Gas Chromato-mass Spectrometry Research Articles

ANALYSİS OF THE SESQUİTERPENE LACTONE AND COUMARİN CONTENT OF THE AERİAL PART OF THE GENUS CENTAUREA (CENTAUREA SOLSRİTALİS L.) OF ASTERACEAE DUMORT FAMİLY WAS MADE BY GAS CHROMATO-MASS SPECTROMETRY METHOD.

The article provides information on the medical and practical importance of sesquiterpene lac-tones, coumarin derivatives of the aerial part of Centaureae solsritalis L. -sunflower-rose spe-cies. The purpose of the study is to obtain and study by gas chromatography-mass spectrometry bio-logically active substances obtained parts of Centaureae salstritalis L Materials and methods. As the object of the study, substances obtained from the aerial part of Centaureae solsritalis L., in their essence, collected at the beginning of the flowering phase (July 07, 2019) in the vicinity of the village of Novkhany, Absheron region, were studied. The substances extracted with acetone were studied by gas chromatography-mass spectrometry. Results. As a result of the research, the following biologically active substances were obtained: α-santonin, isobergapten, osthole. Using the gas chromato-mass spectrometry method, the mo-lecular mass and retention time of these substances were determined.

Manifestation of incompatibility of marine residual fuels: a method for determining compatibility, studying composition of fuels and sediment

The results of studying the problem of active sediment formation when mixing residual fuels, caused by manifestation of incompatibility, are presented. A laboratory method has been developed for determining the compatibility and stability of fuels allowing identification of a quantitative characteristic of sediment formation activity. Laboratory studies were performed, and incompatible fuel components were identified. Tests were made to determine the quality indicators of samples and group individual composition of fuels. Results on the content of total and inorganic carbon in the obtained sediments were determined using Shimadzu TOC-V SSM 5000A. Chemical composition was determined and calculated on LECO CHN-628 analyser. Group composition of hydrocarbon fuels contained in the sediment was studied by gas chromato-mass spectrometry on GCMS-QP2010 Ultra Shimadzu. To obtain additional information on the structural group composition of fuel sediment, IR spectrometry was performed on IR-Fourier spectrometer IRAffinity-1. X-ray diffraction analysis of sediment samples was made using X-ray diffractometer XRD-7000 Shimadzu; interplanar distances d002 and d100 as well as Lс and Lа crystallite sizes served as the evaluation criteria. Microstructural analysis of total sediment was performed by scanning electron microscopy. The results of the research confirmed that the content of normal alkanes in the fuel mixture mainly affects sediment formation. Recommendations were drawn on preserving the quality of fuels and reducing sediment formation during storage and transportation.

