A theoretical calculation of dissociation rates of molecular hydrogen in electrical discharges

Dissociation rates of molecular hydrogen in electrical discharges have been calculated at different electron (T_e) and gas (T_g) temperatures (10000 T_e 23000 K, 500 T_g 4000 K), at different pressures p (5 p 50 torr) and electron number densities n_e (0 n_e 10¹² cm⁻³).The results have been obtained by solving a system of master equations, including V---T (vibration-translation), V---V (vibration---vibration) and e---V (electron---vibration) microscopic processes.The results obtained at n_e ≠ O show a “laser-type mechanism” in the dissociation of molecular hydrogen in electrical discharges. In particular one notices a strong increase of dissociation rates with decreasing gas temperature and pressure.The results show that this mechanism is as important as the mechanism of direct dissociation by electron impact.     

Lipids of the seeds ofSecurinega suffruticosa

The lipid composition of the seeds ofSecurinega suffruticosa (Euphorbiaceae) has been studied, and eight classes of lipids have been identified with a predominance of triacylglycerols; the fatty acid compositions and structures of the triacylglycerols have been determined. Among the hydroxy acids of the hydroxyacylglycerols 13 components belonging to saturated, monoenic, and dienic acids of the C₁₇, C₁₈, and C₂₀ series have been identified; 12-hydroxyheptadecanoic and 12-hydroxyeicosanoic acids are new.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 277–281, May–June, 1986.     

Thermodynamics of saturated and unsaturated ketones C<Subscript>13</Subscript> and C<Subscript>18</Subscript> and the energy of specific intermolecular interactions

P-T dependences of the saturated vapor of pseudoionone, hexahydropseudoionone, and saturated and unsaturated ketones C₁₈ were studied using the statistical approach, and the enthalpies and entropies of its vaporization were calculated. The presence of monomer forms of the molecules of these compounds was established by studying the unsaturated vapor pressure. It was demonstrated that the role of isostructural methyl group in ketones is not related to the all-explaining steric effect concealing the real nature of the specific interaction. The energies of specific intermolecular interactions were determined in liquid symmetrical and unsymmetrical ketones.     

Analysis of long-chain fatty acids in grey wastewater with in-vial derivatisation

The presence and levels of long-chain fatty acids (C₆–C₂₀) in grey wastewater from bathrooms have been investigated. The acids were purified and concentrated by solid-phase extraction on strong anion exchange discs, in-vial derivatised to their corresponding methyl ester and subsequently analysed by GC-MS. The method was able to quantify the acids at concentration <1?µg/L with a recovery of 31–97%. The levels of fatty acids were found in the range of <0.5 to 27?100?µg/L and the highest levels were found for the saturated lauric (C₁₂), palmitic (C₁₆) and stearic (C₁₈) acids. The treatment efficiency of a local treatment plant was evaluated by comparing concentrations of fatty acids at the inlet and the outlet. It was found that the treatability decreases with increasing chain length for the saturated acids (19–100% degradation) whereas the corresponding mono unsaturated acids were more easily degraded.     

A thermodynamic interpretation of the behavior of higher fatty alcohols and acids upon the chromatographic paper

An idea was presented of treating the chromatographed substance as a “solute,” and the chromatographic system, composed of the stationary and the mobile phase as a “solvent.” Moreover the concept of “local equilibrium” was introduced, allowing to regard a given chromatographic spot as a “binary solution.” Thus a possibility arose to apply the classical thermodynamic approach, normally used for binary solutions, and namely: μ_i = μ_i + RT ln x_iƒ_i, where μ_i—chemical potential of the “i”-th compound in the solution, μ_i—chemical potential of the pure “i”-th compound, x_i-molar fraction of the “i”-th compound, ƒ_i—its activity coefficient, in a modified form, suitable for the chromatographic purpose.     

Starch Derivatives of High Degree of Functionalization 11: Studies on Alternative Acylation of Starch with Long-chain Fatty Acids Homogeneously in <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethyl acetamide/LiCl

Starch materials of different amylose content were allowed to react with saturated and unsaturated fatty acids of varying chain length from C₁₄ to C₁₈ under homogeneous conditions applying the solvent N,N-dimethyl acetamide in combination with LiCl. As reagent the corresponding acid chlorides and, alternatively, carboxylic acids in situ activated with toluene-4-sulfonyl chloride and N,N′-carbonyldiimidazole (CDI) were studied. Using fatty acid chlorides (FACl) and toluene-4-sulfonyl chloride-activated acids an almost complete substitution of the starch occurs. By in situ activation of the fatty acids with CDI, products with a degree of substitution up to 2 were obtained, which, in particular, represents a simple and very mild procedure.     

