Hydrogenation of furfural on polymer-containing catalysts

The catalytic hydrogenation of furfural with molecular hydrogen has been investigated under mild conditions in the presence of metal complex catalysts with a polymeric macroligand. It has been shown that the reaction proceeds according to a consecutive scheme with the formation of furfuryl and tetrahydrofurfuryl alcohols. The kinetics of furfural hydrogenation has been investigated and the order of the reaction established; the rate constants of the first and second stages have been determined. The influence of the solvent and of the metal-to-polymer ratio on the furfural conversion have been investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 303–307, March, 1986.     

Analysis of human blood and liver tissue for copper,zinc and iron by the method of proton-induced X-ray emission analysis

The method of proton-induced X-ray emission (or PIXE) analysis has been investigated with reference to the study of minor and trace elements in biological tissue. Methods of specimen preparation have been investigated, and optimum instrumental conditions arrived at. The lower limits of detection for lead and zinc in blood have been investigated and have been found to be approximately 0.3 and 0.1 ppm for lead and zinc respectively, for a proton energy of 2.5 MeV. The concentrations of copper, zinc and iron have been studied in normal and diseased human liver tissue. In cirrhotic tissue the copper levels are substantially raised. We note also a diminution in liver iron in a case of alcoholic cirrhosis associated with clinical anaemia; and a blood zinc deficiency in primary biliary cirrhosis. The results are discussed in relation to existing work.     

A mechanistic evaluation of the amperometric response of reduced thiols in quinone mediated systems

The specificity of the reaction of benzoquinone with reduced thiol species has been investigated and the nature of the amperometric electrode response elucidated. The analytical applicability of the methodology has been assessed and it has been shown that through appropriate selection of the redox properties of the indicating quinone, interference from other electroactive species can be minimised. A discrepancy in the reaction stoichiometry has however been found between the glutathione and cysteine quinone adducts and the implications in interpreting the resulting sensor response are rationalised. The adaptation of the approach to disposable, screen printed electrode assemblies has been investigated.     

Use of different anticoagulants for HPLC separation and quantification of the free amino acid content of plasma

Amino acid analysis in plasma samples is a very important and difficult task and could represent a useful tool for preventing the occurrence of some diseases (diabetes, cancer, HIV disease). Even though amino acid analysis has been thoroughly investigated, there are still some steps which are not so clear in this analytical procedure, e.g. the coagulation process of the blood to afford plasma and serum. Various anticoagulants are used in clinical chemistry: in this paper we have investigated three commonly used anticoagulants, heparin, EDTA, and sodium citrate. The blood samples have been divided into three portions and each portion treated with a different anticoagulant. The entire analytical procedure (from blood collection to the coagulation all the way to HPLC analysis) has been extensively investigated; the chromatograms and the amino acid recoveries are reported, and the three anticoagulants compared. Finally, the best anticoagulant has been used to analyze glycemic curves of healthy patients: the behavior of essential amino acids in the different blood samples withdrawn has been studied.     

Study of solvents effect on distribution of configurational and conformational isomers of apo-tirucallol theoretically and experimentally

The adsorption of carbon monoxide on the rutile (1 1 0) and the anatase (1 0 1) surfaces has been investigated by a periodic approach using hybrid-exchange density functional theory; the quantum-mechanical study on the CO adsorption on the anatase surface has been carried out for the first time. The full optimization of the systems has been performed by considering different surface coverages and periodicities. The adsorption energetics have been investigated, on the basis of a recently proposed model, in terms of interaction, distortion and binding energies and the lateral effects have been analyzed using a simple model of nearest and next-nearest neighboring molecules. The experimental adsorbed CO stretching frequencies have been compared with the computed ones obtained by considering the highest investigated periodicity. The Lewis acidity of the two surfaces is comparable and the rutile (1 1 0) acid site seems to be slightly more electrophilic than that of the anatase (1 0 1) one.     

Photochemistry and kinetics of single organic nanoparticles in the presence of charge carriers

This paper describes a preliminary experimental study on charge injection in MEH-PPV polymer nanoparticles incorporated in an OLED type device. The nanoparticles have been investigated with single molecule fluorescence spectroscopy recorded simultaneously with charging and discharging of the particles. Structure and dynamics of an anion/MEH-PPV complex, proposed to be responsible for discrete photobleaching in conjugated polymers, have been investigated with this technique. Device physics and kinetics have been elucidated by using the fluorescent conjugated polymer nanoparticles as probes for detecting the presence of hole polarons, and have been related to the electrically induced oxidation and reduction of the anion/MEH-PPV complex.     

