Cyclization of N-alkyl azinium cations with bifunctional nucleophiles. 21. Regioisomeric 1,3,4-thiadiazino[5,6-b]quinoxalines

Thiobenzhydrazides undergo cyclization with N-alkyl-quinoxalinium salts to give 5-alkyl-substituted 1,4,4a,5,10,10a-hexahydro-1,3,4-thiadiazino[5,6-b]quinoxalines, which undergo isomerization to 10-alkyl-substituted thiadiazinoquinoxalines when they are heated in ethanol or in the presence of acids.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 557–561, April, 1987.     

Biferrocenes and terferrocenes

Russian Chemical Bulletin -     

The structure of the hydrazones formed fromβ-dicarbonyl compounds under the conditions of the azo-coupling reaction

Summary The arylhydrazones formed from -dicarbonyl compounds under the conditions of the azo-coupling reaction have a chelate structure with an intramolecular hydrogen bond attached to one of the carbonyl groups.     

Dichotomy in the reaction between cinnamyl dithiocarboxylates and tetracyanoethylene with the formation of 7,8-dithiabicyclo[3.2.1]octanes and dithioacyloxycyclopentanes

The reaction of cinnamyl dithiocarboxylates (1) containing electron-donating substituents at the central carbon atom of the dithioester group (R = p-MeOC₆H₄, EtO, andp-Tol) with tetracyanoethylene affords 2,2,3,3-tetracyano-4-endo-phenyl-7,8-dithiabicyclo[3.2.1]octanes (2) as well as isomeric 3,3,4,4-tetracyano-2-phenyl-trans-1-dithioacyloxycyclopentanes (3). Dithiabicyclooctanes2 rearrange to the corresponding cyclopentanes3 upon thermolysis.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Deceased in August, 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1804–1808, September, 1995.This work was supported by the Russian Foundation for Basic Research (Project No. 93-03-04290), the International Science Foundation and the Russian Government (Grant M5Y 300), and the Russian State Committee on Higher Education (Scientific and Technical Program Fine Organic Synthesis, Project FT-12).     

Comparison of the absolute calibration method with the method of standard addition for the determination of halothane in blood by gas chromatographic headspace analysis

As long-term exposure to exhaled halothane can be a cause of hepatitis and/or damage to the liver, the determination of halothane in blood is important in clinical practice. Gas chromatographic headspace analysis appears to be the most successful method. In the present study, two methods of quantitative evaluation of the analysis were compared by statistical treatment and direct comparison. The absolute calibration method was found to be unsuitable since it yields entirely unreliable results. This is due to different contents of lipoid and other components in the blood of the normal population, and this influences the vapour phase concentration of halothane and results in different values for the slopes of calibration curves for different blood samples. The standard addition method gives reliable results.     

Revisiting catechol derivatives as robust chromogenic hydrogen donors working in alkaline media for peroxidase mimetics

Colloidal noble metal-based nanoparticles are able to catalyze oxidation of chromogenic substrates by H₂O_2, similarly to peroxidases, even in basic media. However, lack of robust chromogens, which work in high pH impedes their real applications. Herein we demonstrate the applicability of selected catechol derivatives: bromopyrogallol red (BPR) and pyrogallol (PG) as chromogenic substrates for peroxidase-like activity assays, which are capable of working over wide range of pH, covering also basic values. Hyperbranched polyglycidol-stabilized gold nanoparticles (HBPG@AuNPs) were used as model enzyme mimetics. Efficiency of several methods of improving stability of substrates in alkaline media by means of selective suppression of their autoxidation by molecular oxygen was evaluated. In a framework of presented studies the impact of borate anion, applied as complexing agent for PG and BPR, on their stability and reactivity towards oxidation mediated by catalytic AuNPs was investigated. The key role of high concentration of hydrogen peroxide in elimination of non-catalytic oxidation of PG and improvement of optical properties of BPR in alkaline media containing borate was underlined. Described methods of peroxidase-like activity characterization with the use of BPR and PG can become universal tools for characterization of nanozymes, which gain various applications, among others, they are used as catalytic labels in bioassays and biosensors.     

Analysis of data transmission technique based on pulsed laser

Pulsed lasers are used mainly in lidar systems as sources of short and highly energetic light pulses. In data transmission systems continuous wave lasers are typically applied, however it is also possible to use pulsed lasers in such systems. Such approach seems to be especially reasonable for devices where a pulsed laser is applied anyway and executes another function (rangefinding). The article discusses a data transmission concept based on a pulsed laser technology. Advantages and limits of such a transmission method are described. Influence of individual transmission elements on the effective data transmission speed is analysed.     

Preparation and characterisation of gelatine hydrogels predisposed to use as matrices for effective immobilisation of biocatalysts

Physical, enzymatic and chemical methods were used to develop an efficient procedure for preparing gelatine hydrogels of appropriate strength and elastic properties for applications as enzyme carriers. The concentrations of the crosslinking enzyme (transglutaminase), the initial amount of gelatine, the production time and the effect of additional crosslinking with glutaraldehyde were examined. As a result, the following conditions were selected: 0.1 g cm^?3 solution of gelatine, 0.01 g cm^?3 of transglutaminase (mTGase), a minimum of 2 h incubation at 4°C and an additional step of crosslinking with 1.0 vol. % of glutaraldehyde. Next, the absorption properties and storage stability of hydrogels so obtained were determined. From these results, it was observed that, with the exception of the physical gel, the remaining materials presented a relatively high resistance to hydrolytic degradation and retained their original spatial structure without any visible damages. The immobilisation experiments indicated gelatine-based hydrogels crosslinked with transglutaminase as suitable for use as matrices for the entrapment of enzymes, which catalyse the conversion of low-molecular mass compounds. In addition to the potential for effective re-use in subsequent batch processes, the essential advantage of the immobilised β-galactosidase obtained in the current study is a marked reduction in its volume under storage conditions of long duration, without any significant decline in catalytic activity.