The fatty acid composition of the phospholipids of cottonseed oil

Summary 1. The phospholipids of cottonseed oil contain ten fatty acids.2. The positions of the double bonds in the aliphatic chain in the newly discovered unsaturated fatty acids — palmitlinoleic, palmitlinolenic, linolenic, and eicosadienic — have been established by the method of gas-liquid chromatography: they are present at the 6, 9; 6, 9, 12; 9, 12, 15; and 11, 14 carbon atoms, respectively, counting from the carboxyl end of the chain. A saturated fatty acid (myristic) has been found in the phospholipids of cottonseed oil for the first time.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 3, pp. 199–201, 1965     

Lipids of the vegetative and generative organs ofHibiscus sp.

The lipids of the leaves, stems, and roots ofHibiscus sp. have been studied. Their fatty acid compositions have been determined. The greatest amount of unsaturated fatty acids was present in the glycolipids of the leaves and the stems. More than 25% of low-molecular-mass C₁₀-C₁₂ fatty acids have been found in the neutral lipids of the roots.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 705–708, September–October, 1996. Original article submitted March 11, 1996.     

Thermodynamics of vaporization of gallium trichloride

The unsaturated and saturated pressures of gallium trichloride vapor were measured by the static method with membrane-gauge manometers in wide pressure (0.2–760 Torr) and temperature (313–1071 K) intervals. Scanning calorimetry was used to determine the thermodynamic characteristics of GaCl₃ fusion. The thermodynamic characteristics were obtained for sublimation, fusion, vaporization, and association in the vapor of GaCl₃ molecules. The enthalpies of formation and the absolute entropies of GaCl₃ in the liquid and gaseous phases and Ga₂Cl₆ in the gaseous phase were calculated using literature data. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1266–1269, July, 2007.     

Fatty acid composition of some Astragalus species from Turkey

In this study, the fatty acid contents of some Astragalus L. (Fabaceae) species from Turkey were determined by GC and GC-MS techniques. The seed oils of Astragalus sp. (A. echinops Aucher ex. Boiss., A. subrobustos Boriss., A. jodostachys, Boiss. & Buhse., A. falcatus Lam., A. fraxinifolius DC.) contained linolenic (between 23–41.%), linoleic (23–37%), and oleic acids (8–19%) as the major components. Fatty acid composition of the studied Astragalus taxa showed uniform fatty acid patterns. Palmitic and stearic acids were the major saturated fatty acids in the seed oils. The amounts of unsaturated fatty acids were higher than saturated fatty acids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 526–528, November–December, 2006.     

Investigation of the interactions between ginsenosides and amino acids by mass spectrometry and theoretical chemistry

In order to evaluate the essence of the interactions of ginsenosides and proteins which are composed by α-amino acids, electrospray ionization mass spectrometry was employed to study the noncovalent interactions between ginsenosides (Rb₂, Rb₃, Re, Rg₁ and Rh₁) and 18 kinds of α-amino acids (Asp, Glu, Asn, Phe, Gln, Thr, Ser, Met, Trp, Val, Gly, Ile, Ala, Leu, Pro, His, Lys and Arg). The 1:1 and 2:1 noncovalent complexes of ginsenosides and amino acids were observed in the mass spectra. The dissociation constants for the noncovalent complexes were directly calculated based on peak intensities of ginsenosides and the noncovalent complexes in the mass spectra. Based on the dissociation constants, it can be concluded that the acidic and the basic amino acids, Asp, Glu, Lys and Arg, bound to ginsenosides more strongly than other amino acids. The experimental results were verified by theoretical calculations of parameters of noncovalent interaction between ginsenoside Re and Arg which served as a representative example. Two kinds of binding forms, “head–tail” (“H–T”) and “head–head” (“H–H”), were proposed to explain the interaction between ginsenosides and amino acids. And the interaction in “H–T” form was stronger than that in “H–H” form.     

Change in the lipid composition of lichens in the spring period

The dynamics of the amount of total lipids, the ratio of the main classes of lipids, the amount of fatty acids, and the ratio of individual phospholipids in three epiphytic species of lichens from the Zhigulevsk reserve have been followed. It has been shown that all the classes of lipids of the lichens change to some degree or other in this period. The dynamics of the fatty acids has also confirmed a known rule: an increase in the amount of saturated and a decrease in the number of unsaturated fatty acids of the membranes with a rise in the temperature of the environment. This is the first time that the dynamics of the hydroxy acids have been followed.Institute of the Ecology of the Volga Basin, Tol'yatti. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 660–664, September–October, 1993.     

