The seed oil of Catalpa. I

Summary 1. The fatty-acid compositions of the seed oils of catalpas cultivated in the Soviet Union have been studied.2. The oil content of the seeds is 21.2–36.7%, the refractive index 1.4905–1.5400, and the iodine number 184.8–201.7.3. The following fatty acids have been found in catalpa oil (%): palmitic — 1.3–4.3; stearic — 1.1–2.5; heneicosanoic — 0.5–5.2; oleic — 5.5–9.8; linoleic — 39.6–50.3; linolenic — 0.4–1.8; and eleostearic — 32.8–46.2.4. The most accurate results for characterizing the degree of unsaturation of the fatty acids of the catalpa seed oils are given by Woburn's method of determining iodine numbers. The iodine numbers obtained experimentally agree with those calculated and consequently the addition of halogen to the system of double bonds takes place at all the double bonds.5. The degree of unsaturation of the fatty acids of catalpa oil characterized by the iodine numbers and refractive indices increases in the sequence of species southern, northern, teas, Chinese and has a tendency to rise on passing to more northerly zones, which is one more piece of evidence confirming the correctness of S. L. Ivanov's climatic theory of the structure of fats.Kalinin Polytechnic Institute. Moscow Branch of the All-Union Scientific-Research Institute of Fats. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 331–337, May–June, 1977.     

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.     

Simple and sensitive assay for nucleic acids by use of the resonance light-scattering technique with copper phthalocyanine tetrasulfonic acid in the presence of cetyltrimethylammonium bromide

On the basis of enhancement of resonance light scattering (RLS) of copper phthalocyanine tetrasulfonic acid (CuTSPc) by nucleic acids and cetyltrimethylammonium bromide (CTMAB) under suitable conditions, a new RLS method for determination of nucleic acids in aqueous solutions has been developed. At pH 9.80–10.95 and ionic strength 0.01 mol L^–1 (NaCl), the interaction of copper phthalocyanine tetrasulfonic acid with nucleic acids in the presence of cetyltrimethylammonium bromide results in enhanced RLS signals at 282.0 nm, 383.6 nm, and 616.2 nm in the enhanced regions. It was found that the enhanced RLS intensity at 383.6 nm was proportional to the concentration of nucleic acids within suitable ranges. The limits of detection were 10.6 ng mL^–1 for fish sperm DNA and 32.4 ng mL^–1 for calf thymus DNA when the concentration of copper phthalocyanine tetrasulfonic acid was 2.0×10^–6 mol L^–1. This method is rapid, simple and sensitive. In addition, the reagents used are relatively inexpensive, stable, and easily synthesised. The method can be applied to the determination of nucleic acids in the presence of coexisting substances, and we have applied it to the determination of DNA in synthetic samples, with satisfactory results.     

Analysis of anthropogenic and biogenic lipids in the aerosol of a coastal area in East Mediterranean Sea

Summary The concentrations of lipids were determined in atmospheric particle samples, collected seasonally, in an urban coastal area of the Island of Crete. Lipid compound classes, such as n-alkanes, hopanes and steranes, PAH, fatty alcohols, fatty acids and fatty acids selts, were determined by GC-FID and GC-MS analysis. The concentrations ranged between 56–215 ng/m³ for n-alkanes, 10–52 ng/m³ for PAH, 2–31 ng/m³ for fatty alcohols, 13–279 ng/m³ for fatty acids and 24–220 ng/m³ for fatty acid salts. -Oxocarboxylic acids were also determined as salts, indicating the atmospheric oxidation of unsaturated fatty acids.     

Study of the reactivity of ammonium carboxylates in the synthesis of amides under high-pressure deformation conditions

On deformation under pressures up to 10 GPa the ammonium salts of aliphatic and aromatic acids, as well as mixtures of a free carboxylic acid with the ammonium salts of strong mineral acids, are converted into the corresponding amides. The amide yields increase with pressure, the magnitude of shearing deformation, and temperature. The temperature and pressure coefficients for amide formation are low and have values of 2.5–4 kJ/mole and –1 to –2 cm³/mole, respectively. The reactivity of ammonium salts in the synthesis of amides alternates in the homologous series of aliphatic acids in a similar way to the shear stress of these salts. The reactivity of the ammonium salts of aliphatic acids increases when the reaction is conducted in a matrix of an ammonium salt which possesses plasticity and a high shear stress.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2289–2292, October, 1989.     

Fruit lipids of four rose varieties

A study has been made of the fruit lipids of four vitamin-bearing varieties of rose: Vorontsovskii-1, Vorontsovskii-3, Besshipnyi, and Vitaminnyi of VNIIVI [All-Union Scientific-Research Institute of the Vitamin Industry], that have been introduced into Tashkent Botanical Garden. It has been found that the oil is concentrated mainly in the seeds — about 9% — and the carotenoids in the pericarp — 2613–3933 mg% of the weight of the lipids. Essential fatty acids make up 61.5–70.6% of the weight of the fruit fatty acids.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 674–675, September–October, 1995. Original article submitted April 22, 1995.     

