Reactions of diterpenoids on solid supports II. Behavior of di- and tricyclic diterpenoids on alumina containing oxidants

The behavior of epimanool (1), epimanool oil, larixol (2), cis-abienol (3) and methyl dehydroabietate (4) on alumina impregnated with oxidants (H₂CrO₄ and KMnO₄) has been studied. This has led to the methyl ketone (5) and norambrenolide (8) - precursors of the perfume substances 14,15,17-trinorlabdane-8,13-dione (6), 8-hydroxy-14,15-bisnorlabd-II-en-13-one (7), and methyl 7-oxodehydroabietate (14). -Levantenolide (11) has been synthesized in one stage from cis-abienol (3)for the first time.Novosibirsk Insitute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 229–234, March-April, 1995. Original article submitted July 25, 1994.     

Calculation of the gas hydrate HS-1 framework structure and its energy estimation

Using the Zimmennan-Pimentel potential, we have calculated the basic atomic coordinates of the unit cell of the gas hydrate HS-lframework. A minimum change in the strain energy of hydrogen bonh U_H fakes place in formation of this framework from ice Ih. The dependence of U_H on the lattice parameters is derived.Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 5, pp. 175–178, September–October, 1993.Translated by T. Yudanova     

Methane Hydroxylation by Methane Monooxygenase: On the Problem of the Process Dynamics

Published data on the kinetic isotope effects of the hydroxylation of deuterium-substituted methane molecules (CHD₃, CH₂D₂, and CH₃D) by methane monooxygenase are examined in the framework of the two-step nonradical mechanism through the intermediate formation of a complex containing pentacoordinate carbon. The kinetic schemes with the first step involving one, two, and three hydrogen atoms of the oxidized substrate are considered. Contrary to the widely accepted oxygen rebound mechanism, the experimental results obtained for the oxidation of various substrates by methane monooxygenase and cytochrome P450 can be explained from the viewpoint of the dynamics of a general nonradical mechanism.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXVIII. Effect of the Nature of the Verdazyl Indicator on Salt Effects in Dehydrobromination of 3-Bromocyclohexene in Nitrobenzene

The salt effect on the rate of dehydrobromination of 3-bromocyclohexene in PhNO2 depends on the nature of the verdazyl indicator. With triphenylverdazyl and its chloro and nitro derivatives in the presence of Et₄NClO₄, a normal salt effect is observed, in the presence of bromides, a superposition of normal and special salt effects, while in the presence of chlorides, a superposition of normal and special negative salt effects. With the dimethoxy verdazyl derivative, a normal salt effect is always observed.     

An immobiline DryStrip application method enabling high-capacity two-dimensional gel electrophoresis

In the field of proteomics the need to detect low-abundance cellular components, such as regulatory proteins, is of critical importance. Two-dimensional polyacrylamide gel electrophoresis (2-D PAGE) is one of the most commonly used separation tools for these biological investigations. In this paper we report an alternative micropreparative 2-D PAGE sample application method, called the "paper bridge loading" method. This method makes it possible to apply a larger sample volume to commercially available immobilized pH gradient (IPG) strips. The Vh products required for focusing are only marginally longer than those used in analytical experiments. The method was compared to traditional cup loading and in-gel rehydration. With 18 cm long narrow-range Immobiline DryStrip pH 4.5-5.5, the "paper bridge" method allowed the application of 10 mg human plasma proteins compared to 3 mg with traditional loading methods. The corresponding figures using Escherichia coli sample was found to be 6 mg and less than 2 mg, respectively. The paper bridge method also showed the best results in terms of spot resolution and separation of high molecular weight proteins.     

Synthesis and polymerization of N-vinylindole

The reaction of indole with acetylene under pressure is investigated. It is shown that under the action of KOH in aqueous dioxane at 220° C, N-vinylindole C₁₀H₉N is formed in 66% yield, and that this compound undergoes free radical and cationic polymerization.     

Alkylation ofβ-diketones of the hexahydroindan series and their enamines

Conclusions The reactions of hexahydro-1,3-indandlone with ammonia and some amines were studied, and the structures of the products formed were proved. In the alkylation of-diketones of the hexahydroindan series and their enamines under the usual conditions C-alkylation products are not formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1214–1218, July, 1966.     

Hydrolysis study of organic acid anhydrides by differential thermal analysis-I Pyromellitic dianhydride

A technique for following the hydrolysis of pyromellitic acid dianhydride (PMDA) by differential thermal analysis (DTA) is described. On exposure of PMDA to moisture, an endothennic peak is initiated between 190 and 200 degrees . As the degree of hydrolysis increases, this peak becomes more intense and shifts to higher temperatures. The formation of pyromellitic acid (PMA) during the hydrolysis of PMDA can be determined qualitatively by DTA.