Studies in sesquiterpenes—LVI: Isolongifolene (part 7): mechanism of rearrangement of longifolene to isolongifolene—II

The question of possible neutral intermediates which may lie on the reaction pathway in going from longifolene to isolongifolene has been investigated using BF₃·Et₂O-AcOD and D₃PO₄-dioxane, as reagents. It has been found that longicyclene is not an obligatory intermediate. The mode of cleavage of cyclopropane ring in longicyclene has been investigated.     

Ring-closing alkyne metathesis mediated synthesis of cyclic β-turn mimetics

The application of ring-closing alkyne metathesis to synthesise conformationally restricted peptidic β-turn mimics has been investigated. A range of oligopeptides containing either two acetylenic amino acids, or two cysteine residues have been synthesised and subjected to suitable cyclisation conditions. The structures of the cyclic compounds are investigated by 2D NMR analysis.     

Synthesis and properties of sol-gel submicron silica powders doped with partly oxidized iron particles

Magnetic powders based on metallic iron crystallites encapsulated in submicron-sized spherical silica particles have been obtained and investigated. The metallic iron clusters have been produced by the exploding wire method. The silica shells have been prepared via the modified sol-gel Stöber method and the metallic particles have been entrapped by occlusion during the silica powder formation. The entrapped iron particles are partially oxidized due to the nature of the synthetic methods employed. The obtained hybrid materials have been investigated by electron microscopy, X-ray diffraction, magnetic and ζ-potential techniques. Such materials can be employed in such applications as e.g. magnetically-controlled drug vectors or electromagnetic field-shielding.     

Characterization of surface modifications of stainless steel samples after electron and ion bombardment by SEM, AES, and XPS

The interaction of inert or reactive gas plasmas with the surface of stainless steel has been investigated with the aim, to modify the surface and hence to reduce the outgassing rate of the material, an important factor for the production of an ultrahigh vacuum. The plasma treatments investigated may be an alternative to the common used in situ baking. The samples have been exposed to electrons, argon and oxygen ions either in a DC glow discharge or in a microwave discharge. The DC glow discharge in Ar/O₂, the most effective plasma treatment reduces the outgassing rate by a factor of 10. After this treatment the surfaces of the samples have been investigated with respect to the topography and the chemical composition (depth profile) by Secondary Electron Microscopy (SEM), Auger Electron Spectroscopy (AES) and X-ray Photoelectron Spectroscopy (XPS), respectively. The surface modifications resulting from the different treatments of the samples have been correlated to the outgassing rate.     

Studies on electroosmotic and electrophoretic behavior of cholesterol in aqueous solutions

Electrical properties of cholesterol interfaces have been investigated. For this purpose electroosmotic and hydrodynamic permeation of water, sodium chloride, barium chloride, aluminum chloride, and urea solutions across a cholesterol plug have been investigated. Dependence of electroosmotic permeability on concentration of electrolytes has also been studied. Electrophoretic mobility of cholesterol particles of known size distribution and dispersed in solutions of varying concentrations of electrolytes and urea has also been studied. The data have been used to estimate ζ potentials in order to have a plausible picture of the electrical double layer at the cholesterol/ solution interfaces.     

ESR and polarography of nitroazoles. 7. Anion-radicals of isomers of N-methyl-C-nitro-1,2,4-triazole

The anion-radicals of N-methyl-substituted 3-nitro-1,2,4-triazole have been studied by polarography, ESR, and quantum-chemical methods. The difference in electrochemical behavior of the N-methyl isomers of 3-nitro-1,2,4-triazole has been analyzed. The spin distributions in their anion-radicals have been investigated by quantum-chemical methods. The theoretical data obtained are in poor agreement with experiment. By varying the structural characteristics of the anion-radicals internal geometric parameters have been separated out which prove to have the greatest effect on spin distributions. Geometric structures were established for the investigated isomers by minimizing the functional describing the disagreement of the theoretical and experimental spin distributions on the magnetic nuclei. The calculated hyperfine structure constants for the magnetically active nuclei for the structures obtained were in good agreement with experiment. The influence of solvation effects on the electronic structure parameters of the nitrotriazole anion-radicals has been investigated. Hydrated complexes containing four molecules of water proved to be the most stable. Structural deformation of the solvated anion-radicals occurs in the same direction as on minimizing the functional.For part 6 see [1].Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk 664033, Russia; e-mail: vti@irioch.irk.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 193–202, February, 2000.     

A pragmatic procedure for predicting regioselectivity in nucleophilic substitution of aromatic fluorides

The scope and limitations of a method for predicting the regioisomer distribution in kinetically controlled nucleophilic substitution reactions of aromatic fluorides have been investigated. This method is based on calculating the relative stabilities of the isomeric σ-complex intermediates using DFT. A wide set of substrates and anionic nucleophiles have been investigated. Predictions from this method can be used quantitatively—these agree to an average accuracy of ±0.5 kcal/mol with experimental observations in eleven of the twelve investigated reactions.     

Application of phosphine-phosphite ligands in the iridium catalyzed enantioselective hydrogenation of 2-methylquinoline

The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites, has improved the enantioselectivity of the reaction up to 73% ee. The influence of additives in this reaction has also been investigated. Contrary to the beneficial influence observed in related catalytic systems, iodine has a deleterious effect in the present case. Otherwise, aryl phosphoric acids produce a positive impact on catalyst activity without a decrease on enantioselectivity.     

The colorimetric determination of silicate with special reference to sea and natural waters

The optimum conditions for the determination of silicate in natural waters by a molybdenum blue method have been investigated p-Methylaminophenol sulphate has a number of advantages over other reducing agents for the reduction of silicomolybdic acid to molybdenum blue. Beer's law is obeyed up to concentrations of at least 3 mg/l.The interference of several inorganic ions has been investigated; none of those encountered in natural waters is likely to cause error. The method has been applied to the analysis of sea-water and the “salt error” correction evaluated.     

Synthesis of Active Porous Silica Gel Matrices and Investigation of Their Properties

Adsorption-structural and mechanical properties and heat treatment behaviour of alkoxy-derived hydrogels prepared by acid-catalyzed reaction of tetraethoxysilane have been investigated. Conditions for synthesizing xerogels as transparent, active mesoporous matrices have been found. The relation between the amount of immobilized optical active components and the textural features of matrices have been investigated.     

Radiochemical separations by adsorption on some oxides of groups IVB and VB

The interactions between titanium dioxide, niobium pentoxide and tantalum pentoxide and 55 elements have been studied by batch experiments in nitric acid. The variation of the distribution ccefficients with nitric acid concentration is presented and discussed. The adsorption mechanism for some ions has also been investigated. Column experiments have been carried out to check the practical use of the investigated oxides in radiochemical separations. A^99mTc generator based on the use of TiO₂ is also presented.     

Powder X‐Ray Diffraction Investigation of Xylazine Hydrochloride Solid Phase Transformation Kinetics

The kinetics of the solid‐state phase transformation of xylazine hydrochloride form X to A has been investigated using powder X‐ray diffraction and differential thermal analysis. Three different kinetic models have been used to describe transition kinetics: the Avrami–Erofeev equation, the Cardew equation, and the methodology for simulation of solid‐state phase transition kinetics by the combination of nucleation and nuclei growth processes. The latter has been recently developed and has been tested in this paper for the case of a real solid‐state transition. The relative humidity, mechanical pressure, temperature, and sample‐preparation effect on phase‐transition kinetics have been investigated, and rate constant changes have been analyzed.     

稀土铌钽矿中铌、钽、锆量的电感耦合等离子-原子发射光谱法测定

本文研究了用电感耦合等离子-原子发射光谱(ICP-AES)法测定稀土铌钽矿中的铌、钽、锆。实验考察了不同溶样方法及其对样品的溶解程度,确定了称样量及其熔融物提取的方法,选择了分析线波长,确定了仪器工作条件,考察了共存元素的干扰情况。对方法的准确度及精密度进行了考察。本法测定Nb、Ta和Zr的线性范围分别为0.50~5.00μg/mL、0.10~1.00μg/mL和5.00~50.00μg/mL,对于0.050%~0.20%Nb2O5、0.010%~0.20%Ta2O5、0.50%~5.00%ZrO2测定的相对标准偏差均小于7%。