Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

SOL-detectability of liver SPECT--analysis of the structure of ROC-curve

The purpose of this study is to evaluate the clinical efficacy of liver SPECT (single photon emission computed tomography). The two examinations were performed in 76 cases with SOL (space occupying lesion) and 58 normal cases. The results of the image reading by the planar image only (PS) and that of the image reading by the combination of PS and SPECT (PS + SPECT) were analyzed by ROC (receiver operating characteristic) analysis. The ROC curves showed that SPECT appears to reduce the number of results which were equivocal by the image reading of PS only. The detectability of SPECT for SOL in the left lobe of liver was less than that of PS without statistical significance. However, the performance of SPECT for SOL in the right lobe of liver was significantly better than that of PS.     

Determination of degree of crystallinity of drawn polymers by means of density measurements

The well known procedure of determining the degree of crystallinity by means of measuring the density presupposes the knowledge of both the densities ρ_c and ρ_a of the crystalline and of the noncrystalline regions. By combination of small-angle and wide-angle x-ray scattering and of density measurements it can be shown that this method is not justified in the case of drawn polyethylene if the values of ρ_c and ρ_a known from isotropic material are used. Both ρ_c and ρ_a depend considerably on annealing and drawing conditions. In addition the effective density ρ_c^* of the more densely packed phase in a two-phase structure is much lower than the value ρ_c calculated from the positions of the x-ray reflections due to a large number of lattice defects. This conclusion is based on the results of three independent sets of experiments: determination of the mean-square fluctuation of density 〈η²〉 by means of x-ray small-angle scattering; x-ray wide-angle measurements of the positions of the crystal reflections and of the halo arising from the noncrystalline regions; and comparison of densities and long periods of samples treated at various annealing temperatures.     

Phospholipids of the seeds of two species of Erysimum

Summary The phospholipid complexes of the seeds ofErysimum diffusum andE. sylvestris have been investigated. It has been found that the amount of phospholipids in the seeds ofE. diffusum is lower than in those ofE. sylvestris, but their qualitative compositions are similar. The fatty-acid compositions of the triglycerides and of the total phospholipids of the two plants investigated have been studied. It has been established that the total phospholipids of the species ofErysimum under consideration and individual fractions of them differ by the degree of saturation and the qualitative and quantitative composition of the acids that they contain and, consequently, the phospholipids present in greatest amount differ in their molecular compositions.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 623–627, September–October, 1977.     

Prediction of latent heat of vaporization of multicomponent mixtures

A very simple method has been developed for predicting the differential latent heat of vaporization involved in vapor-liquid equilibria of multicomponent mixtures. The technique uses the UNIFAC method for predicting activity coefficients.In order to establish this method, 88 binary systems and 13 ternary systems, both nonazeotropic and azeotropic, were tested successfully. On the basis of the 101 systems investigated, the mean overall deviation between the observed and predicted values was found to be 4.6%. Despite the fact that the majority of the systems tested were azeotropic, a consequence of the small amount of data available for the differential heats of nonazeotropic systems, the method proposed is equally applicable to nonazeotropic systems.For azeotropic mixtures, it is possible to predict the latent heat (integral or differential) by means of an analytical equation which involves only the parameters of Antoine's equation, with a mean overall deviation of 6.1%.From the differential heats obtained by the proposed method, it is possible to calculate integral heats by applying equations derived here which relate these quantities.     