МЕТАБОЛИТЫ АВТОТРОФНЫХ И ГЕТЕРОТРОФНЫХ ЛИСТЬЕВ АМАРАНТА Amaranthus tricolor L. СОРТА EARLY SPLENDOR

An important area of systemic biology (metabolomics) is the study of the composition and properties of low-molecular metabolites of agricultural plants with different modes of nutrition. The use of metabolic technologies expands the possibilities of analyzing biochemical changes in the composition and structural modifications of metabolites occurring during the transition from autotrophic to heterotrophic nutrition. Most photosynthetic plants are capable of autotrophic nutrition, but in their lifetime, there are periods of appearance of the achlorophyllic organs which receive nutritients from the organic substances stored earlier. Thus, among Amaranthus tricolor L. plants there are varieties with leaves which differ from each other in the way of nutrition. For example, Early Splendor variety plants form brightly colored red heterotrophic leaves along with green photosynthesis leaf blades at the end of the vegetative phase. The comparative study of the low-molecular metabolites composition in these leaves is important for understanding the relationship between heterotrophic and autotrophic nutrition in the whole plant. In this paper, significant qualitative differences in metabolites composition between autotrophic and heterotrophic leaves were stated for the first time during the metabolome analysis of water and alcohol extracts of heterotrophic and autotrophic amaranth leaves of Early Splendor variety using the method of gas chromato-mass spectrometry. It was found that the low-molecular metabolites of autotrophic and heterotrophic leaves contained both non-specific metabolites common for both type of nutrition and specific metabolites characteristic for each of the ways separately. On the one hand, it indicates the close interaction between two ways of nutrition and, on the other hand, the ability to synthesize and modify the metabolites which demonstrates partial autonomy of heterotrophic leaves. The purpose of the work is to study the composition of low-molecular metabolites and to identify new biologically active metabolites antioxidants in heterotrophic and autotrophic amaranth leaves of Early Splendor variety. Experiments were carried out in 2017-2019 with amaranth plants of the Early Splendor variety at the end of flowering—the beginning of seed formation phase. The plants were grown in a film greenhouse (the Federal Research Center for Vegetable Growing). The fresh red-colored heterotrophic leaves formed at the top of the main stem and the underlying photosynthetic leaves with a fully formed leaf blade were collected for analysis. The leaves were homogenized (T18 homogenizer, IKA, Germany) and extracted for 30 min at 24 °C with either 96 % ethanol or distilled water (leaves weighing batch: extragent 1:10). The metabolites were profiled by gas chromato-mass spectrometry method (GH-MC) with a chromograph GH-MC JMS-Q1050GC (JEOL Ltd., Japan). According to the mass spectra library of the NIST-5 National Institute of Standards and Technology (USA), a total of 87 metabolites were totally identified. Heterotrophic leaves contained 19 substances in water extracts and 38 metabolites in alcohol extracts, while photosynthetic leaves contained 21 substances in the water extract and 57 metabolites in alcohol extracts. Twenty-nine identical metabolites were found in water and alcohol extracts. In heterotrophic and autotrophic amaranth leaves of Early Splendor variety squalene (C30H50), a biologically active compound with antioxidant properties was identified for the first time. Also, in heterotrophic leaves monopelargonine (monononanoin) (C15H11O7) was identified. Monopelargonine is an intermediate product of flavonoid o-glycosylation, is referred to phenolic compounds and possesses high antioxidant activity. Metabolites have been identified that are present in both autotrophic and heterotrophic amaranth leaves, which suggests a close interaction of the two types of nutrition during the appearance, growth and development of heterotrophic leaves. At the same time, photosynthesizing leaves serve as donors of key metabolites for heterotrophic leaves, while the latter are not only acceptors, but also can synthesize and modify metabolites necessary for cell formation. Due to revealed rich composition of carbohydrates, essential amino acids, lipids and organic acids, the photosynthesizing leaf biomass is a source of antioxidants and biologically active substances. It should be stressed that not all metabolites were identified. Nevertheless, the set of metabolites that we identified in the photosynthetic leaves allows us to suggest these substances to be key and sufficient compounds for the construction and functioning of cells and tissues in heterotrophic leaves.

