Carbenes,related intermediates,and small-sized cycles: contribution from Professor Nefedov’s laboratory

The review summarizes some of the most prominent results obtained in the laboratory headed by Academician Oleg M. Nefedov at the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences in the field of chemistry of carbenes, their heavy analogs, and related intermediates, as well as small-sized cycles. Those include elaboration of safe methodology of cyclopropanation using diazomethane, development and extension of synthetic applications of diazoesters and other diazo compounds in the preparation of valuable chemical products, design of functionalized alkynylcyclopropanes on the basis of alkynylcarbene reactions, creation of versatile synthetic approaches to preparation of various practically useful fluoroorganic compounds on the basis of reactions of fluorocarbenes, development of synthetic applications of heavy carbene analogs and synthesis of small-sized heterocycles containing silicon and germanium atoms, analysis of mechanisms of some important reactions of carbenes, their analogs and related intermediates on the basis of physicochemical studies, direct spectroscopic studies of various labile intermediates of chemical reactions.     

Application of nonspecific biosensors methodology for right choice of diagnostic criteria for food allergy and intolerance on the basis of specific human IGG determination

Under consideration is the application of a methodology of nonspecific biomarkers to the interpretation of the titers of specific immunoglobulins of type IgG for the purpose of accurate determination of a threshold between normal and abnormal values. Proposed is a mathematical model of assessment of a phase status of a biological entity based on the ranking of a series of concentrations of specific immunoglobulins of type IgG.     

Die Wasserstoffbrückenbildung als primärer Elementarvorgang bei der Ionisation schwacher Säuren und bei Säure-Basen-Katalysen in wäßriger Lösung

The mechanism of the ionisation of weak acids was elucidated according to the interpretation of the acid—base-catalysis of the mutarotation of α-glucose by the author. The primary elementary reaction of the ionisation of weak acids is the exothermic formation of the hydrogen bridge of the acid with the polar solvent. The secondary reaction is the endothermic total transfer of the proton to the solvent. The thermodynamic values of both elementary reactions were determined for the ionisation of different weak acids in aqueous solution and in this way a contribution was made to the thermodynamics of intermediate reactions which was propagated by the autorh. The formation of hydrogen bridge at the acid—base-catalysis of the mutarotation of α-glucose is discussed from the point of view of the mechanism of ionisation of weak acids. Furthermore the limits of the validity of theBrönsted equation for the acid—base-catalysis of the mutarotation of α-glucose were demonstrated.     

Photosensitized Damage Inflicted on Plasma Membranes of Live Cells by An Extracellular Generator of Singlet Oxygen—A Linear Dependence of A Lethal Dose on Light Intensity

We describe a study of the influence of a dose rate, i.e. light intensity or photon flux, on the efficiency of induction of a loss of integrity of plasma membranes of live cells in culture. The influence of a photon flux on the size of the light dose, which was capable of causing lethal effects, was measured in an experimental system where singlet oxygen was generated exclusively outside of live cells by ruthenium(II) phenantroline complex. Instantaneous, sensitive detection of a loss of integrity of a plasma membrane was achieved by fluorescence confocal imaging of the entry of this complex into a cell interior. We demonstrate that the size of the lethal dose of light is directly proportional to the intensity of the exciting light. Thus, the probability of a photon of the exciting light inflicting photosensitized damage on plasma membranes diminishes with increasing density of the incident photons.     

Selectivity of the stationary phase in gas-liquid chromatography

The use of molar refractions is insufficient to describe the retention volumes and thermodynamic functions of solutions in nonpolar stationary phases. The heats of dissolution of monofunctional derivatives of the alkanes are proportional to the polarizability and inversely proportional to the sixth power of the van der Waals' radius of the interacting particles. The heat of dissolution of substances being analyzed, with the same number of carbon atoms, in aromatic solvents depends on the conditions of contact between the molecules of the substances being analyzed and the benzene rings of the solvent. The order of the heats of dissolution of substances being analyzed in different nonpolar solvents does not remain the same, indicating that the theory of regular solutions cannot be applied to these systems. To determine the order of the heats of dissolution of isomers in nonpolar stationary phases it is necessary to take account of the electron density distribution in the molecules of the reacting substances and the probability of molecular arrangement for the most favorable interaction.     