Estimation of contamination of atmosphere of Moscow in winter

To establish the priority pollutants in the atmosphere of Moscow in winter 8 snow samples were collected along the perimeter (109 km) of the Moscow Ring Road. Mass spectrometry was used as an analytical tool to identify individual organic compounds (gas chromatography/mass spectrometry) and the most environmentally relevant chemical elements (inductively coupled plasma with mass spectrometric detection). As a result several hundred organic compounds belonging to various classes, including representatives of the list of priority pollutants of the USA Environmental Protection Agency were identified. Their levels as well as the levels of chemical elements were quantified. The importance of accurate mass measurements for the efficient structural elucidation and reliability of quantitative measurements has been demonstrated. The data obtained allow estimating atmospheric pollution in Moscow in the period between December and March and proposing a list of priority pollutants for the atmosphere of Moscow.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evaluation of the uncertainty of environmental measurements of radioactivity

Results obtained by measurement of radioactivity have traditionally been associated with an expression of their uncertainty, based on the so-called counting statistics. This is calculated together with the actual result on the assumption that the number of counts observed has a Poisson distribution with equal mean and variance. Most of the nuclear scientific community has, therefore, assumed that it already complied with the latest ISO 17025 requirements. Counting statistics, however, express only the variability observed among repeated measurements of the same sample under the same counting conditions, which is equivalent to the term repeatability used in quantitative analysis. Many other sources of uncertainty need to be taken into account before a statement of the uncertainty of the actual result can be made. As the first link in the traceability chain calibration is always an important uncertainty component in any kind of measurement. For radioactivity measurements in particular we find that counting geometry assumes the greatest importance, because it is often not possible to measure a standard and a control sample under exactly the same conditions. In the case of large samples we have additional uncertainty components associated with sample heterogeneity and its influence on self-absorption and counting efficiency. In this paper we prepared an uncertainty budget for existing data for ¹³⁷Cs in Danish soil, which is shown to account adequately for all sources of uncertainty. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of methods of preparation of 1,4-diglycidyltetrazolone. New synthesis of triglycidylisocyanurate

1,4-Digtycidyltetrazolone was synthesized for the first time by the reaction of tetrazolone and epichlorohydrin with subsequent treatment of the products of addition with a base. The basic directions of the reaction of carbamoyl azide with epichlorohydrin, which yields triglycidylisocyanurate and diglycidylcarbamoyl dude, were investigated. The features of the synthesis and properties of the substances obtained were described.     

Phospholipids of the seeds of experimental varieties of kenaf

Phospholipids of the seeds of kenaf of the variety Opytnyi-1931 are similar with respect to their set of components and the qualitative composition of the fatty acids of homogeneous classes to the phospholipids of the variety Opytnyi-1972, but differ with respect to the amounts of individual acids. The fatty-acid composition of the lysophosphatidylcholines and lysophosphatidylinositols of experimental varieties of kenaf seeds have been studied for the first time.Institute of the Chemistry of Plant Substances of the Academy of Sciences of the Uzbekh SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 158–160, March–April, 1986.     

Development of certified reference samples of solutions of trihalomethanes

A method for the metrological certification of reference samples (RS) of solutions of organic compounds was proposed. The method is based on a procedure of sample preparation that uses both calculated and experimental data and involves the evaluation of the purity of the reagents employed. Impurity components were identified. Procedures for the determination of impurity components in source materials by gas chromatography with flame-ionization detection were developed. Calibration coefficients for halogen-containing impurity components in reference to an internal standard were determined experimentally or calculated. Certified reference samples of solutions of trichloromethane, bromodichloromethane, dibromochloromethane, and tribromomethane were designed for the quality control of drinking water     

Effect of composition of coordination sphere on value of constant of additional hyperfine structure of EPR spectra

Conclusions Replacing the oxygen atoms by sulfur atoms in the coordination sphere of nitrogen-containing copper complexes leads to a substantial increase in the constant of the additional hyperfine structure from the nitrogen atoms, and consequently also to an increase in the degree of covalency of the Cu-N bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 704–706, March, 1974.The authors thank V. I. Nefedov for taking the x-ray electronic spectra of compounds (I) and (II).     

Effect of the Method of Modification of Zeolite X on Selectivity of Catalytic Methylation of Toluene

Theoretical and Experimental Chemistry - The effect of the method of modification of catalysts based on zeolite X by cesium and magnesium cations (ion exchange and impregnation) on the selectivity...