RESUMEN
BACKGROUND: In Serbia, delicatessen fruit alcoholic drinks are produced from autochthonous fruit-bearing species such as cornelian cherry, blackberry, elderberry, wild strawberry, European wild apple, European blueberry and blackthorn fruits. There are no chemical data on many of these and herein we analysed volatile minor constituents of these rare fruit distillates. Our second goal was to determine possible chemical markers of these distillates through a statistical/multivariate treatment of the herein obtained and previously reported data. RESULTS: Detailed chemical analyses revealed a complex volatile profile of all studied fruit distillates with 371 identified compounds. A number of constituents were recognised as marker compounds for a particular distillate. Moreover, 33 of them represent newly detected flavour constituents in alcoholic beverages or, in general, in foodstuffs. With the aid of multivariate analyses, these volatile profiles were successfully exploited to infer the origin of raw materials used in the production of these spirits. It was also shown that all fruit distillates possessed weak antimicrobial properties. CONCLUSION: It seems that the aroma of these highly esteemed wild-fruit spirits depends on the subtle balance of various minor volatile compounds, whereby some of them are specific to a certain type of fruit distillate and enable their mutual distinction.
Asunto(s)
Bebidas Alcohólicas/análisis , Aromatizantes/análisis , Frutas/química , Odorantes/análisis , Aceites Volátiles/análisis , Gusto , Compuestos Orgánicos Volátiles/análisis , Humanos , Extractos Vegetales/análisis , Rosaceae , SambucusRESUMEN
INTRODUCTION: Recently, a potent anti-staphylococcal activity of Inula helenium L. (Asteraceae) root essential oil was reported. Also, bioassay guided fractionation of the oil pointed to eudesmane sesquiterpene lactones and a series of unidentified constituents as the main carriers of the observed activity. OBJECTIVE: To identify nine new constituents (long-chain 3-methyl-2-alkanones) from a fraction of this root essential oil with a low minimum inhibitory concentration value (0.8 µg/mL) by employing a synthetic methodology that leads to the formation of a small combinatorial library of these compounds. METHODS: The identity of these constituents was inferred from mass spectral fragmentation patterns and GC retention data. A library of 3-methyl-2-alkanones (C11 -C19 homologous series) was synthesised in three steps starting from methyl acetoacetate and the corresponding alkyl halides. The synthetic library was also screened for in vitro anti-microbial activity. RESULTS: Gas chromatographic analyses of I. helenium essential oil samples with spiked compounds from the synthesised library corroborated the tentative identifications of the long-chain 3-methyl-2-alkanones. The availability of these anti-microbial compounds from this library made it possible to construct GC/FID calibration curves and determine their content in the plant material: 0.08 - 24.2 mg/100 g of dry roots. CONCLUSION: The small combinatorial library approach enabled the first unequivocal identification of long-chain 3-methyl-2-alkanones as plant secondary metabolites, and, also, allowed determination of not only a single compound and biological properties, but those of a group of structurally related compounds.
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Antiinfecciosos/química , Antiinfecciosos/farmacología , Inula/química , Aceites Volátiles/análisis , Raíces de Plantas/química , Bibliotecas de Moléculas Pequeñas/síntesis química , Bibliotecas de Moléculas Pequeñas/farmacología , Calibración , Candida albicans/efectos de los fármacos , Cromatografía de Gases , Pruebas de Sensibilidad Microbiana , Estructura Molecular , Aceites Volátiles/química , Bibliotecas de Moléculas Pequeñas/químicaRESUMEN
Herein, we report, for the first time, the results of detailed chemical and statistical analyses of the essential oils from the roots of two Echinops species (Asteraceae), E. bannaticus Rochel ex Schrad., and E. sphaerocephalus L., from the weed flora of Serbia. Among 106 and 81 constituents, respectively, S-containing polyacetylene compounds and triquinane sesquiterpenoids made up ca. 80% of the oils. Several of these compounds are reported here as new metabolites for the two species or even for the genus Echinops. A multivariate statistical comparison of the essential-oil composition data for these two and additional six taxa of this genus available from the literature permitted an examination of the mutual relationships of the taxa within this morphologically highly uniform genus. Principal component analysis (PCA) and agglomerative hierarchical clustering revealed a grouping of E. bannaticus and E. sphaerocephalus (both belonging to the section Echinops), and their close relationship with E. grijsii, suggesting a circumscription of this Chinese taxon to the section Echinops. PCA Correlation matrix offered valuable insight into the biosynthetic links between essential-oil constituents, and these agreed excellently with the currently proposed ones for the polyacetylene S-containing compounds, triquinanes, and monoterpenes.
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Echinops (Planta)/química , Aceites Volátiles/química , Análisis por Conglomerados , Cromatografía de Gases y Espectrometría de Masas , Aceites Volátiles/aislamiento & purificación , Raíces de Plantas/química , Análisis de Componente PrincipalRESUMEN
Herein, we report on the synthesis, spectral, crystallographic and electrochemical properties of a small library of N-substituted 2-ferrocenyl-1,3-thiazolidin-4-ones, designed as novel GABAA benzodiazepine-binding site ligands. The anxiolytic properties of the title compounds were evaluated in several different in vivo models, whereas the involvement of the GABAA receptor complex in the activity of the most potent compound, 2-ferrocenyl-3-(4-methoxyphenylethyl)-1,3-thiazolidin-4-one, was inferred from experiments with known GABAA-targeting agents. Ligand docking experiments revealed that the high, dose-dependent, anxiolytic activity of the new compounds might be due to their favorable interactions with the benzodiazepine-binding site of the GABAA receptor complex. The incorporation of the ferrocene core and fine tuning of the distance between the thiazolidinone core and an additional aromatic ring were judged to be crucial structural requirements for the observed anxiolytic effect.
Asunto(s)
Ansiolíticos/metabolismo , Ansiolíticos/farmacología , Benzodiazepinas/metabolismo , Diseño de Fármacos , Compuestos Ferrosos/metabolismo , Compuestos Ferrosos/farmacología , Receptores de GABA-A/metabolismo , Animales , Ansiolíticos/química , Sitios de Unión , Cristalografía por Rayos X , Electroquímica , Compuestos Ferrosos/química , Masculino , Ratones , Simulación del Acoplamiento Molecular , Unión Proteica , Conformación Proteica , Receptores de GABA-A/químicaRESUMEN
A reversed-phased HPLC method with fluorescence detection was optimized and validated for determination of DOXY in human saliva and gingival crevicular fluid (GCF) with tetracycline as internal standard. Single step extraction with acetonitrile for both types of samples was performed. The separation was achieved at Zorbax Extend-C18 analytical column at 30°C. Mobile phase was consisted of an aqueous phase containing magnesium acetate, ammonium acetate, Na2EDTA, triethyl-ammonium acetate buffered to pH 7.5 with ammonium hydroxide solution and acetonitrile. The volume ratio of the buffered water mixture of salts and acetonitrile was 86:14. Fluorescence detector was set at λex=380 nm and λem=520 nm. Under the optimized experimental conditions, good linearity was found in the range of 5.0-250.0 ng/mL for GCF with LOD of 1.63 ng/mL and LOQ of 4.93 ng/mL and 20.0-500.0 ng/mL for saliva with LOD of 6.36 ng/mL and LOQ of 19.28 ng/mL. This method was successfully applied for determination of DOXY in saliva and GCF obtained from patients with chronic periodontal disease.