Oxygenated acids of the reserve lipids of Rumex paulsenianus

The composition of the fatty mono- and dihydroxy acids of the fruit ofRumex paulsenianus Rech. fil. (familyPolygonaceae) has been determined by a combination of IRS, UVS, GLC, and mass-spectrometric methods. (22) Monohydroxy acids of the C₁₄–C₂₀ series, including isomers and isologues, and four dihydroxy acids from C₁₈ to C₂₀, including a new isomeric 9-OH-10, 12–17:2 acid have been detected.Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 762–765, November–December, 1991.     

Thermal Analysis Studies on Human Skin and Skin Barrier Modulation by Fatty Acids and Propylene Glycol

The thermal behaviour of human stratum corneum (SC) with various hydration levels was studied using differential thermal analysis DSC within the temperature range of –130 to 120°C. SC containing 20% water, resembling the intact condition, shows thermal transitions at around –20°C (representing water in skin), –10, 40, 70°C (representing skin lipids), 85°C (representing protein-associated lipids) and 100°C (representing skin protein). Dehydration of SC causes the transitions at –20 and 100°C to be invisible. Lipid extraction followed by dehydration eliminates all transitions. Further hydration produces a transition of water at around 0°C with a huge change in enthalpy. The perturbation effects of penetration enhancers fatty acids (FA) and propylene glycol (PG) were studied using DTA on SC after pretreatment with PG alone and FA/PG. The application of PG alone shifted the transitions at 70 and 85°C to lower temperatures. Additionally, the application to dehydrated stratum corneum removes the transitions at –10°C. Saturated fatty acids, e.g. nonanoic and decanoic acids, exert barely noticeable effects on the thermal behaviour of SC suggesting that they easily mix with the skin lipids. Thermal analysis also revealed that the cis-9- and 13-isomers of octadecenoic acid (monounsaturated fatty acids) form a separate domain containing mostly the pure fatty acids within the SC lipids and suppress the lipid transitions at 70/80°C. Polyunsaturated fatty acids linoleic and -linolenic acids — form separate domains but do not completely suppress the SC lipid transitions at 70/80°C as monounsaturated acids do. This study suggests different ways of perturbation by various fatty acids.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of Hydroxamic Acids by Thermal-Lens Spectrometry

Conditions are determined for the determination of salicylhydroxamic and acetylhydroxamic acids by thermal-lens spectrometry using iron(III) in an aqueous medium. The detection limits are 6 × 10^–8 and 3 × 10^–8 M, respectively. The sensitivity can be enhanced 3–6 times with the use of aqueous–organic media.     

PVC Membrane electrode for trinitrobenzenesulfonate and its use for indirect determination of amino acids

A PVC membrane electrode of the conventional type was prepared which is selective for trinitrobenzenesulfonate (TNBS^–). It showed a rapid Nernstian response within the TNBS^– concentration range 1.0 × 10^–5 to 1.0 × 10^–2 M at 25 ± 0.1°C. The electrode was selective, precise (RSD < 0.87% for TNBS^– and < 1.32% for amino acids) and usable within the pH range 2.5–12. The standard electrode potentials,E°, were determined at different temperatures and used to calculate the isothermal temperature coefficient of the cell. Selectivity coefficients for numerous compounds are given. The electrode has been used for the direct determination of trinitrobenzenesulfonic acid in aqueous solutions either by the standard additions method or by potentiometric titration against cetyltrimethylammonium bromide (CTABr) at pH 7. The electrode has been also applied successfully for the indirect microdetermination of neutral, acidic and basic amino acids separately, and as binary or ternary mixtures of neutral amino-acids. Total amino acids were determined in urine samples.     

Reaction of dialkylboric anhydrides with 2-amino- and 2-hydroxypyridine

Conclusions The anhydrides of dialkylboric acids react with 2-aminopyridine at 150–190° and with 2-hydroxypyridine at 100–170° to give cyclic coordination compounds of boron and saturated hydrocarbons.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1919–1921, August, 1977.     

Fractionation and amino acid compositon of proteins of the woody verdure of sea buckthorn

The woody verdure of sea buckthorn is rich in protein substances. Among the soluble proteins, water- and alkali-soluble fractions predominate. The presence of 17 amino acids in the water-soluble proteins has been established. The sum of the essential amino acids amounts to 42.12–49.51%. The water-soluble proteins of the woody verdure of sea buckthorm possess a high biological value.Siberian Technological Institute, Krasnoyarsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 409–412, May–June, 1988.     