Kinetic Regularities Governing the Reaction of Electrodeposition of Iron from Solutions of Citrate Complexes of Iron(III)

The kinetics of a multistep reaction of electrodeposition of iron out of aqueous citrate-containing solutions of trivalent iron is investigated. It is shown that concentrations of major solution components affect the partial current density of discharge of ions of divalent iron. It is established that the deposition of metallic iron occurs as a result of discharge of intermediates, which are hydroxy complexes of divalent iron. Kinetic parameters and mechanism of the reaction of discharge of complexes [FeOH]⁺ to a metallic state are determined. It is mentioned that the formation of poorly soluble hydroxy compounds of trivalent iron in a near-electrode layer leads to a decrease in the iron deposition current.     

Thermal decomposition of kerogens: Mechanism and analytical application

Specific features of the chemical structures of organic matter (Lerogen) in oil shales caused by the nature of the starting materials for the formation of shales and the routes of their subsequent alteration are reflected in the composition of shale semicoking (retorting) oil. In order to establish the analytical possibilities of the thermal decomposition method in elucidating the kerogen structure and to obtain more data on the mechanism of the pyrolysis of kerogens, the effect of a series of factors (rate of heating, pressure, presence of carrier gases, water and mineral matter of shale, treatment with reagents) on the yield and composition of the pyrolysis products of oil shales was investigated.The yield of shale oil and the phenol content in the latter increase when semicoking is performed in a stream of hydrogen at atmospheric pressure. In shale pyrolysis in the presence of water under pressure, the yield of oil and, in particular, water-soluble organic compounds also increase, as well as the content of neutral heteroatomic compounds in oil. With increasing content of mineral substances in shale, the yield of the semicoking oil (kerogen basis) and the content of polar compounds in it diminish owing to an increasing influence of oil adsorption on the mineral matter and its additional decomposition as a result.In the initial stage of thermal decomposition, both longer aliphatic substituents and side-chains of iso-structures split off and alkenes with a double bond in the middle of the chain (probably the products of elimination and dehydration of the aliphatic substituents with a hydroxyl group) are formed. The formation of n-1-alkenes, particularly those of even carbon number, which originate from the side-chains of odd carbon number by the cleavage of carbon–carbon bonds in the β-position to the cyclic nucleus of kerogen, becomes more pronounced in the final stage of pyrolysis when, owing to significant aromatization of the cyclic part of kerogen, the selectivity of the β-cleavage increases.     

Estimation of limits of detection and determination in X-ray fluorescence analysis by the dependence of the relative standard deviation on analyte concentration

An experimental dependence of the relative standard deviation on analyte concentration of hyperbolic type, characterizing the precision of quantitative chemical analysis, was used to estimate the limits of detection and determination in the X-ray fluorescence analysis. A method is proposed for the determination of their values using the approximation of the experimental dependence of the relative standard deviation on the analyte concentration by a power function. The choice of the values of the relative standard deviation, being criteria for the estimation of these limits, is substantiated. A concept of the limits of detection and determination of an analytical procedure is formulated, according to which the limit of detection of an analytical procedure is an objective value depending only on the precision of determinations, and the limit of determination of an analytical procedure is a subjective value depending not only on the precision of determinations but also on the requirements to their limiting (admissible) accuracy. The limits of detection and determinations of an analytical procedure found by this approach completely characterize the possibilities of an analytical procedure in determining low concentrations of analytes. The proposed approach can be used for the estimation of the limits of detection and determination of analytical procedures and in other methods of chemical analysis with the hyperbolic dependence of the relative standard deviation on the analyte concentration.     

Synthesis of Multicomponent Oxide Low-Dimensional Systems on the Surface of Porous Silicon Dioxide Using the Molecular Layering Method

Reflecting the research in the field of the surface chemistry of solids over the last 25-30 years, the results related to the application of the molecular layering method for the synthesis of surface low-dimensional structures of complex composition are presented. The regularities of formation of multicomponent mono-, multilayers on the surface of solid-phase matrices are studied on examples of chemical interactions, by a preset program, of chlorides and oxychlorides of titanium, vanadium, phosphorus, chromium, zinc, and iron with hydroxy and secondary functional groups of porous silicon dioxide. On the basis of chemical-analytical and spectroscopic data, structural schemes of synthesized products are proposed and functional interactions in multicomponent monolayers on the surface are considered. The reactivity of the element chlorides and oxychlorides as a function of the chemical composition of surface functional groups of silica and on synthesis conditions is estimated. In view of the revealed regularities of formation of complex low-dimensional systems on silica surface, prospects of application of the resulting data are considered for elaboration of scientific foundations of the chemical nanotechnology of production of solid-phase materials of various functional use, based on the molecular layering method.     