New Method of Analysis of Intermolecular Contacts in the Crystal Structure: π-Complexes

A new method for analysis of intermolecular contacts in the crystal structure based on characteristics of the Voronoi-Dirichlet polyhedra (VDP) is considered using metal π-complexes as examples. The crystal data of the compounds were used to determine the surface area of the VDP faces corresponding to all intermolecular contacts in one π-complex, the total volume of the pyramids with VDP faces as bases and the nuclei of atoms involved in the intermolecular contacts at the vertices, and the total solid angle at which the “intermolecular” VDP faces are seen from the corresponding nuclei of the molecule. A common linear correlation between the enthalpy of sublimation of π-complexes and saturated or unsaturated hydrocarbons and the molecular VDP characteristics was elucidated. On the basis of the results, the enthalpies of sublimation were calculated for some iron π-complexes (for which data on the crystal structure were available) and C₆₀ and C₇₀ fullerenes.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 7, 2005, pp. 495–505.Original Russian Text Copyright © 2005 by Serezhkin, Shevchenko, Serezhkina.     

Analysis of the Dynamic Decomposition of Unsaturated Fatty Acids and Tocopherols in Commercial Oils During Deep Frying

The decomposition of unsaturated fatty acids and tocopherols in 10 commercial edible oils during deep frying was investigated. The dominant tocopherol in oils rich in polyunsaturated fatty acids (PUFAs) was γ-tocopherol, except for natural perilla oil (δ-tocopherol dominant), and the main tocopherol in oleic acid-rich oils was α-tocopherol. The PUFA-rich oils had higher tocopherol contents than the oleic acid-rich oils. Both the reduction rate of total unsaturated fatty acid (TUFA) and total tocopherol (TToc) were linear with frying time (t). The decomposition rate of TToc is faster than that of TUFA since the slope values obtained from fitting equations (Y?=?k t) k_TToc (1.520–14.483) were obviously larger than for k_TUFA (0.155–0.270). By establishing a dynamic decomposition index, unsaturated fatty acids and tocopherol in oils showed dynamic decomposition over multiple frying cycles. The obtained results showed that decomposition characteristics of oils are related to their fatty acid compositions.     

Accurate analytic potential energy function and spectroscopic study for CH(XΠ) radical using coupled-cluster theory in combination with the correlation-consistent quintuple basis set

The coupled-cluster singles-doubles-approximate-triples [CCSD(T)] theory in combination with the correlation-consistent quintuple basis set (aug-cc-pV5Z) is used to investigate the spectroscopic properties of the CH(X²Π) radical. The accurate adiabatic potential energy curve is calculated over the internuclear separation ranging from 0.07 to 2.45 nm and is fitted to the analytic Murrell–Sorbie function, which is employed to determine the spectroscopic parameters, ω_eχ_e, α_e and B_e. The present D_e, R_e, ω_e, ω_eχ_e, α_e and B_e values are of 3.6261 eV, 0.11199 nm, 2856.312 cm⁻¹, 64.9321 cm⁻¹, 0.5452 cm⁻¹ and 14.457 cm⁻¹, respectively. Excellent agreement is obtained when they are compared with the available measurements. With the potential obtained at the CCSD(T)/aug-cc-pV5Z level of theory, a total of 18 vibrational states is predicted when J = 0 by numerically solving the radial Schrödinger equation of nuclear motion. The complete vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants are reproduced for the CH(X²Π) radical when J = 0 for the first time, which are in good agreement with the available RKR data.     

The composition of the organic acids of CO2 extracts of some spice-aromatic plants

Summary 1. It is desirable to analyze the composition of the organic acids of CO₂ spice extracts after their preliminary separation into individual groups according to their physicochemical properties: steam-volatile, ester-bound obtained after the hydrolysis of esters of nonglyceride nature, and acids forming components of the triglycerides.2. Characteristic for the fraction of steam-volatile free acids and for the ester-bound acids in the CO₂ extracts obtained after the hydrolysis of esters of nonglyceride nature are the C₁–C₇ low-molecular-weight saturated acids of the alipatic series: formic, isovaleric, valeric, caproic, etc. The higher fatty acids present include acids with even and odd numbers of carbon atoms from C₈ to C₁₈ and also acids with saturated and unsaturated bonds.3. The compositions of the lower acids in the extracts of all the samples studied are qualitatively very similar. Their quantitative compositions differ fundamentally. At the same time, differences both in the qualitative and in the quantitative compositions of the glyceride acids of the samples investigated are more pronounced. This is due to the circumstance that fruit was subjected to extraction in one case and leaves and rhizomes in another.Krasnodar Scientific-Research Institute of the Food Industry. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 763–767, November–December, 1977.     