Oxidation of 1-(4-nitrophenyl)-2-formylpyrrole

Pyrrole aldehydes interact with oxidizing agents to yield products which are oxidized to different degrees. Pyrrolecarboxylic acids are formed under the influence of silver oxides, an alkaline solution of permanganate, and 2–10% sulfuric acid [1–3]. With peroxidation of hydrogen, 5-unsubstituted pyrrole aldehydes convert to pyrrolone [4], and pyrrol-2-aldehyde converts to succinimide [5]. Chromacetate and chromium sulfuric acids oxidize pyrrole aldehydes to maleinimides [3].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 495–499, April, 1982.     

A new method for quantitative mass-spectrometric analysis of solutions

Summary The mass-spectrometric method for the analysis of inorganic solutions is not only a very sensitive technique but also one of broad applicability. The study of the behaviour of solutions of mineral acids chilled to –70°C under a r.f. voltage from 7 to 15 kV indicated that solutions of hydrochloric acids containing 20–32% of hydrogen chloride allow to obtain stable ion currents. The equipment for the analysis of solutions on the spark source mass-spectrometer is designed and the procedure of analysis is described. The detection limits of 47 elements are in the range from 10^–7 to 10^–11 g. The accuracy of the determinations was established by the added-found method. The reproducibility is 0.1–0.34 for content levels of 10^–7–10^–9 g. The analytical possibilities of different spark source mass-spectroscopic methods for the analysis of solutions are compared.     

Photoreduction of rhenium(VII) in hydrochloric and sulfuric acids and their mixtures

Pulse photolysis has been used to investigate the photochemical reactions that take place in the series of oxochloride complexes of Re(VII), Re(VI), and Re(V) in concentrated hydrochloric and sulfuric acids and their mixtures. The kinetics of the formation and decay of the short-lived complex ReOCl ₅ ^– have been studied as a function, of the composition of the medium (the concentration of the acids and water). The causes of the stabilization of ReOC ₅ ^– in concentrated H₂SO₄ have been elucidated. It has been found that the anion radical Cl ₂ ^– formed in the photolysis of HCl oxidizes the complex ReOCl ₅ ^2– to ReOCl ₅ ^– .Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 3, pp. 296–302, May–June, 1986.     

Research in the imidazole series

The hydrolysis of 7-cyano derivatives of pyrrolo[1,2-a]imidazole in 85–90% sulfuric acid at 100°C gives amides of pyrroloimidazole-7-carboxylic acids. Under more severe conditions, the resulting carboxylic acids are decarboxylated to the corresponding pyrroloimidazole derivatives with a free 7 position.See [1] for communication XC.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1659, December, 1976.     

Gas chromatographic determination of serum bile acids — Application of a novel extraction procedure

Summary The profile of serum bile acids is a result of their liver metabolism and enterohepatic circulation.In the present work size exclusion chromatography is used for extraction of serum bile acids to optimize the methodology for analyzing serum bile acids by high resolution gas chromatography.Compared to other extraction methods like adsorption-[1–3] or reversed phase chromatography [4,5], this novel technique yielded a satisfactory recovery (75–104%) with high reproducibility. Therefore a reliable determination of serum bile acids is possible.     

Synthesis and properties of some Lewis and Brönsted acids of the indole series

It is shown that the products of condensation of a number of cyclic CH acids and 3-formylindole are Brönsted acids, whereas Lewis acids are obtained in the case of N-substituted 3-formylindole and 2-formylindole. The possibility of the catalytic hydrogenation of Brönsted and Lewis acids in alkaline media was established. The corresponding hydrogenation products are obtained in 80–85 and 36% yields.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1343–1348, October, 1978. Original     

Gas-Chromatographic Determination of Organic Compounds in Water with the Use of Supercritical Fluid Extraction

Procedures were developed for the determination of some organic compounds (n-alkanes, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, Cl,P,N-pesticides, phthalic acid esters, chlorophenols, aliphatic acids, and methyl esters of aliphatic acids) in water on the basis of direct supercritical fluid extraction with the subsequent gas-chromatographic analysis of the entire extract without using organic solvents. The detection limits were 10^–11–10^–7% depending on the nature of the analyte.     

Biamperometric end-point detection with quinhydrone electrodes in coulometric neutralization titrations in nonaqueous media

Some new possibilities for continuous coulometric titration of bases, alone and in mixture, as well as of mineral acids, alone and in mixture, were investigated with acetic anhydride-anhydrous acetic acid as solvents. The titration end point was determined biamperometrically. It was established that quinhydrone electrodes with platinum, palladium, and gold as the metal phase can be equally satisfactorily applied to the end-point determination of both the titrations of bases or acids alone, and of their two-component mixtures. Amounts of 6–10 μequiv. of bases, i.e., 20–47 μequiv. of mineral acids, were determined with the maximal average deviation of 1.4%. Results of biamperometric determinations of bases are compared to those of catalytic thermometric determinations, while those of acids are compared with the results of photometric titrations. The agreement between the methods is satisfactory.