Kinetics and mechanism of photolysis of 2,6-di-tert-butyl-1,4-benzoquinone diazide in benzene and deuterobenzene

Conclusions It has been established by kinetic and spectral methods that the cyclohexadiene carbene generated in the photolysis of 2,6-di-tert-butyl-1,4-benzoquinone diazide in benzene predominantly in the singlet state reacts with benzene to form a norcaradiene derivative, which isomerizes thermally to 4-phenylcyclohexadiene-2,5-one. The latter is converted thermally to 2,6-di-tert-butyl-4-phenylphenol.Translated from Izvestiya Akadeinii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2680–2685, December, 1986.     

Oxidative dehydrogenation of C5 hydrocarbons in the presence of hydrochloric acid

Conclusions The oxidative dehydrogenation of C₅ paraffin hydrocarbons on Fe catalysts in the presence of HCl leads mainly to the formation of unsaturated hydrocarbons, which have the same structure of the carbon skeleton as the starting hydrocarbon, in which connection the yield of olefinic hydrocarbons proved to be substantially higher (25% from isopentane and 32% from n-pentane) than the yield of dienes (respectively 15% of isoprene and 11% of piperylene).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2599–2601, November, 1972.     

2-(8-quinolylazo)-7-phenylazochromotropic acid as an analytical reagent

2-(8-Quinolylazo)-7-phenylazochromotropic acid (QAPAC) has been synthesized by coupling diazotized 8-aminoquinoline with 2-phenylazochromotropic acid as well as by coupling diazotized aniline with 2-(8-quinolylazo)chromotropic acid. The properties of QAPAC and the spectrophotometric characteristics of some metal-QAPAC complexes are reported.     

Interaction between 18-crown-6-tetracarboxylic acid and positional substituents of enantiomers and simultaneous separation of positional enantiomers of methyl-DL-tryptophans by capillary electrophoresis

18-Crown-6-tetracarboxylic acid (18C6H4) is a chiral selector with high selectivity for the enantioseparation of solutes bearing the primary amine function. This work presents the simultaneous separation of positional enantiomers of methyl-DL-tryptophans by using 18C6H4 as an additive to the background electrolyte. Separation conditions such as pH, the concentration of 18C6H4, and the applied voltages have critical inference on the simultaneous separation. The addition of cyclodextrins as anionic surfactants to the background electrolyte did not improve the separation. The selector-selectand interactions between 18C6H4 and the positional enantiomers have been investigated. It was observed that both the position and type of substituents contribute to the enantioselectivity. The migration order and resolution depended on the distance from the substituents to the asymmetric carbon of the enantiomers.     

Surface recombination in breakdown time delay experiments: Effect of different cathode materials

The late afterglow in nitrogen with iron electrode is studied by the breakdown time delay method, i.e., by measuring the breakdown time delay t_d as a function of the afterglow time . It is proposed that the cause of the secondary electrons initiating the breakdown is the energy of the surface recombination of nitrogen atoms on the iron electrode. The gas-phase and macrokinetic diffusive models are used to describe the experimental breakdown time delay data. By fitting the theoretical curve to the experimental data: (1) it has been confirmed that the recombination on the molybdenum glass is of the second order and the value of the surface recombination coefficient is determined at 4 mbar; (2) it has been shown that the surface recombination on the iron electrode is of the second order, and the effective recombination coefficients are determined; (3) the analytical form of the recombination coefficient as a function of the adsorption characteristics of surfaces and the pressure of the parent gas has been derived. In addition, the orders of surface recombination on the molybdenum-, aluminum-, and gold-plated electrode were determined by the same method.     

Microdetermination of proteins using m-carboxychlorophosphonazo as detection probe by enhanced resonance light scattering spectroscopy

Proteins can be determined using a common spectrofluorometer to detect the intensity of resonance light scattering (RLS). Under acidic conditions, the reaction between m-carboxychlorophosphonazo (CPA-mK) and proteins enhances the weak light scattering of CPA-mK drastically. This enhanced intensity is proportional to the concentration of proteins. The linear ranges for human serum albumin are 0.5-35.0 microg/mL, with detection limits of 0.104 microg/mL. The method yields results comparable to those of the calorimetric method using Coomassie Brilliant Blue G-250 (CBB) with relative standard deviations of 0.72-2.10% (n = 10). There is almost no interference by amino acids and most of the metal ions.     

A thermogravimetric analyzer for condensable gas adsorption under subatmospheric conditions

Potential alternative to petrochemical polymers, soy protein isolate (SPI), a plentily available, natural biopolymer is chemically modified with thiourea at 2.5, 5, 7.5, 10, 15 and 20 mass/mass% for better processing of plastic as a raw material. From the FTIR studies, it has been ascertained that there is no bonding reaction between SPI and thiourea and it acts as a modifier only. Thermogravimetric analysis of the modified material has been followed using a computer analysis method, LOTUS package, developed by us for assigning the degradation mechanism. A number of equations have been used to evaluate the kinetic parameters. The mechanism of degradation of the biopolymer is explained on the basis of the kinetic analysis.