexamethyldisilazane is accompanied by the trimethylsililation of the amino groups.
109-112 195
In this paper concentrated and dilute solutions of a styrene-isoprene thermoplastic elastomer in volatile organic solvents of different nature and films formed of them were studied. The influence of the solvent on the complex of technological and operational properties of the adhesive compositions is shown.
113-117 190
In this work the preparation of polymeric composite materials (PCM) based on an ED-20 grade epoxy resin with the use of carbon nanotubes (MWNT), technical carbon (N220) and aerosol (A380) and the influence of midget additives of these fillers on the complex of optical, rheological and physicomechanical properties were investigated.

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