RESUMEN
Gas-phase tautomerism in 1-phenylazonaphthalene-4-ol (1) was studied by using electron ionization (EI) mass spectrometry on the basis of the fragmentations of the model enol and keto tautomers, where the movable proton is replaced by a methyl group. These fixed tautomers were obtained as an easy separable mixture by simple methylation of the cheap and easily accessible diazene (1). It was found that their EI mass spectral fragmentations are in full congruence with the already published theoretical predictions. The relative energies required for bond cleavage in 1 and its fixed tautomers were estimated by stepwise increasing of the electron energy of the ion source of the mass spectrometer. A simple equation for the approximate estimation of the molar fractions of the individual tautomers was suggested. It was shown that the enol form is dominant in the temperature range of 200-300 degrees C.
RESUMEN
Four groups of metabolites from the halophyte plant Stachys maritima Gouan, family Lamiaceae, were investigated: lipids, sterols, volatiles and polar compounds. Most of the metabolites have been previously reported to possess biological activity. Two of the main substances in the volatile fraction--phenidone and naphthalene, unusual for plants--were products of environmental contamination. This is a typical example of how marine pollutants could transfer and threaten terrestrial organisms via the trophic chain. The n-butanol extract possessed a relatively high antibacterial activity against S. aureus and Candida albicans, but was not active against Escherichia coli.
Asunto(s)
Ecosistema , Stachys/química , Bulgaria , Cloruro de Sodio/química , Agua/química , Contaminantes Químicos del AguaRESUMEN
We examined metabolic profiles of acetone and butanol extracts obtained from the leaves of 18 seedlings of the Bulgarian wine-making cultivar Storgozia. The acetone extracts contained the components from the leaf surface, while the butanol extracts were enriched with polar components from inside the leaf tissue. The leaves displayed different degrees of resistance and susceptibility to the etiological agent downy mildew, Plasmopara viticola. Based on the statistically significant correlations (P<0.05) between the GC-MS data of the identified metabolites and the estimated leaf resistances, 10 individual components were proposed as possible biomarkers for the downy mildew resistance and susceptibility in grapevine. All were found in the butanol extracts, and can be considered to form two groups: compounds with high correlations (r=+/-0.50 to +/-1.00) - 3-hydroxybutanoic acid, 2,3,4-trihydroxybutanoic acid, 2,3,4-trihydroxybutanoic acid (isomer), hexadecanoic acid, 3-hydroxyhexanoic acid and myo-inositol, and compounds with moderate correlations (r=+/-0.30 to +/-0.49) hydroxybutanedioic acid, alanine, glutamine, arabinoic acid and aldohexoses. Among them, the more polar compounds were related to sensitivity, and only hexadecanoic and the monohydroxycarboxylic acids were related to resistance in grapevine.
Asunto(s)
Inmunidad Innata , Oomicetos/fisiología , Enfermedades de las Plantas/inmunología , Enfermedades de las Plantas/microbiología , Vitis/inmunología , Vitis/microbiología , Biomarcadores/metabolismo , Susceptibilidad a Enfermedades , Cromatografía de Gases y Espectrometría de Masas , Extractos Vegetales/metabolismo , Hojas de la Planta/metabolismo , Hojas de la Planta/microbiologíaRESUMEN
We examined the leaf chemical composition of six seedlings obtained by self-pollination of the Bulgarian wine-making variety Storgozia as well as the cultivar Bouquet, which is the susceptible parent of Storgozia. The chemical composition was investigated in the framework of a program for identification of metabolites associated with disease resistance in grape-vine. Acetone, dichloromethane and butanol extracts, as well as volatiles obtained from fresh material were analyzed by GC/MS. Based on the correlations of the GC/MS data and estimated resistance of the leaves towards the etiological agents of powdery mildew, downy mildew and botrytis as biomarkers for the fungal resistance, we proposed 16 individual metabolites--alpha- and gamma-tocopherol, squalene, alpha-amyrine, stigmasta-3,5-diene-7-one, hexahydrofarnesyl acetone, glycolic acid, 3-hydroxybutanoic acid, 3-hydroxycaproic acid, malic acid, tartaric acid, erythronic acid, arabinoic acid, monoethyl phosphate, undecyl laurate and isopropyl myristate. The obtained correlations were confirmed by cluster analysis.
