RESUMEN
This is the first study to use chemometric methods to differentiate among 21 cultivars of Camellia sinensis from China and between leaves harvested at different times of the year using 30 compounds implicated in the taste and quality of tea. Unique patterns of catechin derivatives were observed among cultivars and across harvest seasons. C. sinensis var. pubilimba (You 510) differed from the cultivars of C. sinensis var. sinensis, with higher levels of theobromine, (+)-catechin, gallocatechin, gallocatechin gallate and theasinensin B, and lower levels of (-)-epicatechin, (-)-epigallocatechin (EGC) and (-)-epigallocatechin gallate (EGCG), respectively. Three cultivars of C. sinensis var. sinensis, Fuyun 7, Qiancha 7 and Zijuan contained significantly more caffeoylquinic acids than others cultivars. A Linear Discriminant Analysis model based on the abundance of 12 compounds was able to discriminate amongst all 21 tea cultivars. Harvest time impacted the abundance of EGC, theanine and afzelechin gallate.
Asunto(s)
Camellia sinensis/metabolismo , Glutamatos/análisis , Fenoles/análisis , Extractos Vegetales/análisis , Estaciones del Año , Xantinas/análisis , Camellia sinensis/crecimiento & desarrollo , Catequina/análogos & derivados , Catequina/análisis , China , Flavonoides/análisis , Hojas de la Planta/químicaRESUMEN
Phenylethanoid glycosides were among the major UV-absorbing components in 80% aq. CH3OH extracts of the tepals of Magnolia salicifolia (Siebold & Zucc.) Maxim. (Magnoliaceae; Magnolia subgenus Yulania). Structural characterisation of isolated compounds by spectroscopic and chemical methods revealed three previously unrecorded examples, yulanoside A, yulanoside B and 2'-rhamnoechinacoside, and the known compounds echinacoside and crassifolioside; chromatographic methods also identified verbascoside in the tepal extract. Yulanoside A is the first reported example of a phenylethanoid pentaglycoside, namely hydroxytyrosol 1-O-{ß-D-glucopyranosyl-(1â4)-ß-D-glucopyranosyl-(1â6)-[3,4-dihydroxycinnamoyl-(â4)][α-L-rhamnopyranosyl-(1â3)][α-L-rhamnopyranosyl-(1â2)]-ß-D-glucopyranoside}. A survey of Magnolia sensu lato and Liriodendron (the two genera of Magnoliaceae) suggested that yulanoside A and its deglucosyl derivative (yulanoside B) were a feature of the tepal chemistry of Magnolia subgenus Yulania (except Magnolia acuminata, the sole member of section Tulipastrum, which did not accumulate phenylethanoid glycosides). The two species of Liriodendron and examined examples of Magnolia subgenus Magnolia sections Magnolia and Rytidospermum (subsection Oyama) also accumulated phenylethanoid glycosides in their tepals and in these species, and in subgenus Yulania, the major compounds were one or more of echinacoside, 2'-rhamnoechinacoside, crassifolioside and verbascoside. Levels of phenylethanoid glycosides were found to be much lower in species studied from Magnolia sections Gwillimia, Macrophylla and Rytidospermum (subsection Rytidospermum), although yulanoside A was detectable in M. macrophylla and this may have some bearing on the placement of section Macrophylla, which is currently uncertain. In the isolates of yulanoside B and echinacoside, minor phenylethanoid glycosides were determined to be analogues of these compounds with ß-D-xylose at C-3' of the primary glucose rather than α-L-rhamnose.