Heterocyclic nitro compounds XIX. Kinetics of the methylation of 3(5)-nitro-1,2,4-triazoles with dimethyl sulfate

The effect of a substituent in the triazole ring and of the composition of the solvent on the reaction rate was established as a result of a study of the kinetics of methylation of sodium salts of 3(5)-nitro-1,2,4-triazoles in water and water-dioxane mixtures. The relationships found are due to the different degree of dissociation of intimate ion pairs of anions of nitrotriazoles with sodium and the specific character of the solvation of the anions by water.     

直链醇链长对层状液晶结构与稳定性的影响

作为助表面活性剂,直链醇在层状溶致液晶的制备中是非常重要的。本文以层状液晶的相行为和小角度X射线衍射测量,研究了直链醇链长对层状液晶结构与稳定的影响。     

The oxidative destruction of lignin in the ozonation of wood

The oxidative destruction of lignin in the ozonation of aspen wood was studied. The kinetic curves of ozone consumption for samples with different contents of water were obtained. The consumption of ozone increased as the content of water grew. The second derivatives of the UV absorption spectra of lignin were obtained to show that the principal direction of lignin transformations under the action of ozone was the destruction of its aromatic constituents with the formation of carboxyl- and carbonyl-containing compounds. Measurements of the UV diffuse reflectance and EPR spectra of wood showed that the ozonation of wood caused the destruction of lignin quinoid structures. Part of lignin remained unchanged under the action of ozone. A key role in the destruction of wood lignin was played by ozone dissolved in water. Varying the content of water in wood samples allows various lignin transformation products to be obtained through ozonation.     

Ultraviolet absorption of flavonoids. V. The structure of 3- and 5-hydroxyflavones

Summary 1. The peculiarities of the properties of 3-hydroxyflavone are due to the fact that the introduction of the proton-donating hydroxy group directly into the heterocycle leads to an increase in the aromaticity of the pyrone fragment through the stabilization of a pyrylium structure.2. The causes of the decreased acidity and basicity of 5-hydroxyflavone are the formation of an intramolecular hydrogen bond of the chelate type and a disturbance of the coplanarity of the molecule. The combination of these factors explains the anomalously high position of the band of the stretching vibrations of the carbonyl group of this compound.Irkutsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 583–587, September–October, 1975.     

Thermal lens spectrometry for the synthesis and study of nanocomposites on the basis of silver salts absorbed by a polyacrylate matrix

Thermal lens spectrometry is applied to determine the absorption of transparent nanocomposite materials, which are produced by the thermal decomposition of silver salts absorbed in the bulk of a polymethacrylate matrix. The high spatial resolution of determination, corresponding to the size of laser beams, makes it possible to evaluate the homogeneity for the distribution of coloration in the matrix. The advantages of thermal lens spectrometry over spectrophotometry include the weak effect of sample scattering on the results of its absorption determination and a higher sensitivity of determination, which may exceed that of spectrophotometry by one or two orders of magnitude. The possibility of achieving local syntheses of nanosized particles in the bulk of the matrix by virtue of the photoinduced decomposition of silver salts in initial polyacrylate materials is shown. Thermal lens experiments also allow the combination of the synthesis of silver nanoparticles and control of the absorbance for the prepared structural units.     

Analytical Chemistry of Phases of Variable Composition and the Principles of Stoichiographic Determination of Such Phases in Multielement Multiphase Samples

The general problems of determining the stoichiometry and content of solid phases of variable composition in multielement multiphase substances are discussed. The possibilities and conditions of application of a reference-free stoichiographic method based on the differential dissolution (DD) of components for the analysis of samples containing spatially homogeneous and inhomogeneous phases are considered. The results of mathematical modeling of the DD process for a mixture of phases of constant and variable composition are presented. These data substantiate the use of the stoichiogram affinity criterion for the identification of spatially inhomogeneous phases of variable composition. Examples of applying the DD method to the phase analysis of various substances containing phases of variable composition are given.     