Asunto(s)
Hongos/fisiología , Inmunidad Innata/inmunología , Enfermedades de las Plantas/inmunología , Enfermedades de las Plantas/microbiología , Hojas de la Planta/microbiología , Vitis/microbiología , Biomarcadores/análisis , Cromatografía de Gases y Espectrometría de Masas , FilogeniaRESUMEN
BACKGROUND: Mushrooms in the genus Agaricus have worldwide distribution and include the economically important species A. bisporus. Some Agaricus species are inedible, including A. placomyces and A. pseudopratensis, which are similar in appearance to certain edible species, yet are known to possess unpleasant odours and induce gastrointestinal problems if consumed. We have studied the chemical composition of these mushrooms using GC-MS. RESULTS: Our GC-MS studies on the volatile fractions and butanol extracts resulted in the identification of 44 and 34 compounds for A. placomyces and A. pseudopratensis, respectively, including fatty acids and their esters, amino acids, and sugar alcohols. The most abundant constituent in the volatiles and butanol were phenol and urea respectively. We also identified the presence of ergosterol and two Delta7-sterols. In addition, 5alpha,8alpha-Epidioxi-24(xi)-methylcholesta-6,22-diene-3beta-ol was isolated for the first time from both mushrooms. Our study is therefore the first report on the chemical composition of these two species. CONCLUSION: The results obtained contribute to the knowledge of the chemical composition of mushrooms belonging to the Agaricus genus, and provide some explanation for the reported mild toxicity of A. placomyces and A. pseudopratensis, a phenonomenon that can be explained by a high phenol content, similar to that found in other Xanthodermatei species.
RESUMEN
From a biologically active fraction of extract from the fungus Fomitopsis pinicola, a new lanostane triterpene was isolated, 3alpha-acetyloxylanosta-8,24-diene-21-ol (1), along with two known triterpenic acids, (2) and (3). The structures of the compounds were elucidated based on their spectral properties. [structure: see text]
Asunto(s)
Polyporales/química , Triterpenos/química , Animales , Artemia/efectos de los fármacos , Espectroscopía de Resonancia Magnética , Espectrometría de Masas , Estructura Molecular , Staphylococcus aureus/efectos de los fármacos , Triterpenos/aislamiento & purificación , Triterpenos/farmacologíaRESUMEN
The compositions of the volatile and polar fractions from two coexisting Black Sea invertebrates, the mussel Mytilus galloprovincialis and the beadlet anemone Actinia equina, were established. The main metabolites in the volatile fraction from the investigated animals appeared to be methyl esters of fatty acids and fatty aldehydes. In the polar fraction from both animals low concentrations of free acids and nitrogen-containing compounds were obtained. Free carbohydrates were in much higher concentrations in M. galloprovincialis than in A. equina. Some sterols, probably as polar conjugates, were identified mainly in A. equina. Significant changes among all compounds appeared after treatment of both invertebrates with two different concentrations of cobalt ions. The variety of changes in each invertebrate could be due to their different evolutionary status. The effect of cobalt ions was often stronger at medium cobalt-ion concentrations.
Asunto(s)
Cobalto/farmacología , Mytilus/química , Mytilus/metabolismo , Anémonas de Mar/química , Anémonas de Mar/metabolismo , Animales , Evolución Biológica , Carbohidratos/análisis , Cobalto/efectos adversos , Ácidos Grasos/análisis , Ácidos Grasos/química , Ácidos Grasos/metabolismo , Cromatografía de Gases y Espectrometría de Masas , Iones , Mytilus/efectos de los fármacos , Anémonas de Mar/efectos de los fármacos , Esteroles/análisis , Esteroles/metabolismo , Volatilización , Contaminantes Químicos del Agua/efectos adversos , Contaminantes Químicos del Agua/farmacologíaRESUMEN
The lipid and sterol fractions of the mussel Mytilus galloprovincialis and the anemone Actinia equina were analyzed before and after incubation with cobalt ions. There were significant changes in the lipid and sterol composition, strongly depending on the cobalt ions concentrations. The changes in the lipid composition of both invertebrates were different for neutral lipids and phospholipids. These changes concern the length of the fatty acid chains as well as their unsaturation. The cobalt ions inhibited the oxidation of sterols and their alkylation at C-24. Because of these results we can assume that some of the changes caused by cobalt ions might possess adaptive value.
