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1.
Talanta ; 278: 126512, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38970964

RESUMEN

The tetracycline (TC) residue in water environment has caused serious public safety issue. Thus, efficient sensing of TC is highly desirable for environmental protection. Herein, biomass-derived nitrogen-doped carbon dots (N-CDs) synthesized from natural Ophiopogon japonicus f. nanus (O. japonicus) were used for TC detection. The unique solvent synergism efficiently enhanced detection sensitivity, and the detailed sensing mechanism was deeply investigated. The blue fluorescence of N-CDs was quenched by TC via static quenching and inner filter effect. Moreover, the enhancement of green fluorescence from deprotonated TC was firstly proposed and sufficiently verified. The solvent effect of N-methyl pyrrolidone (NMP) and the fluorescence resonance energy transfer (FRET) with N-CDs achieved an instantaneous enhancement of the green emission by 64-fold. Accordingly, a ratiometric fluorescence method was constructed for rapid and sensitive sensing of TC with a low detection limit of 6.3 nM within 60 s. The synergistic effect of N-CDs and solvent assistance significantly improved the sensitivity by 7-fold compared to that in water. Remarkably, the biomass-derived N-CDs displayed low cost, good solubility, and desired stability. The deep insights into the synergism with solvent can provide prospects for the utilization of biomass-based materials and broaden the development of advanced sensors with promising applications.


Asunto(s)
Biomasa , Carbono , Pirrolidinonas , Puntos Cuánticos , Solventes , Tetraciclina , Contaminantes Químicos del Agua , Pirrolidinonas/química , Pirrolidinonas/análisis , Carbono/química , Puntos Cuánticos/química , Solventes/química , Contaminantes Químicos del Agua/análisis , Tetraciclina/análisis , Tetraciclina/química , Límite de Detección , Transferencia Resonante de Energía de Fluorescencia/métodos , Espectrometría de Fluorescencia/métodos
2.
Anal Methods ; 16(24): 3968-3982, 2024 Jun 20.
Artículo en Inglés | MEDLINE | ID: mdl-38853581

RESUMEN

Concerns have been raised about synthetic cannabinoids (SCs), which are among the most often trafficked and used illegal substances. An analytical method that holds promise for determining illicit drug use in the general population is wastewater-based epidemiology (WBE). Unfortunately, the concentration of SCs in wastewater is often extremely low on account of their hydrophobic nature, thus presenting a significant obstacle to the accurate detection and quantification of SCs using WBE. In this study, we present novel magnetic nanomaterials as amphiphilic adsorbents for pretreatment of wastewater using magnetic solid phase extraction (MSPE). Polydopamine-modified Fe3O4 nanoparticles were used as the magnetic core and further functionalized with poly(divinylbenzene-N-vinylpyrrolidone). Coupled with UHPLC-MS/MS analysis, an analytical method to simultaneously detect nine SCs at trace-levels in wastewater was developed and validated, enriching 50 mL wastewater to 100 µL with limits of detection (LOD) being 0.005-0.5 ng L-1, limits of quantification (LOQ) being 0.01-1.0 ng L-1, recoveries ranging from 73.99 to 110.72%, and the intra- and inter-day precision's relative standard deviations less than 15%. In comparison to the time-consuming conventional column-based solid phase extraction, the entire MSPE procedure from sample pre-treatment to data acquisition could be finished in one hour, thus largely facilitating the WBE method for drug surveillance and control.


Asunto(s)
Cannabinoides , Indoles , Límite de Detección , Polímeros , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Aguas Residuales , Contaminantes Químicos del Agua , Indoles/química , Polímeros/química , Aguas Residuales/química , Aguas Residuales/análisis , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Espectrometría de Masas en Tándem/métodos , Cannabinoides/análisis , Cannabinoides/química , Nanopartículas de Magnetita/química , Cromatografía Líquida de Alta Presión/métodos , Pirrolidinonas/química , Pirrolidinonas/análisis , Adsorción
3.
Fitoterapia ; 162: 105267, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35961597

RESUMEN

A new alkaloid featured with a dibenz[c,e]azepin-5-one scaffold, namely emililactam A (3), together with a known pyrrolidine alkaloid (emilisonchine, 1) and a known flavonoid alkaloid [8-(2″-pyrrolidinone-5″-yl)-quercetin, 2] were isolated from the aerial parts of Emilia sonchifolia. Compounds 1 and 2 were isolated as racemic forms which were further separated, for the first time, to their corresponding enantiomers [(+)-1/(-)-1 and (+)-2/(-)-2], respectively, by using chiral-phase HPLC. The structure of new compound 3 was elucidated by extensive spectroscopic analysis. In addition, the absolute configurations of optically pure (+)-1/(-)-1 and (+)-2/(-)-2 were determined by the time-dependent density functional theory electronic circular dichroism (TDDFT-ECD) calculations. In an in vitro bioassay, compounds (+)-1, (-)-1, (±)-1, and 3 exhibited moderate neuroprotective effects against corticosterone-induced injuries of PC12 cells.


Asunto(s)
Alcaloides , Asteraceae , Fármacos Neuroprotectores , Alcaloides/química , Asteraceae/química , Dicroismo Circular , Corticosterona , Estructura Molecular , Fármacos Neuroprotectores/farmacología , Componentes Aéreos de las Plantas/química , Pirrolidinas , Pirrolidinonas/análisis , Quercetina
4.
Sci Rep ; 11(1): 24466, 2021 12 28.
Artículo en Inglés | MEDLINE | ID: mdl-34963683

RESUMEN

Biomarkers for the measurement of islets of Langerhans could help elucidate the etiology of diabetes. Synaptic vesicle glycoprotein 2 A (SV2A) is a potential marker reported to be localized in the endocrine pancreas. [11C]UCB-J is a novel positron emission tomography (PET) radiotracer that binds to SV2A and was previously evaluated as a synaptic marker in the central nervous system. Here, we evaluated whether [11C]UCB-J could be utilized as a PET tracer for the islets of Langerhans in the pancreas by targeting SV2A. The mRNA transcription of SV2A was evaluated in human isolated islets of Langerhans and exocrine tissue. In vitro autoradiography was performed on pancreas and brain sections from rats and pigs, and consecutive sections were immunostained for insulin. Sprague-Dawley rats were examined with PET-MRI and ex vivo autoradiography at baseline and with administration of levetiracetam (LEV). Similarly, pigs were examined with dynamic PET-CT over the pancreas and brain after administration of [11C]UCB-J at baseline and after pretreatment with LEV. In vivo radioligand binding was assessed using a one-compartment tissue model. The mRNA expression of SV2A was nearly 7 times higher in endocrine tissue than in exocrine tissue (p < 0.01). In vitro autoradiography displayed focal binding of [11C]UCB-J in the pancreas of rats and pigs, but the binding pattern did not overlap with the insulin-positive areas or with ex vivo autoradiography. In rats, pancreas binding was higher than that in negative control tissues but could not be blocked by LEV. In pigs, the pancreas and brain exhibited accumulation of [11C]UCB-J above the negative control tissue spleen. While brain binding could be blocked by pretreatment with LEV, a similar effect was not observed in the pancreas. Transcription data indicate SV2A to be a valid target for imaging islets of Langerhans, but [11C]UCB-J does not appear to have sufficient sensitivity for this application.


Asunto(s)
Islotes Pancreáticos/diagnóstico por imagen , Glicoproteínas de Membrana/análisis , Proteínas del Tejido Nervioso/análisis , Tomografía de Emisión de Positrones , Piridinas/análisis , Pirrolidinonas/análisis , Animales , Femenino , Masculino , Tomografía Computarizada por Tomografía de Emisión de Positrones , Radiofármacos/análisis , Ratas Sprague-Dawley , Porcinos
5.
Environ Int ; 146: 106221, 2021 01.
Artículo en Inglés | MEDLINE | ID: mdl-33113467

RESUMEN

N-methyl-2-pyrrolidone (NMP) and its substitute N-ethyl-2-pyrrolidone (NEP) are aprotic solvents used in many technical applications, but also in carpets, and consumer products such as cleaning agents, and cosmetics. NMP and NEP are classified as reproductive toxicants. As a substance of very high concern (SVHC), NMP is included in the European REACH (Registration, Evaluation, Authorisation of Chemicals) candidate listfor authorisation. NMP and NEP metabolites were measured in more than 2100 urine samples of 3- to 17-year-old children and adolescents, participating in the population-representative German Environmental Survey for Children and Adolescents 2014-2017 (GerESV). The two NMP metabolites 5-hydroxy-N-methyl-2-pyrrolidone (5-HNMP) and 2-hydroxy-N-methylsuccinimide (2-HMSI) could be detected and quantified in all urine samples, and the two NEP metabolites 5-hydroxy-N-ethylpyrrolidone (5-HNEP) and 2-hydroxy-N-ethylsuccinimide (2-HESI) in 32% and 87% of the urine samples. Geometric mean concentrations were 103.1 µg/L (88.21 µg/gcreatinine) for the sum of NMP metabolites and 11.86 µg/L (10.15 µg/gcreatinine) for the sum of NEP metabolites, thus remaining below the current health-based human biomonitoring values. For NMP, highest exposure was found in young children, but exposure pathways could not be revealed. Exposure to NEP was highest in adolescents and participants with low socio-economic status or migration background. Associations to usage of personal care products suggested the choice of products to have a distinct impact on NEP exposure. The presented data can be used by the German Human Biomonitoring Commission to derive new reference values (RV95) for NMP and NEP for children and adolescents in Germany. This will facilitate to recognise changing exposure levels in this population group in Germany.


Asunto(s)
Monitoreo Biológico , Pirrolidinonas , Adolescente , Niño , Preescolar , Monitoreo del Ambiente , Alemania , Humanos , Pirrolidinonas/análisis , Solventes/análisis
6.
J Chromatogr A ; 1621: 461053, 2020 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-32276857

RESUMEN

The chromatographic properties of a new coated amylose tris(3-chloro-5-methylphenylcarbamate) were evaluated in supercritical fluid chromatography for the separation of enantiomers of chiral 1-aryl-5-aryl-pyrrolidin-2-one derivatives, potential anticancer agents, and some commercial drugs. The mobile phase consisted of CO2-modifier mixtures with 30% of either methanol or ethanol, the flow rate was 3 mL/min. The column oven temperature was 40 °C and the outlet pressure was 15 MPa, in order to limit the compressibility of the CO2, thus limiting density variation along the column. The obtained results were then compared to those observed toward 3 other stationary phases: the coated amylose tris(3,5-dimethylphenylcarbamate), the immobilized amylose tris(3,5-dimethylphenylcarbamate) and the coated amylose tris(5-chloro-2-methylphenylcarbamate). It was shown that the new coated amylose tris(3-chloro-5-methylphenylcarbamate) was the most retentive column whatever the studied compounds, particularly for thalidomide and omeprazole with retention factors up to 73.3 and 29.5for the second enantiomer, respectively. Concerning the enantioselectivity, even most of the compounds are separated on all the four columns, the coated amylose tris(3-chloro-5-methylphenylcarbamate) allows the best resolution for most of the ten studied analytes (except omeprazole for which the resolution values are equal to 7.8 and 9.7 on the coated amylose tris(3-chloro-5-methylphenylcarbamate) and amylose tris(3,5-dimethylphenylcarbamate), respectively). Acting in complementary ways, the two chlorinated stationary phases permitted the complete separation of enantiomers of nine compounds out of the ten.


Asunto(s)
Amilosa/análogos & derivados , Cromatografía con Fluido Supercrítico/métodos , Amilosa/química , Antineoplásicos/análisis , Antineoplásicos/aislamiento & purificación , Carbamatos/química , Preparaciones Farmacéuticas/análisis , Preparaciones Farmacéuticas/aislamiento & purificación , Fenilcarbamatos/química , Pirrolidinonas/análisis , Pirrolidinonas/aislamiento & purificación , Dióxido de Silicio/química , Estereoisomerismo
7.
Luminescence ; 35(5): 728-737, 2020 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-31994341

RESUMEN

A novel approach on fluorescence quenching of tyrosine and l-tryptophan is presented for spectrofluorimetric determination of aniracetam in drug substances and products. The quenching mechanism was investigated using Stern-Volmer plots and ultraviolet spectra figures of quencher-fluorophore mixtures. Binding constant and stoichiometry were calculated using double-log plots. The spectrofluorimetric method was optimized for the experimental conditions affecting fluorescence quenching including fluorophore concentration, diluent, and reaction time. Moreover, the pH-rate profile of aniracetam was studied using simple kinetics and found to be stable within the pH range 5-8. Fluorescence quenching of tyrosine and l-tryptophan were observed on addition of aniracetam in aqueous medium at pH 5.5-6.5. Aniracetam quenched the fluorescence of tyrosine and l-tryptophan in the concentration range 1-20 µg/ml and 0.3-20 µg/ml, respectively, with binomial relationships between quenching values (ΔF) and aniracetam concentration. Limits of detection were found to be 0.10 µg/ml for tyrosine-aniracetam and 0.14 µg/ml for l-tryptophan-aniracetam. Method validation was performed as per ICH guidelines and demonstrated that the developed spectrofluorimetric method was accurate, precise, specific, and suitable for analysis of aniracetam in routine quality control laboratories. All experimental materials and solvents used are eco-friendly, indicating that the cited spectrofluorimetric procedure is an excellent green method.


Asunto(s)
Fluorescencia , Colorantes Fluorescentes/química , Nootrópicos/análisis , Pirrolidinonas/análisis , Triptófano/química , Tirosina/química , Estructura Molecular , Espectrometría de Fluorescencia
8.
Food Res Int ; 125: 108635, 2019 11.
Artículo en Inglés | MEDLINE | ID: mdl-31554114

RESUMEN

Storage has a dramatic influence on the chemical composition, sensory qualities, biological activity, and therefore the commercial value of white tea. In this study, the metabolites in white teas stored for 1, 3, 7, and ≥ 10 years were comprehensively compared by a nontargeted metabolomics investigation. Most metabolites, including catechins, flavonol/flavone glycosides, amino acids, nucleosides, organic acids, aroma precursors, lipids, and carbohydrates, decreased with increasing storage duration, while 8-C N-ethyl-2-pyrrolidinone-substituted flavan-3-ols (EPSFs) and pyroglutamic acid increased. The absolute quantifications of 24 storage-related compounds combined with linear regression analysis showed that a panel of 5 indexes based on EPSFs has a good predictive ability for the storage duration of white teas (correlation coefficients were 0.9294 and 0.8812 in the model and test sets, respectively). The errors between the predicted and the actual storage durations ranged from -1.75 to 1.84 years for the white teas stored for <10 years.


Asunto(s)
Camellia sinensis/química , Flavonoides/análisis , Almacenamiento de Alimentos/métodos , Metabolómica/métodos , Pirrolidinonas/análisis , Té/química , Catequina/análisis , Flavonoles/análisis , Manipulación de Alimentos/métodos , Glicósidos/análisis , Extractos Vegetales/química , Ácido Pirrolidona Carboxílico/análisis , Factores de Tiempo
9.
J Agric Food Chem ; 66(27): 7209-7218, 2018 Jul 11.
Artículo en Inglés | MEDLINE | ID: mdl-29921123

RESUMEN

White teas of different stored ages have varied flavor, bioactivity, and commercial value. In this study, a liquid chromatography-mass spectrometry-based metabolomics investigation revealed that there are distinct differences among the compound patterns of Baihaoyinzhen (BHYZ) and Baimudan (BMD) white teas with various storage durations. The levels of flavan-3-ols, procyanidins, theasinensins, theaflavins, flavonol- O-glycosides, flavone- C-glycosides, and most of the amino acids were reduced after long-term (>4 years) storage. More importantly, 8-C N-ethyl-2-pyrrolidinone-substituted flavan-3-ols (EPSFs), including seven novel compounds discovered in white teas for the first time, were formed from theanine and flavan-3-ols during storage, and their contents were positively correlated with the storage duration. These findings were further confirmed by the linearly increasing formation of EPSFs in reaction solution and BMD white teas stored in an environment-controlled cabinet. In conclusion, EPSFs were detected in white teas for the first time and were discovered as marker compounds and potential indicators for long-term storage of white tea.


Asunto(s)
Biomarcadores/análisis , Flavonoides/análisis , Almacenamiento de Alimentos , Pirrolidinonas/análisis , Té/química , Biflavonoides/análisis , Camellia sinensis/química , Catequina/análisis , Cromatografía Líquida de Alta Presión/métodos , Flavonoides/química , Flavonoles/análisis , Análisis de los Alimentos/métodos , Glicósidos/análisis , Espectrometría de Masas , Metabolómica/métodos , Proantocianidinas/análisis , Pirrolidinonas/química , Reproducibilidad de los Resultados , Té/metabolismo
10.
Water Sci Technol ; 2017(2): 329-339, 2018 May.
Artículo en Inglés | MEDLINE | ID: mdl-29851385

RESUMEN

In this study, four different membranes were fabricated by using polyetherimide and polyacrylonitrile polymers, N-methyl-2-pyrrolidone and polyvinylpyrrolidone (PVP) via phase inversion method to improve the membrane performance in fruit juice wastewater (FJWW) treatment. The addition of PVP to the casting solution increased membrane hydrophilicity, water content, contact angle, porosity, Fourier transform infrared spectroscopy peaks, membrane thickness, average roughness and viscosity of cast solutions compared to the bare membrane. It can be said that the addition of a lower polymer concentration and PVP intensively increases the pure water flux of the membrane. However, as the flux increased, a small decrease in FJWW rejection was observed.


Asunto(s)
Resinas Acrílicas/análisis , Polímeros/análisis , Povidona/análisis , Pirrolidinonas/análisis , Ultrafiltración/métodos , Eliminación de Residuos Líquidos/métodos , Jugos de Frutas y Vegetales/análisis , Membranas Artificiales , Aguas Residuales/análisis
11.
Artículo en Inglés | MEDLINE | ID: mdl-29665472

RESUMEN

Brivaracetam (BRV) is a new high affinity synaptic vesicle protein 2A ligand recently approved for adults with partial-onset seizures. As a support to in vitro metabolism assays, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method coupled to off-line solid phase extraction (SPE) was developed to quantify BRV acid metabolites, that is, BRV-AC (carboxylic derivative derived from BRV hydrolysis) and BRV-OHAC (corresponding to hydroxylated BRV-AC). The method was validated for various incubates (liver and kidney tissue homogenates and blood, all from humans) and applied to in vitro metabolism assays. The analytes were isolated from buffered samples using ISOLUTE C8 96-well SPE plates. Chromatographic separation was achieved on a Waters Atlantis T3 C18 analytical column (2.1 mm × 50 mm, 5 µm) with detection accomplished using a Waters Premier tandem mass spectrometer in positive ion electrospray and multiple reaction monitoring (MRM) mode. The standard curves, which ranged from 1.00 to 200 ng/mL for BRV-AC, BRV-OHAC, were fitted to a 1/x2 weighted linear regression model. The intra-assay precision and inter-assay precision (expressed as coefficient of variation -%CV) were <8.5%, and the assay accuracy (deviation - %Dev) was within ±7.1% for the different matrices. This accurate, precise, and selective SPE/LC-MS/MS method has been successfully applied to in vitro assays aimed at characterizing the kinetics of BRV hydrolysis. BRV was found to be a better substrate for hydrolysis than its hydroxylated metabolite BRV-OH. BRV hydrolysis was detected in blood, liver and kidneys, demonstrating the broad distribution of the enzyme catalyzing the reaction.


Asunto(s)
Cromatografía Liquida/métodos , Pirrolidinonas/análisis , Pirrolidinonas/metabolismo , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Humanos , Hidrólisis , Riñón/citología , Riñón/metabolismo , Límite de Detección , Modelos Lineales , Microsomas Hepáticos/metabolismo , Pirrolidinonas/química , Pirrolidinonas/aislamiento & purificación , Reproducibilidad de los Resultados
12.
J Econ Entomol ; 110(5): 1993-2001, 2017 10 01.
Artículo en Inglés | MEDLINE | ID: mdl-28961741

RESUMEN

Owing to the recent declines in honey bee (Apis mellifera L.) populations, there is a need for field and laboratory studies to investigate threats to pollinator health. This study examines the hypothesis that the organophosphate alternative, Rimon 0.83EC, can have consequences to honey bee health by combining newly acquired field residue data, laboratory bioassays, and colony level feeding studies. Following label rate applications of Rimon 0.83EC to apple trees, average residue concentrations of the active ingredient, novaluron, were found to be 3.38 ppm in tree-collected pollen. Residues of the major co-formulant in Rimon 0.83EC, N-methyl-2-pyrrolidone (NMP), were below the limit of detection in the field, but a growth chamber study described here found that NMP can persist in pollen for up to 7 d with average concentrations of 69.3 ppm. Concurrent larval rearing studies found novaluron and NMP to be toxic to developing honey bees at doses as low as 100 ppb and 100 ppm, respectively. Nucleus colony feeding studies found that chronic exposure to Rimon 0.83EC at doses as low as 200 ppm (18.6 ppm novaluron) can result in interruptions to brood production that can last for up to 2 wk after exposure. Taken together, these data indicate the use of Rimon 0.83EC on blooming flowers is a significant threat to honey bee reproduction, and suggest the need for more strict and clear usage guidelines.


Asunto(s)
Abejas/efectos de los fármacos , Insecticidas/toxicidad , Residuos de Plaguicidas/toxicidad , Compuestos de Fenilurea/toxicidad , Pirrolidinonas/toxicidad , Animales , Abejas/crecimiento & desarrollo , Insecticidas/análisis , Larva/efectos de los fármacos , Larva/crecimiento & desarrollo , Residuos de Plaguicidas/análisis , Polen/química , Pirrolidinonas/análisis , Reproducción/efectos de los fármacos
13.
J Pharm Biomed Anal ; 126: 98-102, 2016 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-27179187

RESUMEN

In this work, a simple, sensitive and fast ultra performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS) method was developed and validated for the quantitative determination of tivantinib in rat plasma. Plasma samples were processed with a protein precipitation. The separation was achieved by an Acquity UPLC BEH C18 (2.1mm×50mm, 1.7µm) column with a gradient mobile phase consisting of 0.1% formic acid in water and acetonitrile. Detection was carried out using positive-ion electrospray tandem mass spectrometry via multiple reaction monitoring (MRM). The validated method had an excellent linearity in the range of 1.0-100ng/mL (r(2)>0.9967) with a lower limit of quantification (1.0ng/mL). The extraction recovery was in the range of 79.4-84.2% for tivantinib and 80.3% for carbamazepine (internal standard, IS). The intra- and inter-day precision was below 8.9% and accuracy was from -7.2% to 9.5%. No notable matrix effect and astaticism was observed for tivantinib. The method has been successfully applied to a pharmacokinetic study of tivantinib in rats for the first time, which provides the basis for the further development and application of tivantinib.


Asunto(s)
Antineoplásicos/sangre , Cromatografía Líquida de Alta Presión/métodos , Pirrolidinonas/sangre , Quinolinas/sangre , Espectrometría de Masas en Tándem/métodos , Animales , Antineoplásicos/análisis , Límite de Detección , Masculino , Pirrolidinonas/análisis , Quinolinas/análisis , Ratas , Ratas Sprague-Dawley , Reproducibilidad de los Resultados , Espectrometría de Masa por Ionización de Electrospray/métodos
14.
J Chromatogr A ; 1446: 134-40, 2016 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-27083261

RESUMEN

A rapid and sensitive gas chromatography with tandem mass spectrometry (GC-MS/MS) method has been developed and validated to quantitatively determine cosmetic ingredients, such as toluene, N-methylpyrrolidone, 2,4-dihydroxybenzophenone (benzophenone-1, BP-1), and diethylene glycol dimethacrylate, in nail products. In this procedure, test portions were extracted with acetone, followed by vortexing, sonication, centrifugation, and filtration. During the extraction procedure, BP-1 was derivatized making it amenable to GC-MS analysis, using N,O-​bis(trimethylsilyl)​trifluoroacetamide. The four ingredients were quantified by GC-MS/MS in an electron ionization mode. Four corresponding stable isotopically labeled analogues were selected as internal standards, which were added at the beginning of the sample preparation to correct for recoveries and matrix effects. The validated method was used to screen 34 commercial nail products for these four cosmetic ingredients. The most common ingredients detected in the nail products were toluene and BP-1. Toluene was detected in 26 products and ranged from 1.36 to 173,000µg/g. BP-1 ranged from 18.3 to 2,370µg/g in 10 products.


Asunto(s)
Cosméticos/análisis , Acetamidas/química , Acrilatos/análisis , Benzofenonas/análisis , Glicoles de Etileno/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Humanos , Metacrilatos , Uñas , Pirrolidinonas/análisis , Espectrometría de Masas en Tándem/métodos , Tolueno/análisis , Compuestos de Trimetilsililo/química
15.
Food Chem ; 202: 389-95, 2016 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-26920309

RESUMEN

Dispersive liquid-liquid microextraction was used to preconcentrate three spirocyclic tetronic/tetramic acid derivatives (spirotetramat, spiromesifen and spirodiclofen) and five neonicotinoid (thiamethoxam, chlotianidin, imidacloprid, acetamiprid and thiacloprid) insecticides previously extracted from fruit and vegetable matrices with acetonitrile. The organic enriched phase was evaporated, reconstituted in 25µL acetonitrile and analyzed by reversed-phase liquid chromatography with tandem mass spectrometry using a triple quadrupole in selected reaction monitoring mode. Enrichment factors in the 15-100 range were obtained. A matrix effect was observed, the detection limits varying between 0.025 and 0.5ngg(-1), depending on the compound and the sample matrix. The developed method was applied to the analysis of 25 samples corresponding to five different fruit and vegetable matrices. Only thiamethoxam was detected in a lemon sample at a concentration close to the quantification limit, and spiromesifen and spirotetramat at concentrations between 11.6 and 54.5ngg(-1).


Asunto(s)
Frutas/química , Insecticidas/análisis , Microextracción en Fase Líquida/métodos , Verduras/química , Cromatografía Líquida de Alta Presión , Neonicotinoides , Nitrocompuestos/análisis , Oxazinas/análisis , Pirrolidinonas/análisis , Espectrometría de Masa por Ionización de Electrospray , Tiametoxam , Tiazoles/análisis
16.
J Fish Dis ; 39(5): 565-76, 2016 May.
Artículo en Inglés | MEDLINE | ID: mdl-26096159

RESUMEN

Edwardsiella tarda has long been known as a pathogen that causes severe economic losses in aquaculture industry. Insights gained on E. tarda pathogenesis may prove useful in the development of new methods for the treatment of infections as well as preventive measures against future outbreaks. In this report, we have established the correlation between the presence of virulence genes, related with three aspects typically involved in bacterial pathogenesis (chondroitinase activity, quorum sensing and siderophore-mediated ferric uptake systems), in the genome of E. tarda strains isolated from turbot in Europe and their phenotypic traits. A total of 8 genes were tested by PCR for their presence in 73 E. tarda isolates. High homogeneity was observed in the presence/absence pattern of all the strains. Positive results in the amplification of virulence-related genes were correlated with the detection of chondroitinase activity in agar plates, in vivo AHL production during fish infection and determination of type of siderophore produced by E. tarda. To the best of our knowledge, this is the first study carried out with European strains on potential virulence factors. Furthermore, we demonstrated for the first time that E. tarda produces the siderophore vibrioferrin.


Asunto(s)
Proteínas Bacterianas/genética , Edwardsiella tarda/genética , Edwardsiella tarda/patogenicidad , Infecciones por Enterobacteriaceae/veterinaria , Enfermedades de los Peces/microbiología , Peces Planos/microbiología , Factores de Virulencia/genética , Animales , Citratos/análisis , Citratos/metabolismo , Edwardsiella tarda/aislamiento & purificación , Infecciones por Enterobacteriaceae/microbiología , Europa (Continente) , Pirrolidinonas/análisis , Pirrolidinonas/metabolismo
17.
J Chromatogr A ; 1425: 62-72, 2015 Dec 18.
Artículo en Inglés | MEDLINE | ID: mdl-26614172

RESUMEN

The sensitivity of gas chromatography (GC) combined with the full evaporation technique (FET) for the analysis of aqueous samples is limited due to the maximum tolerable sample volume in a headspace vial. Using an acetone acetal as water scavenger prior to FET-GC analysis proved to be a useful and versatile tool for the analysis of high boiling analytes in aqueous samples. 2,2-Dimethoxypropane (DMP) was used in this case resulting in methanol and acetone as reaction products with water. These solvents are relatively volatile and were easily removed by evaporation enabling sample enrichment leading to 10-fold improvement in sensitivity compared to the standard 10µL FET sample volumes for a selection of typical high boiling polar residual solvents in water. This could be improved even further if more sample is used. The method was applied for the determination of residual NMP in an aqueous solution of a cefotaxime analogue and proved to be considerably better than conventional static headspace (sHS) and the standard FET approach. The methodology was also applied to determine trace amounts of ethylene glycol (EG) in aqueous samples like contact lens fluids, where scavenging of the water would avoid laborious extraction prior to derivatization. During this experiment it was revealed that DMP reacts quantitatively with EG to form 2,2-dimethyl-1,3-dioxolane (2,2-DD) under the proposed reaction conditions. The relatively high volatility (bp 93°C) of 2,2-DD makes it possible to perform analysis of EG using the sHS methodology making additional derivatization reactions superfluous.


Asunto(s)
Acetales/química , Acetona/análogos & derivados , Acetona/química , Agua/química , Antibacterianos/análisis , Cefotaxima/análogos & derivados , Cefotaxima/análisis , Cromatografía de Gases/métodos , Dioxolanos/química , Indicadores y Reactivos , Pirrolidinonas/análisis , Solventes , Volatilización
18.
Phytochemistry ; 110: 29-36, 2015 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-25561401

RESUMEN

Guggul gum resin from Commiphora wightii (syn. Commiphoramukul) has been used for centuries in Ayurveda to treat a variety of ailments. The NMR and GC-MS based non-targeted metabolite profiling identified 118 chemically diverse metabolites including amino acids, fatty acids, organic acids, phenolic acids, pregnane-derivatives, steroids, sterols, sugars, sugar alcohol, terpenoids, and tocopherol from aqueous and non-aqueous extracts of leaves, stem, roots, latex and fruits of C. wightii. Out of 118, 51 structurally diverse aqueous metabolites were characterized by NMR spectroscopy. For the first time quinic acid and myo-inositol were identified as the major metabolites in C. wightii. Very high concentration of quinic acid was found in fruits (553.5 ± 39.38 mg g(-1) dry wt.) and leaves (212.9 ± 10.37 mg g(-1) dry wt.). Similarly, high concentration of myo-inositol (168.8 ± 13.84 mg g(-1) dry wt.) was observed from fruits. The other metabolites of cosmeceutical, medicinal, nutraceutical and industrial significance such as α-tocopherol, n-methylpyrrolidone (NMP), trans-farnesol, prostaglandin F2, protocatechuic, gallic and cinnamic acids were identified from non-aqueous extracts using GC-MS. These important metabolites have thus far not been reported from this plant. Isolation of a fungal endophyte, (Nigrospora sps.) from this plant is the first report. The fungal endophyte produced a substantial quantity of bostrycin and deoxybostrycin known for their antitumor properties. Very high concentrations of quinic acid and myo-inositol in leaves and fruits; a substantial quantity of α-tocopherol and NMP in leaves, trans-farnesol in fruits, bostrycin and deoxybostrycin from its endophyte makes the taxa distinct, since these metabolites with medicinal properties find immense applications as dietary supplements and nutraceuticals.


Asunto(s)
Commiphora/química , Suplementos Dietéticos/análisis , Metabolómica , Carbohidratos/análisis , Cromatografía Líquida de Alta Presión , Frutas/química , Cromatografía de Gases y Espectrometría de Masas , Hidroxibenzoatos/análisis , Resonancia Magnética Nuclear Biomolecular , Extractos Vegetales/química , Gomas de Plantas/química , Hojas de la Planta/química , Pirrolidinonas/análisis , Ácido Quínico/análisis , Resinas de Plantas/análisis , alfa-Tocoferol/análisis
19.
Artículo en Alemán | MEDLINE | ID: mdl-25248818

RESUMEN

The German Ad-hoc Working Group on Indoor Guidelines of the Indoor Air Hygiene Committee and the States' Supreme Health Authorities is issuing indoor air guide values to protect public health. No human studies of sufficient quality are available for health evaluation of 1-methyl-2-pyrrolidone in air. In a well-documented chronic inhalation toxicity study in rats significant impairment of weight gain development has been observed (LOAEC = 400 mg/m(3)). The Working Group used this LOAEC as the point of departure for the derivation of guide value II. The conversion of repeated inhalation to continuous exposure (6-24 h; 5-7 days) used a factor of 5.6. By applying an interspecies factor of 2.5 for toxicodynamics, a factor of 10 to account for individual differences and an additional factor of 2 to include sensitive subgroups, results in a health hazard guide value (RW II) of 1 mg 1-methyl-2-pyrrolidone/m(3) indoor air (rounded). By using the NOAEC of 40 mg/m(3) from the same study and applying the same assessment factors as above a precautionary guide value (RW I) of 0.1 mg 1-methyl-2-pyrrolidone/m(3) is calculated.


Asunto(s)
Contaminación del Aire Interior/análisis , Contaminación del Aire Interior/prevención & control , Monitoreo del Ambiente/normas , Exposición por Inhalación/análisis , Exposición por Inhalación/prevención & control , Pirrolidinonas/análisis , Animales , Alemania , Guías como Asunto , Pirrolidinonas/toxicidad , Ratas
20.
J Agric Food Chem ; 62(32): 8187-96, 2014 Aug 13.
Artículo en Inglés | MEDLINE | ID: mdl-25033321

RESUMEN

Thermal treatment of meat proteins induces a range of observable and molecular-level changes. In order to understand and track these heat-induced modifications at the amino acid level, various analytical techniques were used. Changes were observed both in the soluble and in the insoluble fractions after hydrothermal treatment of minced beef samples. Redox proteomics clearly indicated increasing oxidative modification of proteins with increased heat exposure. Collagens in the soluble fraction and myosin in the insoluble fraction were found to be highly susceptible to such modifications. Maillard reaction products in the insoluble and pyrrolidone formation in the soluble fraction steadily increased with increased heat exposure. Fluorescence studies indicated a rapid increase in fluorescence with heat, suggesting the formation of advanced glycation end products. Overall these results provide a deeper understanding of the effect of cooking on meat proteins and the possible relationship to processing conditions in meat-derived food.


Asunto(s)
Culinaria , Proteínas en la Dieta/química , Carne/análisis , Proteínas Musculares/química , Músculo Esquelético/química , Mataderos , Aminoácidos/análisis , Animales , Bovinos , Productos Finales de Glicación Avanzada/análisis , Productos Finales de Glicación Avanzada/química , Humanos , Reacción de Maillard , Nueva Zelanda , Valor Nutritivo , Oxidación-Reducción , Fragmentos de Péptidos/análisis , Fragmentos de Péptidos/química , Proteolisis , Pirrolidinonas/análisis , Pirrolidinonas/química , Solubilidad , Factores de Tiempo
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