THE METABOLITES OF AUTOTROPHIC AND HETEROTROPHIC LEAVES OF Amaranthus tricolor L. EARLY SPLENDOR VARIETY

An important area of systemic biology (metabolomics) is the study of the composition and properties of low-molecular metabolites of agricultural plants with different modes of nutrition. The use of metabolic technologies expands the possibilities of analyzing biochemical changes in the composition and structural modifications of metabolites occurring during the transition from autotrophic to heterotrophic nutrition. Most photosynthetic plants are capable of autotrophic nutrition, but in their lifetime, there are periods of appearance of the achlorophyllic organs which receive nutritients from the organic substances stored earlier. Thus, among Amaranthus tricolor L. plants there are varieties with leaves which differ from each other in the way of nutrition. For example, Early Splendor variety plants form brightly colored red heterotrophic leaves along with green photosynthesis leaf blades at the end of the vegetative phase. The comparative study of the low-molecular metabolites composition in these leaves is important for understanding the relationship between heterotrophic and autotrophic nutrition in the whole plant. In this paper, significant qualitative differences in metabolites composition between autotrophic and heterotrophic leaves were stated for the first time during the metabolome analysis of water and alcohol extracts of heterotrophic and autotrophic amaranth leaves of Early Splendor variety using the method of gas chromato-mass spectrometry. It was found that the low-molecular metabolites of autotrophic and heterotrophic leaves contained both non-specific metabolites common for both type of nutrition and specific metabolites characteristic for each of the ways separately. On the one hand, it indicates the close interaction between two ways of nutrition and, on the other hand, the ability to synthesize and modify the metabolites which demonstrates partial autonomy of heterotrophic leaves. The purpose of the work is to study the composition of low-molecular metabolites and to identify new biologically active metabolites antioxidants in heterotrophic and autotrophic amaranth leaves of Early Splendor variety. Experiments were carried out in 2017-2019 with amaranth plants of the Early Splendor variety at the end of flowering—the beginning of seed formation phase. The plants were grown in a film greenhouse (the Federal Research Center for Vegetable Growing). The fresh red-colored heterotrophic leaves formed at the top of the main stem and the underlying photosynthetic leaves with a fully formed leaf blade were collected for analysis. The leaves were homogenized (T18 homogenizer, IKA, Germany) and extracted for 30 min at 24 °C with either 96 % ethanol or distilled water (leaves weighing batch: extragent 1:10). The metabolites were profiled by gas chromato-mass spectrometry method (GH-MC) with a chromograph GH-MC JMS-Q1050GC (JEOL Ltd., Japan). According to the mass spectra library of the NIST-5 National Institute of Standards and Technology (USA), a total of 87 metabolites were totally identified. Heterotrophic leaves contained 19 substances in water extracts and 38 metabolites in alcohol extracts, while photosynthetic leaves contained 21 substances in the water extract and 57 metabolites in alcohol extracts. Twenty-nine identical metabolites were found in water and alcohol extracts. In heterotrophic and autotrophic amaranth leaves of Early Splendor variety squalene (C30H50), a biologically active compound with antioxidant properties was identified for the first time. Also, in heterotrophic leaves monopelargonine (monononanoin) (C15H11O7) was identified. Monopelargonine is an intermediate product of flavonoid o-glycosylation, is referred to phenolic compounds and possesses high antioxidant activity. Metabolites have been identified that are present in both autotrophic and heterotrophic amaranth leaves, which suggests a close interaction of the two types of nutrition during the appearance, growth and development of heterotrophic leaves. At the same time, photosynthesizing leaves serve as donors of key metabolites for heterotrophic leaves, while the latter are not only acceptors, but also can synthesize and modify metabolites necessary for cell formation. Due to revealed rich composition of carbohydrates, essential amino acids, lipids and organic acids, the photosynthesizing leaf biomass is a source of antioxidants and biologically active substances. It should be stressed that not all metabolites were identified. Nevertheless, the set of metabolites that we identified in the photosynthetic leaves allows us to suggest these substances to be key and sufficient compounds for the construction and functioning of cells and tissues in heterotrophic leaves.

STUDIES OF THE ORGANIC ORIGIN CHEMICAL COMPOUNDS OF BROWN COALS AND CARBONIZED PLANT RESIDUES FROM NORTHERN TIMAN

The results of the physical and chemical studies of the organic matter of Devonian brown coals and rocks with carbonized plant residues from Northern Timan (Russian Arctic) are presented. We used a complex of physical and chemical methods, including IR spectroscopy, EPR spectroscopy, quantitative chemical analysis, pyrolytic gas chromato-mass spectrometry. For comparative studies we used Devonian (Middle Timan) and Jurassic (Griva, Komi Republic, Russia) carbonized plant residues and lignins, isolated from modern wood and non-wood plants. Organic structures of aromatic nature, which are products of the metamorphic transformation of lignins of coal-forming plants, were found in the investigated samples. It was shown that lignin’s relics show pronounced paramagnetic properties, mainly due to the presence of phenoxyl radicals. The concentration of paramagnetic centers reaches a value that is close to the maximum value nорг for carbonaceous substances. Based on quantitative analysis of phenolic products of pyrolysis the composition of lignin relics was calculated, taking into account the ratio of the main structural H, G and S units. Experimental data allowed to put forward the hypothesis that in the composition of Devonian coal-forming plants, as one of the first representatives of forest communities on the planet, included compositionally homogeneous protolignins of H-type, built mainly from p-coumaric structural units.

EXTRACTING SUBERIN ACIDS FROM BIRCH BARK WHEN EXPOSED TO A MICROWAVE FIELD

The present study focuses on the identification of the components included in the suberin of birch bark, as well as the development of the method of intensification of hydrolysis of birch bark in the allocation of suberin.Identification suberin derived from the technical of birch bark in conditions the microwave field was conducted the method of IR-spectroscopy (IRS). In the study of the chemical composition of suberin acids using gas chromatomass spectrometry (GC/MS) revealed the following dominant acid: docosanedioic (phellogenic) acid and 22-hydroxydocosanoic (phellonic) acid.It is established that processing of birch bark in a microwave field allows 2 times to reduce the duration of process of water-alkaline hydrolysis. By the planned experiment, mathematical description of the process of hydrolysis of birch bark in conditions of microwave radiation was obtained; the influence of the main parameters was installed and the optimal conditions for suberin acids secretion were determined. Concentration of alkali, %; power, W; duration, min were selected How were the independent variables. It is noted that the increase in alkali concentration and duration of hydrolysis leads to a positive result. On the basis of economic considerations, the optimum concentration of KOH for microwave hydrolysis is 5%, duration – 15 min, power – 600 W. The power consumption is 37,5 kWh/kg birch bark.

Thermal decomposition of 1-alkyl-3-methylpyridinium based ionic liquids

Products of thermodegradation of 1-alkyl-3-methylpyridinium halides are investigated by the method of gas chromatomass spectrometry. The main products of the reaction are 3-methylpyridine and the corresponding alkyl halide. It was supposed that thermodecomposition of pyridinium ionic liquids proceeds similar to that of imidazolium ionic liquids by dealkylation with elimination of the substituent at the nitrogen atom of the pyridinium ring via SN2 mechanism. The presence of 5 wt % of cellulose decreases the onset temperature of thermodecomposition by 15–20°С.

A new approach to comparison of original pharmaceuticals and generics based on comparison of multidimensional impurity profiles using supercritical fluid extraction, liquid extraction, and GC-MS

This paper reports on our effort to study the possibility of comparing the original pharmaceuticals and their analogs (generics) based on comparisons of the multidimensional profiles of impurities isolated from samples by supercritical fluid extraction and liquid extraction and recorded by gas chromato-mass spectrometry (GC-MS) with electron ionization (EI) and atmospheric pressure photochemical ionization (APPhCI). Using the suggested approach makes it possible to increase the number of recorded impurities, to show that the pharmaceutical samples are authentic, and to compare the original pharmaceuticals and generics according to their quality.

Non-cultural methods of human microflora evaluation for the benefit of crew medical control in confined habitat

Current control of human microflora is a great problem not only for the space medicine but also for practical health care. Due to many reasons its realization by classical bacteriological method is difficult in practical application or cannot be done. To evaluate non-cultural methods of microbial control of crews in a confined habitat we evaluated two different methods. The first method is based on digital treatment of microbial visual images, appearing after gram staining of microbial material from natural sample. This way the rate between gram-positive and gram-negative microbe could be gained as well as differentiation of rods and cocci could be attained, which is necessary for primary evaluation of human microbial cenosis in remote confined habitats. The other non-culture method of human microflora evaluation is gas chromatomass spectrometry (gcms) analysis of swabs gathered from different body sites. Gc-ms testing of swabs allows one to validate quantitative and special microflora based on specific lipid markers analysis.

Formation of 2,5-diamino-4-hydroxy-6-(2'-deoxyribosyl)-formamidopyrimidine from 2'-deoxyguanosine in aqueous solution irradiated with 60Co gamma-rays.

2'-Deoxyguanosine in aqueous solution (5 x 10(-4) mol/dm3) was irradiated with 60Co gamma-rays under N2O. Products were separated by gel chromatography (Cellulofine GC-15-m) and high performance liquid chromatography (Inertsil ODS-2). 2-Amino-4-hydroxy-5-formamido-6-(2'-deoxyribosyl)-aminopyrimidine was one of the main radiolytic products. The formation of 2,5-diamino-4- hydroxy-6-(2'-deoxyribosyl)-formamidopyrimidine was detected, this compound being verified by measuring its ultraviolet absorption spectrum and analyzing its trimethylsilylated derivative by gas chromato-mass spectrometry. Its yield in terms of 2-amino-4-hydroxy-5-formamido-6-(2'-deoxyribosyl)- aminopyrimidine was 1:3.

1145 AMMONIA METABOLISM OF A PATIENT WITH ORNITHINE TRANSCARBAMYLASE DEFICIENCY DETECTED BY 15N TRACER METHOD

Glutamine and glutamate are said to serve to remove excess of NH4 in animals. But the detailed relationship in ammonia metabolism between NH4 and amino acids was not known in urea cycle enzymopathies. We investigated the ammonia metabolism of a patient with OTC deficiency (an 8-year-old female) using 15N tracer method. 15NH4Cl was administered orally to the patient (500mg) and a volunteer (lg). The 15N excess ratios of amino acids and urea in the serum were examined during time course after the administration of 15NH4Cl. The 15N excess ratios of amino acids were examined in the form of the N-TFA-O butylester derivatives using gas chromato-mass spectrometry. Urea 15N was assayed using an isotope ratio mass spectrometry. The incorporation of 15N into urea in the patient was decreased to one forth compared to that in the control. The large amount of 15N was incorporated immediately into alanine, asparagine, glutamine(α-N) and glutamate. This pattern is very significant compared to the normal control. But the incorporation of 15NH4C1 into another amino acids in the patient was the same as that in the control. Accordingly, we suggest that alanine and asparagine could serve to remove excess of NH4 in patient with

The Progressive Change of Cresol Content in FC Observed by Means of Simultaneous Aplication of Ultra-Violet Absorptiometry and Gas-Chromatography

The progressive change of cresol content in FC which was stored under the various conditions for 18 months was observed. For the quantitative analysis of cresol, ultra-violet absorptio metry (UV) and gas-chromatography (GLC) were employed at the same time.GLC method has an advantage of high sensibility in estimating cresol isomers, whereas not only total cresol but reaction products formed from cresol are detected by UV method. Therefore it is possible to assume the existence of reaction products by the discrepancy of the 2 kinds of value obtained by the simultaneous application of UV method and GLC method. It was tried to examine statistically when the difference between those 2 kinds of quantitative value became significant.The existence of reaction products in FC stored for 18 months was confirmed by the qualitative analisis of thin-layer-chromatography (TLC). The reaction products was extracted to be subjected to gas-chromato-mass-spectrometry (GC-MS). Following conclusions were obtained:1) When FC is kept sealed at a cold place, cresol content do not show any change. As temperature rises, it shows a tendency to decrease.2) When FC is kept unsealed, cresol content increases remarkably.3) In the case of FC stored either in a sealed container or in an unsealed one, the reaction products is formed from cresol. The reaction becomes noticeable with increasing temperature.4) The reaction products consist of polymers formed by the addition polimerization of cresol and formaldehyde, the main ingredients of FC.