Asunto(s)
Cobalto/farmacología , Ácidos Grasos/metabolismo , Metabolismo de los Lípidos/efectos de los fármacos , Mytilus/metabolismo , Anémonas de Mar/metabolismo , Esteroles/metabolismo , Animales , Ácidos Grasos/análisis , Mytilus/química , Mytilus/efectos de los fármacos , Oxidación-Reducción , Anémonas de Mar/química , Anémonas de Mar/efectos de los fármacos , Especificidad de la Especie , Esteroles/análisisRESUMEN
The sterol and fatty acid composition of three Adriatic Sea sponges (Geodia cydonium and two unidentified Tedania sp.), collected at the same time and same place, was established. Twenty-four sterols and forty fatty acids were identified. The identical ecological conditions, including the diet, allowed us to apply the results obtained for taxonomical conclusions, based on the biodiversity of the investigated sponges. On the basis of the sterol composition they can be separated into two groups: Tedania and Geodia sponges. The sterol and fatty acid composition indicates that the two investigated Tedania samples might be different species or subspecies.
Asunto(s)
Lípidos/análisis , Poríferos/química , Esteroles/análisis , Animales , Bulgaria , Ácidos Grasos/análisis , Cromatografía de Gases y Espectrometría de Masas , Poríferos/clasificación , Agua de MarRESUMEN
The sterol composition of five Black Sea red algae: Callithamnion granulatum, Ceramium rubrum, Ceramium elegans, Laurencia papillosa and Laurencia coronopus was obtained. Monohydroxy sterols and their oxidized derivatives have been identified. The results obtained were compared with some recent data for the composition of sterols in other Black Sea red algae, which occupy different evolutionary positions. On the basis of their composition, some conclusions about the chemotaxonomy and chemoevolution of the species investigated have been proposed.
Asunto(s)
Rhodophyta/química , Esteroles/química , Bulgaria , Océanos y Mares , Esteroles/análisisRESUMEN
This paper shows the changes of the volatile compounds from four Astragalus species at three phenological stages: leaf development, flowering and fructification, which might be connected with the plant defense. After GC/MS analyses of Astragalus glycyphyllos L., A. hamosus L., A. cicer L. and A. spruneri Boiss., different groups of volatile compounds were found: hydrocarbons, alcohols, aldehydes and ketones, esters, terpenes, chlorinated compounds, etc. Identified volatiles were used for a cluster analysis in order to make chemotaxonomic conclusions for these evolutionary different species.
Asunto(s)
Planta del Astrágalo/química , Alcoholes/química , Alcoholes/aislamiento & purificación , Aldehídos/química , Aldehídos/aislamiento & purificación , Planta del Astrágalo/clasificación , Planta del Astrágalo/crecimiento & desarrollo , Ésteres/química , Ésteres/aislamiento & purificación , Flores/crecimiento & desarrollo , Hidrocarburos/química , Hidrocarburos/aislamiento & purificación , Cetonas/química , Cetonas/aislamiento & purificación , Hojas de la Planta/crecimiento & desarrollo , Especificidad de la Especie , VolatilizaciónRESUMEN
Studies were conducted on low molecular metabolites (volatiles and polar compounds) produced by Rosa damascena Mill 1803 cell suspension culture, cultivated under different regimes: as a free suspension (in flasks and in bioreactor) and in a two-phase system (in the presence of Amberlite XAD-4 as a second phase). It was established that the main groups of volatiles were hydrocarbons and free acids and their esters and only traces of terpenoids were found. The main components of polar fraction were free acids, especially amino acids and oxidized acids. Depending on the culture conditions, significant differences were established in the amounts of all compounds under study in biomasses, culture media and adsorbed on the second phase (Amberlite XAD-4).