Enorme Unterschiede in der qualitativen und quantitativen Zusammensetzung der Fettsäurefraktion von rohem und gekochtem Gemüse

Summary Potato tubers und vegetables, introduced into the body contain — in dependance if boiled or not — very different amounts of multiple unsaturated fatty acids. In boiled vegetables linoleic and linolenic acid remain unchanged. In contrast, if the vegetable is shred and then analysed, the content of multiple unsaturated fatty acids is lowered for a factor of 2–5. If vegetable is shred, lipoxygenases are liberated, resulting in oxidizing the multiple unsaturated acids. The lipoxygenases are destroyed if vegetable is cooked before shreding. An easy comparison of the effect of lipoxygenases on fatty acid can be made by gas chromatography. The effect is especially strong incruciferae e.g. in cabbage or cauliflower.

     

Theoretical study of homogeneous electron self-exchange in polar aromatic molecules: the role of the reactant structure

The solvent reorganization energies λ₀ of the electron self-exchange reaction between neutral molecules (nitrobenzene, its five para-substituted derivatives and benzonitrile) and the corresponding radical anions are discussed in terms of the Kirkwood approach combined with a semi-empirical calculation of the reactant structure (AM1 and intermediate neglect of differential overlap (INDO) methods). The theoretical values of λ₀ are compared with the experimental reorganization energies λ calculated from the Marcus equation and the homogeneous rate constants k_ex. It is found that the values of λ₀ obtained using the INDO method are approximately equal to the experimental λ, whereas the AM1 method gives poor results for para-substituted nitrobenzenes. The linear correlation of log k_ex with a_N² where a_N is a nitrogen coupling constant, established for para-substituted nitrobenzenes is interpreted. A simple criterion for slow electron transfer of an arbitrary flat polar arene is formulated in terms of the reactant structure and the model of the “specifying group” suggested earlier by some of the authors.     

Determination of sodium hydroxide in boiler water by a linear titration plot method

A simplified linear titration plot has been developed specifically for determining the sodium hydroxide content of boiler water. A known quantity of strong acid is added, in excess, to the alkaline sample which is then titrated with standard alkali. Functions are constructed from the titration data (pH, volume added) and known constants. These functions are linearly related, so that plotting one against the other gives a straight line of slope V_Y and intercept V_X, where V_X and V_Y are the volumes of titrant required to neutralize the “strong” (including for this purpose acetic and other carboxylic acids) and “weak” (ammonium ion and silicic acid) components. These are sufficient to enable the original sodium hydroxide concentration to be calculated. The constants required for the functions are the autoprotolysis constant of water and the association constant of ammonium ion. The functions can be calculated very easily with a programmable calculator.     

A Novel Labeling Reagent of 2-(12-Benzo[b]acridin-5-(12H)-yl)-acetohydrazide for Determination of Saturated and Unsaturated Fatty Acids in Traditional Chinese Herbs by HPLC-APCI-MS

A new fluorescence labeling reagent 2-(12-benzo[b]acridin-5(12H)-yl)-acetohydrazide (BAAH) has been designed for fatty acids labeling. Eleven fatty acids containing seven saturated and four unsaturated fatty acids were used to evaluate the analytical potential of this reagent. The labeling reaction of BAAH with fatty acids was completed at 85 °C for 60 min using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC·HCl) as the condensing agent. Separation of the derivatized fatty acids was carried out on a reversed-phase Thermo Hypersil Gold C18 column (4.6 mm × 250 mm, 5 μm) in combination with a gradient elution with a good baseline resolution. The fluorescence excitation and emission wavelengths were set at λ_ex 280 and λ_em 510 nm, respectively. The identification was carried out by the online APCI-MS in positive-ion detection mode. Linear correlation coefficients for all fatty acid derivatives were of >0.9994. Detection limits, at a signal-to-noise ratio of 3:1, were 3.89–12.5 nmol L⁻¹ for the labeled fatty acids. The developed method was successfully applied to the accurate determination of fatty acids in five traditional Chinese herbs with satisfactory results.