Harnessing the Capabilities of Spray Granulation in the Food Industry for the Production of Functional Foods

The article is the literature review of a current state of production technologies of powdery foodstuff, concentrates and multicomponent mixes. The need of the food industry for qualitative methods of processing of raw materials of different physical and chemical structure is noted. The authors give the reasons about need and possibility of a choice of granulation as a method of data processing of products. Physical and chemical features of granulation methods of disperse environments of various aggregate states based on the studied regularities and works of other authors are considered. The authors made the assumption of the application prospects of the method of liquid dispersion on the surface of particles in a suspended state for a granulation of foodstuff and they offered the alternative option. The possibility to use whey as binding element is considered. At the end of article authors draw the conclusion about the prospects of use of a method of dispersion of liquid on the surface of particles in a suspended state for a granulation of foodstuff.     

影响磷酸脲生成质量因素的实验研究

目前,关于磷酸脲制备工艺的报道比较含糊、数据不一,原料中杂质对磷酸脲质量的影响探讨不够深入。本文对磷酸与尿素为原料制备磷酸脲工艺中的结晶环节进行了实验研究,采用正交实验方法分析了影响磷酸脲质量的四个因素：中和温度、磷酸浓度、磷酸中硫、氟含量,并用回归分析法从宏观上建立数学模型,以预期和指导生产实际。     

Relative retention analysis in HPLC: The correlation between incremental relationships

It was shown that, in the absence of specific intramolecular interactions, residual silanol groups of reversed-phase sorbents should not affect the linearity of plots in the coordinates used in the method of relative retention analysis for pairs of substances. The validity of the method proposed previously for analysis of the selectivity of separation of substances was supported experimentally (based on the analysis of retention of substituted benzoates). The possibility of the extension of incremental relationships to the system consisting of three different substances was justified.     

An algorithm for three-dimensional Voronoi S-network

The paper presents an algorithm for calculating the three-dimensional Voronoi-Delaunay tessellation for an ensemble of spheres of different radii (additively-weighted Voronoi diagram). Data structure and output of the algorithm is oriented toward the exploration of the voids between the spheres. The main geometric construct that we develop is the Voronoi S-network (the network of vertices and edges of the Voronoi regions determined in relation to the surfaces of the spheres). General scheme of the algorithm and the key points of its realization are discussed. The principle of the algorithm is that for each determined site of the network we find its neighbor sites. Thus, starting from a known site of the network, we sequentially find the whole network. The starting site of the network is easily determined based on certain considerations. Geometric properties of ensembles of spheres of different radii are discussed, the conditions of applicability and limitations of the algorithm are indicated. The algorithm is capable of working with a wide variety of physical models, which may be represented as sets of spheres, including computer models of complex molecular systems. Emphasis was placed on the issue of increasing the efficiency of algorithm to work with large models (tens of thousands of atoms). It was demonstrated that the experimental CPU time increases linearly with the number of atoms in the system, O(n).     

Method of gas mixtures discrimination based on sensor array, temporal response and data driven approach

This work presents a method of gas mixtures discrimination. The principal concept of the method is to apply measurement data provided by a combination of sensors at single time point of their temporal response as input of the discrimination models. The pattern data combinations are selected for classes of target gases based on the criterion of 100% efficient discrimination. Combinations of sensors and time points, which provide pattern data combinations in course or repeated measurements, are encoded in the form of addresses. The designer of sensor system is responsible for their selection and they are included in the software of the final instrument. The study of the method involved the discrimination of gas mixtures composed of air and single chemical: hexane, ethanol, acetone, ethyl acetate and toluene. Two sensor arrays were utilized. Each consisted of six TGS sensors of the same type. The dynamic operation of sensors was employed. As an example the stop-flow mode was chosen. The work provides the evidence of the existence of sensor combinations and time points, which are successful in discrimination of studied classes of target gases. The persistence of addresses was discussed considering the ability of sensor array to recognize analytes, variability of repeated measurement results, number of repeated measurements and a twin sets of sensors. Altogether, the validity of the method was demonstrated.