Asunto(s)
Flores/química , Glicósidos/aislamiento & purificación , Magnoliaceae/química , Glicósidos/química , Estructura Molecular , Resonancia Magnética Nuclear Biomolecular , Alcohol Feniletílico/análogos & derivados , Alcohol Feniletílico/química , Alcohol Feniletílico/aislamiento & purificación , XilosaRESUMEN
Aqueous methanol extracts of Chemlali olive stones were analyzed by reverse phase high-performance liquid chromatography (HPLC) with diode array detection and mass spectrometry [LC-MS/MS]. Oleoside, oleoside 11-methyl ester, nuezhenide, oleoside 11-methyloleoside, nuezhenide 11-methyloleoside, oleuropein, and glycosides of tryosol and hydroxytyrosol glycosides were identified in stones of Chemali olives. The antioxidant activity observed for the extract of the olive stones (IC50 = 13.84 µg/mL, TEAC = 0.436 mM) may be due to the high content of phenolic compounds, of which the main compounds are nuezhenide (325.78 mg/100g), methoxy derivative of nuezhenide (132.46 mg/100g), and nuezhenide-11-methyloleoside (82.91 mg/100g). These results suggest the use of olive stones as sources of natural antioxidants.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Espectrometría de Masas/métodos , Olea/química , Fenoles/química , Extractos Vegetales/química , Frutas/química , Fenoles/aislamiento & purificación , Extractos Vegetales/aislamiento & purificaciónRESUMEN
Use of enhanced LC-MS/MS methods to identify common glycosyl groups of flavonoid glycosides enabled better characterization of the flavonoids in fruits of sea buckthorn (Hippophae rhamnoides). The saccharide moieties of 48 flavonol O-glycosides detected in a methanol extract were identified by these methods. Several of the flavonol glycosides were acylated, two of which were isolated and found to be new compounds. Their structures were determined using spectroscopic and chemical methods as isorhamnetin 3-O-(6-O-E-sinapoyl-ß-D-glucopyranosyl)-(1â2)-ß-D-glucopyranoside-7-O-α-L-rhamnopyranoside (24) and isorhamnetin 3-O-(6-O-E-feruloyl-ß-D-glucopyranosyl)-(1â2)-ß-D-glucopyranoside-7-O-α-L-rhamnopyranoside (30). Analysis of the acylated glycosyl groups of 24 and 30 by serial mass spectrometry provided evidence to suggest the acylation position of 11 other minor flavonol glycosides acylated with hydroxycinnamic or hydroxybenzoic acids. The nitric oxide scavenging activities of 24 and 30 were compared with those of other flavonoids and with ascorbic acid and the potassium salt of 2-(4-carboxyphenyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazolyl-1-oxy-3-oxide (carboxy-PTIO).
Asunto(s)
Flavonoides/análisis , Glicósidos/análisis , Hippophae/química , Acilación , Cromatografía Liquida/métodos , Depuradores de Radicales Libres , Óxido Nítrico , Quercetina/análogos & derivados , Quercetina/análisis , Espectrometría de Masas en Tándem/métodosRESUMEN
LC-UV-MS analyses of inflorescence extracts of Sambucus nigra L. (elder, Adoxaceae) revealed the presence of numerous acyl spermidines, with isomers of N,N-diferuloylspermidine and N-acetyl-N,N-diferuloylspermidine being most abundant. Pollen was the main source of the acyl spermidines in the inflorescence. Three of the major acyl spermidines were isolated and their structures determined by NMR spectroscopy as N5,N¹°-di-(E,E)-feruloylspermidine and the new compounds N¹-acetyl-N5,N¹°-di-(Z,E)-feruloylspermidine and N¹-acetyl-N5,N¹°-di-(E,E)-feruloylspermidine. An isomer of N,N,N-triferuloylspermidine was also obtained and identified as N¹,N5,N¹°-tri-(E,E,E)-feruloylspermidine. In addition to stereoisomers of the isolated acyl spermidines, other acyl spermidines detected by the positive ion LC-UV-MS were isomers of N-caffeoyl-N,N-diferuloylspermidine, N-coumaroyl-N,N-diferuloylspermidine, N-caffeoyl-N-feruloylspermidine, N-coumaroyl-N-feruloylspermidine, N-acetyl-N-caffeoyl-N-feruloylspermidine, and N-acetyl-N-coumaroyl-N-feruloylspermidine. Analysis of commercial elderflower drinks showed that acyl spermidines were persistent in these processed elderflower products. Examination of inflorescence extracts from Sambucus canadensis L. (American elder) revealed the presence of acyl spermidines that were different from those of S. nigra.
