The mechanism of oxidation of indoxyl and its analogs to indigo and indigoides

Conclusions Intermediate formation of 3-oxynaphthenyl-2 radical during oxidation of 3-oxythionaphthene to thioindigo was demonstrated by the inhibitor method. The 1:1 recombination product of this radical and diphenylpicrylhydrazyl was isolated. It is assumed that the postulated oxidation mechanism is general for compounds possessing a methylene group bonded to an electron-donating X group and an electron-accepting C=O group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1168–1170, May, 1970.     

Urinary excretion of methylated purines in man and in the rat after the administration of theophylline

Chromatographic characteristics of urinary metabolites of theophylline were studied by two-dimensional thin-layer chromatography, high-performance liquid chromatography and gas chromatography--mass spectrometry. Quantitative date for the urinary metabolites of theophylline in asthmatic children are given. It was shown that 1,3-dimethyluric acid is the predominant excretory product. In addition, smaller amounts of 1-methyluric acid, 3-methylxanthine and unchanged theophylline were found. Excretory patterns after theophylline ingestion before and during the administration of allopurinol in asthma patients and in rats suggest the existence of three metabolic pathways of theophylline. The administration of this drug to a patient with xanthine oxidase of theophylline. The administration of this drug to a patient with xanthine oxidase deficiency resulted in the excretion of 1-methyluric acid in addition to 1,3-dimethyluric acid, 3-methylxanthine, 1-methylxanthine and unchanged theophylline. It was concluded that in man the oxidation of theophylline is not catalysed by xanthine oxidase.     

Topochemical investigations of peptide systems

The basic principles of the topochemical approach to the investigation of the structure-function relation in peptide systems are formulated. This approach makes use of the new possibility of transforming natural peptides, consisting in the modification of the molecule as a whole and utilization of the resultant analogs to elucidate the boundaries of the stereoelectronic complementarity of the biologically active peptide to the corresponding receptor. In particular, on the example of depsipeptide antibiotics and their topochemical analogs the fruitfulness of using such compounds as tools in elucidating the physicochemical basis of functioning of biological membranes is shown. The topochemical principle has also been applied in preparing specific competitive inhibitors of proteolytic enzymes, whose study may shed light on the nature of the forces binding the substrate to the contact site of the corresponding enzyme.     

Retention of analgin and anesthesin on sorbents with different polarities: The analysis of bellalgin tablets by high-performance liquid chromatography

The effects of acetonitrile and potassium dihydrogen phosphate concentrations in a mobile phase and the pH of the mobile phase on the retention of analgin (dipyrone) and anesthesin (benzocaine) on Symmetry C18 and Nova-Pak CN HP sorbents with grafted octadecylsilanol and nitrile groups, respectively, were studied. It was found that, under identical conditions, retention on the sorbent with grafted nitrile groups was weaker. A rapid and cost-effective procedure was developed for the determination of analgin and anesthesin in the analysis of Bellalgin tablets.     

Structure,tautomerism, and transformations of β-(3-nitro-2-pyridyl)- and β-(3-nitro-4-pyridyl)pyruvic acid esters

It was shown by means of IR, UV, and PMR spectra that -(3-nitro-2-pyridyl)pyruvic acid esters are practically completely enolized in the crystal state and in solution; ethyl -(3-nitro-4-pyridyl)pyruvate has an enol structure in the crystalline state and in pyridine solution but exists as a mixture of keto and enol forms in low-polarity solvents.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 389–393, March, 1974.     

Gas-discharge plasma initiated in air by a radiation pulse

Formation of a nonequilibriuin gas-discharge plasma in air under the action of radiation at a wavelength of 10.6 with a duration of 10^–6 sec is considered. It is shown that the air discharge occurs under nonequilibrium conditions by formation of an autoionization complex with subsequent oscillatory excitation of molecules. The molecular distribution function over oscillatory degrees of freedom is found in the diffusion approximation. The electron temperature and concentration in the breakdown plasma are calculated with consideration of multistep ionization of molecules and dissociative recombination of charged particles. Results are compared with experiment.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 9–13, February, 1985.     

Silicon-29 diffusion-ordered NMR spectroscopy (DOSY) as a tool for studying aqueous silicates

The first use of silicon-29 diffusion-ordered NMR spectroscopy (DOSY) is reported, in a study of the speciation of aqueous silicates.     

Optical waveguide sensors in analytical chemistry: today’s instrumentation, applications and trends for future development

Current concepts for chemical and biochemical sensing based on detection with optical waveguides are reviewed. The goals are to provide a framework for classifying such sensors and to assist a designer in selecting the most suitable detection techniques and waveguide arrangements. Sensor designs are categorized on the basis of the five parameters that completely describe a light wave: its amplitude, wavelength, phase, polarization state and time-dependent waveform. In the fabrication of a successful sensor, the physical or chemical property of the determined species and the particular light wave parameter to detect it should be selected with care since they jointly dictate the sensitivity, stability, selectivity and accuracy of the eventual measurement. The principle of operation, the nature or the detected optical signal, instrumental requirements for practical applications, and associated problems are analyzed for each category of sensors. Two sorts of sensors are considered: those based on direct spectroscopic detection of the analyte, and those in which the analyte is determined indirectly through use of an analyte-sensitive reagent. Key areas of recent study, useful practical applications, and trends in future development of optical waveguide chemical and biochemical sensors are considered.     

Catalysis by Heterogenized Metal Polymers: Advances and Prospects

The current status, trends, and a specific role for macroligands in catalysis by heterogenized metallopolymeric complexes are considered. Relations between homogeneous catalysis, enzyme catalysis, and catalysis by heterogenized metal complexes are traced. The effects of various factors on the catalysis of the main reactions used in organic synthesis—hydrogenation, polymerization (in particular, under the action of immobilized metallocene and postmetallocene catalysts), and redox processes (such as the catalysis of oxygenation, hydroperoxide oxidation, epoxidation, and hydroformylation)—are analyzed. In this review, attention is focused on the nondestructive identification of intermediates and catalytically active species in heterogenized systems. Experimental evidence is presented in support of the fact that the high activity, stability, and selectivity of immobilized catalysts are associated with a dramatic inhibition of concerted reactions in the coordination sphere of a transition metal, which result in catalyst deactivation, as well as with substrate enrichment. Prospects for the development of these highly organized hybrid systems and possibilities to consider the main requirements imposed on metal complex catalysis even at the stage of designing them are predicted.