Asunto(s)
Técnicas de Cultivo de Célula/métodos , Aceites Volátiles/metabolismo , Aceites de Plantas/metabolismo , Rosa/clasificación , Rosa/metabolismo , Células Cultivadas , Tallos de la Planta/metabolismo , VolatilizaciónRESUMEN
Underivatised alkaloid mixtures extracted from intact plants and in vitro cultures of Leucojum aestivum (Amaryllidaceae) were investigated by capillary GC-MS. Excellent peak resolution for the alkaloids was exhibited and isomers of galanthamine and N-formylnorgalanthamine were well separated. Fourteen alkaloids of galanthamine, lycorine and crinane types were identified, 11 in the intact plants and eight in the in vitro cultures.
Asunto(s)
Alcaloides/análisis , Liliaceae/química , Alcaloides/química , Cromatografía de Gases y Espectrometría de Masas , Modelos Químicos , Estructura MolecularRESUMEN
Two new cyclic peptides, cyclo-(glycyl-L-seryl-L-prolyl-L-glutamyl) and cyclo-(glycyl-L-prolyl-L-glutamyl), have been isolated from the cell extract of a Ruegeria strain associated with cell cultures of Suberites domuncula. Three other cyclopeptides have been isolated for the first time from a natural source. Additionally, a new diastereoisomer of a known compound is reported. The structures of isolated compounds have been elucidated by means of spectroscopic data (1D-, 2D-NMR, HRESIMS) and chiral HPLC analysis. The new cyclopeptides exhibited moderate antimicrobial activity against Bacillus subtilis.
Asunto(s)
Antibacterianos/aislamiento & purificación , Bacterias/química , Péptidos Cíclicos/aislamiento & purificación , Poríferos/microbiología , Secuencia de Aminoácidos , Animales , Antibacterianos/química , Antibacterianos/farmacología , Bacillus subtilis/efectos de los fármacos , Cromatografía Líquida de Alta Presión , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Resonancia Magnética Nuclear Biomolecular , Péptidos Cíclicos/química , Péptidos Cíclicos/farmacología , ARN Ribosómico 16S/genética , Agua de Mar , EstereoisomerismoRESUMEN
The fatty acid composition of the lipids from the sponge Hymeniacidon sanguinea was investigated and 73 acids were identified. Three of them were new and their structures, elucidated by gas chromatography/mass spectrometry, were identified as 13-methyl-icosanoic, 15-methyl-docosanoic and 3,13-dimethyl-tetradecanoic. Only 12 sterols were present, with cholestanol predominating in the volatile fraction; 22 compounds were identified, mainly hydrocarbons and fatty acids. In the n-butanol fraction, we found mainly nitrogen-containing compounds. The compositions of sterols and lipids in the sponge collected from two locations with different ecological conditions (Canary Islands and Black Sea) were compared.
Asunto(s)
Poríferos/química , Animales , Butanoles/análisis , Ácidos Grasos/análisis , Ácidos Grasos Volátiles/análisis , Cromatografía de Gases y Espectrometría de Masas , Océanos y Mares , Poríferos/metabolismo , Esteroles/análisisRESUMEN
A GC/MS analysis of alkaloids from leaves, bulbs and roots of Pancratium maritimum was performed. From the identified 16 alkaloids, 5 alkaloids were reported for the first time for this plant. Several compounds with pharmacological activity were found. Haemanthamine was main alkaloid in the leaves and bulbs whereas galanthane was found to be main alkaloid in roots.