Asunto(s)
Bebidas/análisis , Inflorescencia/química , Extractos Vegetales/química , Sambucus nigra/química , Espermidina/análogos & derivados , Acetilación , Acilación , Polen/química , Espermidina/análisis , Espermidina/química , Reino UnidoRESUMEN
Four flavonol glycosides isolated from non-flowering leafy shoots of Iberis saxatilis (Brassicaceae) were characterised by spectroscopic and chemical methods as saxatilisins A-D, the 3-O-ß-D-glucopyranosyl-(1â3)-α-L-rhamnopyranosyl-(1â2)[ß-D-glucopyranosyl-(1â2)-α-L-rhamnopyranosyl-(1â6)]-ß-D-glucopyranoside, 3-O-ß-D-glucopyranosyl-(1â3)-α-L-rhamnopyranosyl-(1â2)[α-L-rhamnopyranosyl-(1â6)]-ß-D-glucopyranoside, 3-O-(6-O-E-sinapoyl)-ß-D-glucopyranosyl-(1â3)-α-L-rhamnopyranosyl-(1â2)[ß-D-glucopyranosyl-(1â2)-α-L-rhamnopyranosyl-(1â6)]-ß-D-glucopyranoside, and 3-O-(6-O-E-feruloyl)-ß-D-glucopyranosyl-(1â3)-α-L-rhamnopyranosyl-(1â2)[ß-D-glucopyranosyl-(1â2)-α-L-rhamnopyranosyl-(1â6)]-ß-D-glucopyranoside of isorhamnetin (3,5,7,4'-tetrahydroxy-3'-methoxyflavone), respectively. Analysis of (2)J(HC) correlations detected with the H2BC (heteronuclear two-bond correlation) pulse sequence aided the unambiguous assignment of glycosidic resonances in the (1)H and (13)C NMR spectra of these compounds. Saxatilisins A, C, and D, are the first flavonol glycosides to be described with a pentasaccharide chain at a single glycosylation site. Several pentaglycosides of kaempferol and quercetin, tentatively assigned as saxatilisin analogues from LC-MS/MS analyses, were present as minor constituents of the extracts.
Asunto(s)
Brassicaceae/química , Flavonoles/química , Cromatografía Liquida , Glicósidos/química , Espectrometría de Masas , Estructura Molecular , Hojas de la Planta/química , Tallos de la Planta/químicaRESUMEN
LC-UV-MS/MS analysis of leaf extracts from 146 accessions of 71 species of Rosa revealed that some taxa accumulated flavonol O-glycosides acylated with 3-hydroxy-3-methylglutaric acid, which are relatively uncommon in plants. The structures of two previously unrecorded examples isolated from Rosa spinosissima L. (syn. Rosa pimpinellifolia L.) were elucidated using spectroscopic and chemical methods as the 3-O-α-L-rhamnopyranosyl-(1â2)-[6-O-(3-hydroxy-3-methylglutaryl)-ß-D-galactopyranosides] of kaempferol (3,5,7,4'-tetrahydroxyflavone) and quercetin (3,5,7,3',4'-pentahydroxyflavone). The corresponding 3-O-[6-O-(3-hydroxy-3-methylglutaryl)-ß-D-galactopyranoside] of quercetin was also present in R. spinosissima, but at lower levels, together with 17 other flavonol O-glycosides for which structures were assigned using LC-UV-MS/MS. The distribution of flavonol 3-hydroxy-3-methylglutarylgalactosides in Rosa was limited to some species of subgenus Rosa section Pimpinellifoliae and Rosa roxburghii Sw. of the monotypic subgenus Platyrhodon, indicating that this character could be of value in phylogenetic analyses of the genus.
Asunto(s)
Glicósidos/química , Quempferoles/química , Meglutol/química , Rosa/química , Acilación , Glicósidos/clasificación , Glicósidos/aislamiento & purificación , Quempferoles/clasificación , Quempferoles/aislamiento & purificación , Espectroscopía de Resonancia Magnética , Meglutol/aislamiento & purificación , Estructura Molecular , Filogenia , Extractos Vegetales/química , Hojas de la Planta/química , Quercetina/química , Especificidad de la EspecieRESUMEN
Personal meanings given to the experience of living with nursing home death were shared by 5 nursing home residents. Data were collected using semi-structured interviews. Using M. van Manen's (1990) hermeneutic phenomenology, the lived experience of residents emerged as a compilation of 5 dynamically occurring themes, including (a) mapping relations, (b) pacing oneself (c) maintaining belongingness, (d) reconciling death as part of life, and (e) engaging in preparatory review. The overarching essence of the lived experienced was defined as reflection toward resolution of dying as a "resident" in a sea of life gains and losses. Residents' expressions revealed that living with peers' dying in a nursing home is closely entwined with how life is experienced during one's final days.
Asunto(s)
Actitud Frente a la Muerte , Muerte , Relaciones Interpersonales , Anciano , Anciano de 80 o más Años , Femenino , Hogares para Ancianos , Humanos , Masculino , Casas de Salud , Investigación CualitativaRESUMEN
The major constituents of leaf extracts of Iris fulva KER GAWL. comprised a known flavone C-glycoside, 5,4'-dihydroxy-7-methoxyflavone-6-C-(6â´-O-(E)-p-coumaroyl-ß-glucopyranosyl)(1â´â2â³)-ß-glucopyranoside (1) and the new monoterpene glycoside, linalyl-6'-O-(3â³-hydroxy-3â³-methylglutaroyl)-ß-D-glucopyranoside (2), both of which were prominent components of Iris brevicaulis RAF. leaf extracts. The structure of a new polyacylated sucrose derivative (3a) obtained from the rhizomes of I. fulva was elucidated as 3-O-(E)-p-coumaroyl-ß-D-fructofuranosyl-(2â1')-[2â³,4â³,6â³-tri-O-acetyl-ß-D-glucopyranosyl-(1â³â3')-(2',6'-di-O-acetyl-4'-O-(E)-p-coumaroyl-α-D-glucopyranoside)]. Selective hydrolysis of the 4â³-O-acetyl moiety of the terminal ß-glucopyranosyl residue of 3a occurred after several hours in solution giving 3-O-(E)-p-coumaroyl-ß-D-fructofuranosyl-(2â1')-[2â³,6â³-di-O-acetyl-ß-D-glucopyranosyl-(1â³â3')-(2',6'-di-O-acetyl-4'-O-(E)-p-coumaroyl-α-D-glucopyranoside)] (3b), which subsequently underwent further deacetylation.
Asunto(s)
Glicósidos/química , Iridaceae/química , Cromatografía Liquida , Glicósidos/aislamiento & purificación , Glicosilación , Espectroscopía de Resonancia Magnética , Conformación Molecular , Hojas de la Planta/química , Rizoma/química , Espectrometría de Masa por Ionización de ElectrosprayRESUMEN
This study documents the work women do to provision for themselves and others. It charts the contours of this work and examines associated responsibilities. The concept of provisioning informed interviews with 100 women. The diversity and range of women's work were surfaced by selecting women from six community groups, marginalized by income, race, and age, in two Canadian provinces. Findings summarize the types of provisioning activities and strategies women use to meet their responsibilities. Because the latter flow through pathways of relationships, negotiating the boundaries of their provisioning responsibilities shapes women's daily work and possibilities for engaging in civil society.
Asunto(s)
Relaciones Familiares , Identidad de Género , Responsabilidad Social , Mujeres Trabajadoras/psicología , Trabajo/psicología , Adulto , Colombia Británica , Femenino , Humanos , Persona de Mediana Edad , Ontario , Solución de Problemas , Política Pública , Apoyo Social , Valores SocialesRESUMEN
BACKGROUND: Exposure to androgens early in development, while activating adaptive aggressive behavior, may also exert long-lasting effects on non-target components of phenotype. Here we compare these organizational effects of perinatal androgens in closely related Nazca (Sula granti) and blue-footed (S. nebouxii) boobies that differ in neonatal social system. The older of two Nazca booby hatchlings unconditionally attacks and ejects the younger from the nest within days of hatching, while blue-footed booby neonates lack lethal aggression. Both Nazca booby chicks facultatively upregulate testosterone (T) during fights, motivating the prediction that baseline androgen levels differ between obligately siblicidal and other species. METHODOLOGY/PRINCIPAL FINDINGS: We show that obligately siblicidal Nazca boobies hatch with higher circulating androgen levels than do facultatively siblicidal blue-footed boobies, providing comparative evidence of the role of androgens in sociality. Although androgens confer a short-term benefit of increased aggression to Nazca booby neonates, exposure to elevated androgen levels during this sensitive period in development can also induce long-term organizational effects on behavior or morphology. Adult Nazca boobies show evidence of organizational effects of early androgen exposure in aberrant adult behavior: they visit unattended non-familial chicks in the colony and direct mixtures of aggression, affiliative, and sexual behavior toward them. In a longitudinal analysis, we found that the most active Non-parental Adult Visitors (NAVs) were those with a history of siblicidal behavior as a neonate, suggesting that the tendency to show social interest in chicks is programmed, in part, by the high perinatal androgens associated with obligate siblicide. Data from closely related blue-footed boobies provide comparative support for this interpretation. Lacking obligate siblicide, they hatch with a corresponding low androgen level, and blue-footed booby adults show a much lower frequency of NAV behavior and a lower probability of behaving aggressively during NAV interactions. This species difference in adult social behavior appears to have roots in both pleiotropic and experiential effects of nestling social system. CONCLUSIONS/SIGNIFICANCE: Our results indicate that Nazca boobies experience life-long consequences of androgenic preparation for an early battle to the death.
Asunto(s)
Andrógenos/fisiología , Conducta Animal , Aves/fisiología , Animales , Aves/embriología , FemeninoRESUMEN
The chromatographic behaviour of steroidal saponins found in Anemarrhena asphodeloides, Asparagus officinalis, Convallaria majalis, Digitalis purpurea and Ruscus aculeatus was studied by HPLC-MS using a C-18 reversed-phase column and aqueous acetonitrile or aqueous methanol mobile phase gradients, with or without the addition of 1% acetic acid. The behaviour was compared to that of triterpene saponins found in Aesculus hippocastanum, Centella asiatica, Panax notoginseng and Potentilla tormentilla. Inclusion of methanol in the mobile phase under acidic conditions was found to cause furostanol saponins hydroxylated at C-22 to chromatograph as broad peaks, whereas the peak shapes of the spirostanol saponins and triterpene saponins studied remained acceptable. In aqueous methanol mobile phases without the addition of acid, furostanol saponins chromatographed with good peak shape, but each C-22 hydroxylated furostanol saponin was accompanied by a second chromatographic peak identified as its C-22 methyl ether. Methanolic extracts analysed in non-acidified aqueous acetonitrile mobile phases also resolved pairs of C-22 hydroxy and C-22 methoxy furostanol saponins. The C-22 methyl ether of deglucoruscoside was found to convert to deglucoruscoside during chromatography in acidified aqueous acetonitrile, or by dissolving in water. Poor chromatography of furostanol saponins in acidified aqueous methanol is due to the interconversion of the C-22 hydroxy and C-22 methoxy forms. It is recommended that initial analysis of saponins by HPLC-MS using a C-18 stationary phase is performed using acidified aqueous acetonitrile mobile phase gradients. The existence of naturally-occurring furostanol saponins methoxylated at C-22 can be investigated with aqueous acetonitrile mobile phases and avoiding methanol in the extraction solvent.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Saponinas/química , Espectrometría de Masa por Ionización de Electrospray/métodos , Estructura Molecular , Reproducibilidad de los Resultados , Saponinas/análisis , Espectrofotometría UltravioletaRESUMEN
An ion trap LC-MS/MS method is described for the analysis of C-glycosylflavone O-glycosides in crude methanolic extracts of plants. The method employs survey scans with and without the application of up-front collision induced dissociation (CID) to generate diagnostic ions for data-directed MS/MS. The spectra acquired allow assignment of the C-linked sugar to either the C-6 or C-8 position of the aglycone and provide data on the molecular mass of the compound, the number and type of O-linked sugars and the molecular mass of the flavone aglycone. These data for the majority of C-glycosylflavone O-glycosides in an extract are obtained automatically in one LC-MS/MS analysis without manual pre-programming. Key to the assignment of the C-6 or C-8 site of C-glycosylation is the generation, by up-front CID, of the (0,1)X+ product ion formed by internal cleavage of the C-linked sugar. MS/MS of this ion is found to have diagnostic value in addition to the (0,2)X+ product ion described by other authors. Ion trap MS/MS spectra of [M+H]+ of the 6,8-di-C-glycosylflavones schaftoside and isoschaftoside show an additional and previously unreported diagnostic product ion that is useful in determining the type of sugar at the C-6 position. The product ion spectra of protonated kaempferol 3-O-glucosylrhamnosides show similarities to the spectra of C-glycosylflavone O-glycosides; this is a potential source of confusion if the analysis of such glycosides is limited solely to MS/MS of [M+H]+.
Asunto(s)
Cromatografía Liquida/métodos , Flavonas/química , Glicósidos/química , Espectrometría de Masas/métodos , Extractos Vegetales/química , Espectroscopía de Resonancia MagnéticaRESUMEN
Solid state dynamic properties have been investigated for the racemic (DL) and enantiomerically pure (L) crystalline forms of the amino acid serine [HO x CH2 x CH(NH3(+)) x CO2(-)] using 2H NMR line shape analysis and 2H NMR spin-lattice relaxation time measurements for samples of DL-serine and L-serine deuterated in the NH3(+) and OH groups. 2H NMR line shape analysis indicates that, for both L-serine and DL-serine, the ND3(+) group undergoes a 3-site 120 degrees jump motion, with jump frequencies in the intermediate motion regime (10(3) s(-1) to 10(8) s(-1)) in the temperature range 153-313 K. However, at a given temperature, the jump frequency is substantially higher for L-serine (e.g., at 233 K, the jump frequency is 5.0 x 10(6) s(-1) for L-serine and 6.0 x 10(4) s(-1) for DL-serine). The OD group is not dynamic on the 2H NMR time scale within the temperature range studied. The results from both 2H NMR line shape analysis (LA) and 2H NMR spin-lattice relaxation time measurements (SLR) indicate that the activation energy for the 3-site 120 degree jump motion of the ND3(+) group is significantly higher for DL-serine [38.0 +/- 1.0 kJ mol(-1) (LA); 39.7 +/- 0.8 kJ mol(-1) (SLR)] than for L-serine [23.4 +/- 0.8 kJ mol(-1) (LA); 23.8 +/- 0.3 kJ mol(-1) (SLR)]. The difference in activation energies between DL-serine and L-serine is substantially greater than any reported previously for an amino acid in different crystal forms.
Asunto(s)
Aminoácidos/química , Cristalización , Espectroscopía de Resonancia Magnética , Serina/química , Estereoisomerismo , TermodinámicaRESUMEN
BACKGROUND: The quality of epilepsy care has often been noted to be poor and fragmentary. Most people with epilepsy are solely under the care of their general practitioner (GP). Many patients report medication side-effects and poor seizure control. Most GPs accept responsibility for epilepsy care; however, many report problems with knowledge of epilepsy and nearly all support guidance on epilepsy management. AIM: To determine whether a GP-completed prompt and reminder card is effective in improving the quality of epilepsy care when used opportunistically. DESIGN OF STUDY: Primary care-based pragmatic cluster-randomised controlled trial. SETTING: People with active epilepsy (n = 1275) from 82 practices. METHOD: Practices were randomly categorised as 'control', 'doctor-held card' (card in patient records), or 'patient-held card' practices. RESULTS: Compared with control practices, recording of seizure frequency was significantly increased in doctor-held card practices (57.4% versus 42.8%, P = 0.003) but not in patient-held card practices (44.6% versus 42.8%). No differences were found in the proportion of seizure-free patients (doctor-held card [56.0%] versus control [51.5%]; patient-held card [58.1%] versus control [51.5%]) or in the proportion on monotherapy. Patients in both intervention groups reported more medication-related side-effects and patients in doctor-held card practices were less satisfied with information provision about epilepsy. Participating GPs found the card useful. The doctor-held card was retrieved and completed more often than the patient-held card. CONCLUSIONS: A doctor-held prompt and reminder card is effective in improving the recording of key clinical information for people with epilepsy, is felt to be useful by GPs, and is completed more often than a patient-held card. However it does not improve outcomes and may result in less patient-centred care.