Asunto(s)
Alcaloides/química , Magnoliopsida/química , Alcaloides/aislamiento & purificación , Alcaloides/metabolismo , Bulgaria , Cromatografía de Gases y Espectrometría de Masas , Hojas de la Planta/química , Raíces de Plantas/química , Plantas Medicinales/químicaRESUMEN
Alkaloid pattern of individuals from 16 Bulgarian Galanthus elwesii populations was investigated by GC/MS and TLC. Twenty-one Amaryllidaceae alkaloids were detected and 14 of them were identified. Crinane type alkaloids, haemanthamine or crinine, dominated alkaloid metabolism in most of the populations. With exception of one population, where the separate individuals showed variable alkaloid profiles (dominated by crinine or haemanthamine) the individuals of the rest of populations have identical and characteristic alkaloid profiles. Some populations showed remarkable differences in respect to their alkaloid pattern-type of biosynthesis, main alkaloids and number of alkaloids. Populations dominated by galanthamine type alkaloids were found as well. These data demonstrate that like the morphological features, the alkaloid metabolism of G. elwesii is also variable.
Asunto(s)
Alcaloides/metabolismo , Galanthus/metabolismo , Alcaloides/química , Cromatografía en Capa Delgada , Galanthus/química , Galanthus/clasificación , Cromatografía de Gases y Espectrometría de Masas , Especificidad de la EspecieRESUMEN
A new class of compounds for the plant family Lamiaceae, benzoxazinoids, was found in Lamium galeobdolon. From the aerial parts of the species were isolated the new 2-O-beta-D-glucopyranosyl-6-hydroxy-2H-1,4-benzoxazin-3(4H)-one (6-hydroxy blepharin) together with four known benzoxazinoids, DHBOA-Glc, blepharin, DIBOA, DIBOA-Glc, as well as harpagide, 8-O-acetyl-harpagide and salidroside. Eight known iridoid glucosides, 24-epi-pterosterone and verbascoside were isolated from Lamium amplexicaule, L. purpureum and L. garganicum. The iridoids, 5-deoxylamiol and sesamoside, as well as the phytoecdysone, 24-epi-pterosterone, were found for the first time for the genus Lamium. The phytochemical data are discussed from a systematic and evolutionary point of view.
Asunto(s)
Iridoides/química , Iridoides/aislamiento & purificación , Lamiaceae/química , Oxazinas/química , Oxazinas/aislamiento & purificación , Ecdisona/química , Ecdisona/aislamiento & purificación , Lamiaceae/genética , Estructura Molecular , Resonancia Magnética Nuclear Biomolecular , Filogenia , Fitosteroles/química , Fitosteroles/aislamiento & purificaciónRESUMEN
Sterols, triterpenes, volatiles, polar and other constituents in aerial parts of Carthamus lanatus were analyzed by gas chromatography-mass spectrometry. Over 90 compounds were identified most of them new for the species. Sitosterol and stigmasterol were the most abundant of 10 sterols identified in the sterol fraction. Taraxasterol, alpha- and beta-amyrine prevailed in the triterpene fraction. Volatiles, sterols and a fraction of the dichloromethane extract showed strong cytotoxicity (Artemia salina assay).
Asunto(s)
Carthamus/química , Componentes Aéreos de las Plantas/química , Plantas Medicinales/química , Esteroles/química , Esteroles/toxicidad , Triterpenos/química , Triterpenos/toxicidad , Animales , Artemia , Supervivencia Celular/efectos de los fármacos , Flores/química , Cromatografía de Gases y Espectrometría de Masas , Región Mediterránea , Esteroles/aislamiento & purificación , Triterpenos/aislamiento & purificaciónRESUMEN
A new phenylethanoid tetraglycoside, physocalycoside (2), was isolated from the aerial parts of Phlomis physocalyx. Its structure was identified as 3-hydroxy-4-methoxy-beta-phenylethoxy-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)]-4-O-feruloyl-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside, on the basis of spectroscopic evidence. In addition, one known iridoid glucoside, lamiide (1) and five known phenylethanoid glycosides, wiedemannioside C (3), verbascoside (= acteoside) (4), leucosceptoside A (5), martynoside (6), and forsythoside B (7) were also characterized. Compounds 2-7 demonstrated radical scavenging properties towards the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical.