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1.
Food Chem ; 336: 127721, 2021 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-32763731

RESUMO

The major aroma-active compounds in clear red raspberry juice were identified by molecular sensory science approaches. Thirty-one aroma-active compounds were identified using detection frequency analysis and aroma extract dilution analysis. Among them, 18 volatiles with aroma activity in red raspberry were identified for the first time, while 14 volatiles with odor activity values (OAVs) ≥ 1 were confirmed as the major aroma-active compounds. Three C6 aldehydes showed the highest detection frequencies of 8, and ß-ionone exhibited the highest OAV of 9507 and flavor dilution factor of 512, which indicated that the floral and grassy note could be dominant in overall aroma. Quantitative descriptive analysis suggested that the grassy, floral, woody, and caramel-like notes can be simulated using aroma recombination model 1. Electronic nose analysis also demonstrated that model 1 had closer similarity to the original juice than others. The combination strategy used here would help improve the knowledge of red raspberry aroma.


Assuntos
Aromatizantes/análise , Sucos de Frutas e Vegetais/análise , Rubus/química , Compostos Orgânicos Voláteis/análise , Análise Discriminante , Nariz Eletrônico , Aromatizantes/isolamento & purificação , Cromatografia Gasosa-Espectrometria de Massas , Norisoprenoides/isolamento & purificação , Análise de Componente Principal , Rubus/metabolismo , Microextração em Fase Sólida , Compostos Orgânicos Voláteis/isolamento & purificação
2.
Food Chem ; 336: 127758, 2021 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-32784062

RESUMO

Heather honey is highly appreciated by consumers for its sensorial profile, which varies depending on the flora used by the honeybees. Volatile compounds contribute to these qualities. Characterisation of the volatile profile related to the botanical origin is of great interest for the standardization of unifloral honey. For this reason, 33 heather honey samples from northwest of the Iberian Peninsula were analysed by headspace solid-phase microextraction (HS-SPME) to identify the key volatile compounds in this type of honey. The aim of this research was to provide a descriptive analysis of these compounds, and to find whether there is any relationship with the main Erica species. A total of 58 volatile organic compounds were found, with hotrienol, phenylacetaldehyde, and cis-linalool being the most abundant. A principal component analysis and Spearman's rank correlation showed the homogeneity of the volatile profile in the samples, and their close relationship with the main pollen types.


Assuntos
Ericaceae/química , Mel/análise , Compostos Orgânicos Voláteis/análise , Animais , Abelhas , Ericaceae/metabolismo , Cromatografia Gasosa-Espectrometria de Massas , Pólen/química , Análise de Componente Principal , Microextração em Fase Sólida , Espanha , Compostos Orgânicos Voláteis/isolamento & purificação
3.
Food Chem ; 334: 127553, 2021 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-32688177

RESUMO

Rice is one of the most important cereals for human nutrition and is a basic staple food for half of the global population. The assessment of rice geographical origins in terms of its authenticity is of great interest to protect consumers from misleading information and fraud. In the present study, a head space gas chromatography mass spectrometry (HS-GC-MS) strategy for characterising volatile organic compounds (VOCs) profiles to distinguish rice samples from China, India and Vietnam is described. Partial Least Square Discriminant Analysis (PLS-DA) model exhibited a good discrimination (R2 = 0.98182, Q2 = 0.9722, and Accuracy = 1.0) for rice samples from China, India and Vietnam. Moreover, Data-Driven Soft Independent Modelling of Class Analogy (DD-SIMCA) and K-nearest neighbors shown good specificity 100% and accuracy 100% in identifying the origin of samples. The present study established VOC fingerprinting as a highly efficient approach to identify the geographical origin of rice.


Assuntos
Oryza/química , Compostos Orgânicos Voláteis/análise , China , Análise Discriminante , Cromatografia Gasosa-Espectrometria de Massas , Índia , Análise dos Mínimos Quadrados , Oryza/metabolismo , Microextração em Fase Sólida , Vietnã , Compostos Orgânicos Voláteis/química , Compostos Orgânicos Voláteis/isolamento & purificação
4.
Chemosphere ; 258: 127367, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32947676

RESUMO

Due to their important roles in salt-producing acid-base reactions, new particle formation (NPF), and as precursors in secondary organic aerosol (SOA) producing reactions, the atmospheric concentrations of particulate volatile amines (dimethylamine (DMA), ethylamine, diethylamine (DEA), propylamine, and butylamine) at Seoul were analyzed and evaluated. To quantify the presence of volatile amines in particulate matter with aerodynamic diameters less than or equal to a nominal 2.5 µm (PM2.5), an efficient and rapid analytical method based on in-matrix ethyl chloroformate (ECF) derivatization followed by headspace solid-phase microextraction (HS-SPME) was developed and validated using gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) in the multiple reaction monitoring (MRM) mode. The annual mean concentration of the total 5 target amines was 5.56±2.76 ng/m3 and the seasonal difference was small. The concentrations of particulate amines measured in this study were lower than those observed in Zongludak, Turkey, Nanjing, China, and Jeju, Korea but slightly higher than that reported in Kobe, Japan. The concentrations of the nitrosamines (nitrosodimethylamine (NDMA) and nitrosodiethylamine (NDEA)), and of the nitramines (dimethylnitramine (DMN) and diethylnitramine (DEN)) measured along with those of the target amines were used in a simple linear regression analysis. It indicates the contribution of DMA to the formation of NDMA in all seasons (except the fall) and DEA to the formation of NDEA in the summer, while DMA and DEA did not significantly contribute to the formation of nitramines.


Assuntos
Poluentes Atmosféricos/análise , Aminas/análise , Monitoramento Ambiental , China , Dietilnitrosamina , Dimetilaminas , Dimetilnitrosamina/análise , Etilaminas , Cromatografia Gasosa-Espectrometria de Massas/métodos , Nitrosaminas/análise , Material Particulado/análise , República da Coreia , Seul , Microextração em Fase Sólida/métodos , Espectrometria de Massas em Tandem
5.
J Pharm Biomed Anal ; 191: 113597, 2020 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-32927419

RESUMO

The multiple pathological effects of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection, and its total novelty, mean that currently a lot of diagnostic and therapeutic tools, established and tentative alike, are needed to treat patients in a timely, effective way. In order to make these tools more reliable, faster and more feasible, biological fluid microsampling techniques could provide many advantages. In this review, the most important microsampling techniques are considered (dried matrix spots, volumetric absorptive microsampling, microfluidics and capillary microsampling, solid phase microextraction) and their respective advantages and disadvantages laid out. Moreover, currently available microsampling applications of interest for SARS-CoV-2 therapy are described, in order to make them as much widely known as possible, hopefully providing useful information to researchers and clinicians alike.


Assuntos
Técnicas de Química Analítica/tendências , Infecções por Coronavirus/diagnóstico , Pneumonia Viral/diagnóstico , Coleta de Amostras Sanguíneas , Infecções por Coronavirus/terapia , Teste em Amostras de Sangue Seco , Humanos , Pandemias , Pneumonia Viral/terapia , Microextração em Fase Sólida , Espectrometria de Massas em Tandem
6.
J Chromatogr A ; 1626: 461354, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797834

RESUMO

The Al-doped mesoporous crystalline material-41 (Al-MCM-41) composite was prepared and applied as fiber coating material of headspace solid-phase microextraction (HS-SPME) for extraction of polycyclic aromatic hydrocarbons (PAHs) from human urine. Five PAHs including acenaphthene, fluorene, phenanthrene, anthracene, and pyrene are chosen as target analytes to evaluate the performance of the material by GC-FID analysis. The mesoporous Al-MCM-41 composite was characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption/desorption measurement, and thermogravimetric analysis. The parameters affecting the extraction efficiency of HS-SPME were investigated. Under the optimal conditions, the method exhibits ideal linearity for target analytes in the range of 0.3-600 ng⋅mL-1 with the coefficients (R2) equal or higher than 0.9906. The enrichment factors are calculated from 540 to 1760. The limits of detection (LODs) and limits of quantitation (LOQs) are between the ranges of 0.06-0.18 and 0.3-0.9 ng⋅mL-1, respectively. The relative standard deviations (RSDs) (n = 5) of intra-day and inter-day are in the ranges of 1.08-7.49% and 2.84-18.3% respectively. The fiber-to-fiber reproducibility (n = 3) is in the range of 6.47-13.9%. The method was successfully applied for the analysis of PAHs in human urine with reasonable recoveries which is ranging from 73.29 to 116.1%.


Assuntos
Alumínio/química , Hidrocarbonetos Policíclicos Aromáticos/urina , Dióxido de Silício/química , Microextração em Fase Sólida/métodos , Adsorção , Cristalização , Humanos , Limite de Detecção , Masculino , Concentração Osmolar , Porosidade , Padrões de Referência , Reprodutibilidade dos Testes , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Fatores de Tempo , Difração de Raios X
7.
J Chromatogr A ; 1626: 461333, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797819

RESUMO

The ultra-trace determination of nicotine and its 4 major metabolites (cotinine, nornicotine, norcotinine and anabasine) from rabbit plasma was achieved by a newly developed solid phase microextraction-liquid chromatography-tandem mass spectrometry method. Extraction of the target analytes was performed with hydrophilic/lipophilic balance-polyacrylonitrile SPME fibers. Dual fiber extraction was necessary to guarantee improved recovery at parts-per-trillion levels. Liquid chromatographic analysis was achieved in a 6-min run using a C18 (1.9 µm C18, 50 mm x 2.1 mm) column with a mobile phase flow rate of 0.4 mL/min. Tandem mass spectrometry was used for detection and quantification in positive electrospray ionization (ESI+) mode for all the targeted analytes. Two stable isotope-labeled internal standards were used for signal correction and accurate quantification. The mass spectrometer with laminar flow ion flux transport, guaranteed improved signal stability, minimal contamination of the ion guide and reproducibility into the first quadrupole analyzer. The method was validated in line with the Food and Drug Administration (FDA) guidelines for bioanalytical method validation. The results met the acceptance criteria as proposed by the FDA: accuracy was tested at 0.35, 10 and 75 µg L - 1 and ranged between 98.3-112.2% for nicotine, 94.1-101.9% for cotinine, 94.7-107.0% for nornicotine, 81.1-107.2% for norcotinine and 94.3-115.2% for anabasine, with precision up to 14.2%. Stability tests indicated that all the targeted analytes were stable in the desorption solution for at least 1 week. LOQs ranged from 0.05 to 1 µg L-1. The method was successfully applied to analyze plasma samples obtained from rabbits following transdermal application of a smoking cessation formulation loaded with solid lipid nanoparticles containing a nicotine-stearic acid conjugate.


Assuntos
Nicotina/sangue , Anabasina/sangue , Anabasina/isolamento & purificação , Anabasina/normas , Animais , Cromatografia Líquida de Alta Pressão/normas , Cotinina/análogos & derivados , Cotinina/sangue , Cotinina/isolamento & purificação , Cotinina/normas , Marcação por Isótopo , Limite de Detecção , Nicotina/análogos & derivados , Nicotina/isolamento & purificação , Nicotina/metabolismo , Nicotina/normas , Coelhos , Padrões de Referência , Reprodutibilidade dos Testes , Abandono do Hábito de Fumar , Microextração em Fase Sólida , Espectrometria de Massas em Tandem/normas , Fatores de Tempo
8.
J Chromatogr A ; 1628: 461428, 2020 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-32822999

RESUMO

A covalent organic framework modified graphitic carbon nitride (g-C3N4@TpBD) was synthesized by modifying the graphitic carbon nitride (g-C3N4) with a covalent organic framework (COF-TpBD). The synthesis conditions including the mass ratio between g-C3N4 and benzidine (BD), solvent type, reaction temperature and reaction time were optimized. Under the optimal synthetic conditions, a novel spiny dendritic g-C3N4@TpBD adsorbent was obtained. The g-C3N4@TpBD was then coated on stainless-steel wire by sol-gel technique and the coated fiber was used for the solid phase microextraction of polycyclic aromatic hydrocarbons prior to gas chromatography-mass spectrometric detection. The established method was successfully applied to determine eight PAHs in six environmental water samples. Under the optimal extraction conditions, a wide linear quantification range for the analytes was obtained from 0.07 to 60.0 ng mL-1 with the coefficients of determination varying from 0.9979 to 0.9998, and the limits of detection (S/N = 3) ranged from 0.02 to 0.05 ng mL-1. The relative recoveries of the analytes for the six environmental water samples at the spiked concentrations of 0.2, 0.5, 3.0 and 30.0 ng mL-1 were between 83.6% and 118% with the relative standard deviations ranging from 2.4% to 11.3%.


Assuntos
Grafite/química , Estruturas Metalorgânicas/química , Compostos de Nitrogênio/química , Hidrocarbonetos Policíclicos Aromáticos/isolamento & purificação , Microextração em Fase Sólida/métodos , Poluentes Químicos da Água/isolamento & purificação , Benzidinas/química , Limite de Detecção , Reprodutibilidade dos Testes , Temperatura
9.
J Chromatogr A ; 1626: 461386, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797858

RESUMO

In this study, the microcrystalline cellulose/metal-organic framework 199 hybrid (MCC/MOF-199) was applied as sorbent for the dispersive micro-solid phase-extraction (D-µSPE) of chlorophenols. The D-µSPE method combined with high-performance liquid chromatography- ultraviolet detection (HPLC-UV) was employed to determine of four chlorophenols including 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,3-dichlorophenol (2,3-DCP), and 2,5-dichlorophenol (2,5-DCP) in aqueous. The main parameters of the D-µSPE process that influence the extraction (i.e. the amount of sorbent, elution condition, extraction time, and pH) were investigated and optimized. Based on the outputs, the presence of MCC on the surface of MOF-199 leads to improve the properties of MOF-199 and the MCC/MOF-199 has the highest sorption capacity, durability, and porosity in comparison with MCC and MOF-199. According to the validation study at the optimized conditions, the linearity for the analytes was achieved in the range from 0.1 to 200 ng mL-1 for 2-CP and 4-CP and 0.15 to 200 ng mL-1 for 2,3-DCP and 2,5-DCP with correlation coefficients between 0.9928 and 0.9965. The limits of detection calculated at S/N=3 were in the range of 0.03-0.05 ng mL-1. Besides, the relative standard deviations (RSDs) for three spiking levels (0.2, 10,100 ng mL-1) do not exceed 6.8% and extraction recoveries are between 81.0% and 88.3%. Finally, the D-µSPE-HPLC-UV method was successfully applied to the analysis of CPs in real water samples (mineral, river and wastewater samples) with good recoveries (95.8 to 99.5%) and satisfactory precisions (RSD < 6.8%).


Assuntos
Celulose/química , Clorofenóis/análise , Estruturas Metalorgânicas/química , Microextração em Fase Sólida/métodos , Clorofenóis/química , Clorofenóis/isolamento & purificação , Cromatografia Líquida de Alta Pressão/métodos , Água Doce/análise , Concentração de Íons de Hidrogênio , Limite de Detecção , Rios/química , Espectrofotometria Ultravioleta , Águas Residuárias/análise
10.
J Chromatogr A ; 1627: 461405, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823110

RESUMO

This study focused on the measurements and validity of relative distribution constants of vaporized hydrocarbons between air and polydimethylsiloxane (PDMS) using commercially available capillary columns. Capillary column gas chromatography (CCGC) measurements, using two columns containing a PDMS stationary phase with different film thicknesses, were conducted to determine the relative distribution constants of n-heptane, toluene, n-octane, p-xylene, n-nonane, and 1,2,4-trimethylbenzene between air and PDMS at 90 and 120 °C. To validate the accuracy of the relative distribution constants via CCGC, the compositions of three headspace samples containing different amounts of hydrocarbons were calculated using the relative distribution constants via CCGC and extracted amounts via PDMS solid phase microextraction (SPME) at 90 and 120 °C. It was found that calculated hydrocarbon compositions of headspace samples were comparable to true headspace hydrocarbon compositions via direct vapor analysis, with an average absolute relative error of 3.2%. Our results indicate that CCGC is an alternative method that can provide a reliable and convenient method to determine the relative distribution constants of various hydrocarbons between air and PDMS for quantitative chemical analysis of headspace.


Assuntos
Ar , Dimetilpolisiloxanos/química , Hidrocarbonetos/análise , Cromatografia de Fase Reversa , Hidrocarbonetos/química , Microextração em Fase Sólida , Volatilização
11.
J Chromatogr A ; 1627: 461413, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823111

RESUMO

Innovations in extraction phases, extraction modes and hyphenated instrument configurations, are the most important issues to address for progress in the solid phase microextraction (SPME) methodology. In this regard, we have embarked on the development of a novel biocompatible 96-monolithic inorganic hollow fiber (96-MIHF) array as a new configuration for high-throughput SPME on a 96-well plate system. An arrangement of highly ordered 96 titania/Hydroxyapatite (TiO2/HAP) nanocomposite hollow fibers and corresponding stainless-steel needles on a Teflon plate holder were used as the extraction module. The inorganic hollow fibers were prepared via a rapid and reproducible template approach (Polypropylene hollow fiber) in combination with a sol-gel method in the presence of polyvinyl alcohol (PVA), as a network maker. The hollow fiber-shape sorbents were obtained with excellent precision by weight (RSD% = 4.98, n = 10) and length (RSD% = 1.08, n = 10) criteria. The proposed design can overcome a number of geometrically dependent drawbacks of conventional high-throughput SPME methods, mainly the ones related to sorbent amount and surface area due to possessing inner/outer surfaces without additional internal supports. The SPME platform, for the first time, was successfully applied for the extraction and preconcentration of doxorubicin from urine and water media without requiring sample preparation and free from significant matrix effect. The extracted analyte was analyzed by liquid chromatography-ion trap tandem mass spectrometry (LC-MS/MS). Highly satisfactory analytical figures of merit were obtained under optimized conditions. The limit of detection (LOD), limit of quantification (LOQ) and linearity of determination were 0.1 ng mL-1, 0.25 ng mL-1 and 0.25 to 4000 ng mL-1, respectively. The interday, intraday and inter sorbent precisions for three concentration levels ranged from 2.01 to 8.09 % (n = 3), 1.02 to 8.65 % (n = 5) and 0.99 to 1.02% (n = 15), respectively. The mean intra-well RSD value for 96 individual wells in 96-MIHF-SPME-LC-MS/MS (n = 3) at the medium concentration level was 7.81%.


Assuntos
Cromatografia Líquida/métodos , Doxorrubicina/urina , Microextração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos , Água/química , Adolescente , Adulto , Daunorrubicina/urina , Feminino , Humanos , Concentração de Íons de Hidrogênio , Limite de Detecção , Masculino , Pessoa de Meia-Idade , Concentração Osmolar , Polipropilenos/química , Porosidade , Reprodutibilidade dos Testes , Fatores de Tempo , Adulto Jovem
12.
J Chromatogr A ; 1627: 461415, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823113

RESUMO

A molecularly imprinted polymeric monolith was synthesized in an aqueous environment in 15 min via UV-irradiation. The imprinted monolith was composed of hydroxyethyl methacrylate as monomer, dimethyl amino ethyl methacrylate as functional monomer, methylene bisacrylamide and piperazine diacrylamide as crosslinkers and human serum albumin as template molecule. The synthesis took place in a PDMS-based device (2.5 cm long) yielding a micro-solid phase extraction column (3 × 5 mm) with two built-in fingertight connectors for an infusion pump and fraction collector. The imprinted monolith displayed the characteristic features of a porous polymeric monolith, had dimethyl amino ethyl methacrylate and human serum albumin as functional groups within the monolith and showed high permeability (0.51 × 10-13 m2). 85% of the imprinted cavities were readily available for rebinding of human serum albumin with an imprinting factor of 1.3. In comparison to a non-imprinted monolith, molecular imprinting increased human serum albumin adsorption by > 30%. Imprinted monolith displayed selectivity for human serum albumin over other competing proteins (human transferrin, ovalbumin and carbonic anhydrase) with similar or different isoelectric points and size. Human serum albumin was adsorbed (in dynamic mode) with > 98% selectivity from diluted human plasma using the imprinted monolith device. Device to device reproducibility and reusability of the device for 5 cycles showcase the imprinted monolith micro-device efficiency.


Assuntos
Impressão Molecular , Proteínas/isolamento & purificação , Microextração em Fase Sólida/instrumentação , Adsorção , Etilaminas/química , Humanos , Metacrilatos/química , Permeabilidade , Polímeros/química , Porosidade , Reprodutibilidade dos Testes , Albumina Sérica Humana/isolamento & purificação , Espectroscopia de Infravermelho com Transformada de Fourier
13.
J Chromatogr A ; 1626: 461360, 2020 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-32797839

RESUMO

Conjugated microporous polymers (CMPs) with uniform morphology have shown fascinating application in the separation science. In this study, metal-free Knoevenagel condensation was adopted to prepare spherical sp2 carbon-conjugated microporous polymers, which used tetrakis(4-formylphenyl)methane and 1,4-phenylenediacetonitrile as monomers. Due to the remarkable extraction capability for carbamate pesticides (CPs), the as-synthesized CMPs were fabricated as the coating for solid-phase microextraction (SPME). After optimized SPME parameters (adsorption time, salt concentration, sample pH, adsorption temperature, desorption time, desorption solvent and desorption volume), ten CPs in water samples were quantified by ultrahigh performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS). Linearity in the range 0.005-100 ng mL-1 with low detection limits of 0.00060-0.017 ng mL-1 was obtained. The intra-day and inter-day precisions expressed as relative standard deviations were 1.5-8.1% and 1.1-8.0%, respectively. Fiber-to-fiber reproducibility was below 7.3%. The CMPs-SPME-UPLC-MS/MS method was applied to detect trace CPs in real water samples with relative recoveries from 91.8% to 108%.


Assuntos
Carbamatos/análise , Microextração em Fase Sólida/métodos , Poluentes Químicos da Água/análise , Adsorção , Carbamatos/isolamento & purificação , Cromatografia Líquida de Alta Pressão , Praguicidas/análise , Praguicidas/isolamento & purificação , Polímeros/química , Porosidade , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/isolamento & purificação
14.
PLoS One ; 15(8): e0237881, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32817641

RESUMO

At present, the identification of honeysuckle aroma depends on experienced tasters, which results in inconsistencies due to human error. The key odorants have the potential to distinguish the different species and evaluate the quality of honeysuckle. Hence, in this study, a more scientific approach was applied to distinguish various honeysuckles. The volatile compounds of different species and parts of honeysuckle were separately extracted by headspace-solid phase microextraction (HS-SPME) and solvent assisted flavor evaporation (SAFE). Compounds with greater volatility such as aldehydes, limonene, γ-terpinene, and terpinolene were preferentially extracted by HS-SPME. As a complementary extraction method to HS-SPME, SAFE was found to recover comparatively more polar compounds such as eugenol, decanoic acid, and vanillin. Subsequently, key odorants with the highest flavour dilution (FD) factors were detected by aroma extract dilution analysis (AEDA). These were benzaldehyde, 4-ethylphenol, decanoic acid, vanillin, 3-methyl-2-butenal, and ß-ionone in honeysuckle flowers and γ-octalactone, 4-ethyl phenol, and vanillin in honeysuckle stem. Finally, principal component analysis (PCA) was conducted to analyze not only the key odorants of species and parts of honeysuckle but also their different origins. The results of PCA suggested that the species of honeysuckle contributed much more to variations in aroma rather than their origins. In conclusion, the application of the key odorants combined with PCA was demonstrated as a valid approach to differentiate species, origins, and parts of honeysuckle.


Assuntos
Lonicera/química , Odorantes/análise , Olfatometria/métodos , Microextração em Fase Sólida/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Lonicera/classificação , Lonicera/metabolismo , Solventes/química
16.
Sci Total Environ ; 747: 140966, 2020 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-32768766

RESUMO

Analytical performance and optimization of figures of merit of a portable nano liquid chromatograph (NanoLC) with UV detection at 255 nm have been established for in place analysis. Methylxanthines: caffeine, theophylline and theobromine were selected as target analytes. A fast lab method based on IT-SPME coupled on line with capillary liquid chromatograph (CapLC) with diode array detection (DAD) was employed for comparative studies. IT-SPME and solid phase extraction were coupled off-line to NanoLC for improving instrumental parameters, mainly detection capacity and selectivity. IT-SPME or SPE/portable NanoLC based methods were superior in terms of chromatographic resolution and organic solvent consumption per sample, around 200 µL vs 10 mL for IT-SPME-CapLC-DAD. Limits of detection (LODs) obtained with the SPE/portable NanoLC were 2-10 ng/mL, which can be suitable for testing the presence of the analytes in several environmental waters in the field. As predictable, the lab method provided better LODs, between 0.1 and 0.5 ng/mL. Good linearity was achieved for both methods and precision was similar for them (≤7%). Both systems were tested for the analysis of real water samples with suitable results.


Assuntos
Microextração em Fase Sólida , Poluentes Químicos da Água , Cafeína , Cromatografia Líquida de Alta Pressão , Cromatografia Líquida , Limite de Detecção , Teofilina , Poluentes Químicos da Água/análise
17.
J Chromatogr A ; 1627: 461400, 2020 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-32823105

RESUMO

In this work, a single cross-linking functional monomer, 2,5-divinylterephthalaldehyde, was designed and synthesized to simplify the preparation of molecularly imprinted polymers (MIPs). In the presence of estradiol as a template, MIPs were successfully prepared using 2,5-divinylterephthalaldehyde along with a solvent and initiator. This method reduced most of the complex variables encountered in the traditional synthesis. Characterization of the morphology and structure of the MIPs was performed by scanning electron microscopy, Fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis. Compared with non-imprinted polymers, the MIPs had higher adsorption capacities for five estrogens with imprinting factors above 2.9. The MIPs had high extraction efficiencies, good functional properties, long lifetimes, and good reproducibility, which made them suitable for solid-phase microextraction (SPME). Coupled with ultra-high performance liquid chromatography tandem mass spectrometry, the MIP-based fibers were applied to SPME for the analysis of five estrogens in milk samples. Under the best conditions, the established method had a wide linear range (0.5-10000 ng kg-1), low limits of detection (0.08-0.26 ng kg-1) and quantification (0.26-0.87 ng kg-1), good precision (3.2-8.1%, n = 6), and fiber-to-fiber reproducibility (4.3%-8.8%, n = 3). The MIPs-based fibers can be reused at least 60 times without apparent loss of extraction efficiency. Finally, this method was applied to the determination of target estrogens in milk samples with satisfactory relative recoveries (84.3%-105%, relative standard deviation ≤ 7.8%).


Assuntos
Estrogênios/isolamento & purificação , Leite/química , Impressão Molecular , Polímeros/química , Microextração em Fase Sólida/métodos , Adsorção , Animais , Cromatografia Líquida de Alta Pressão , Estradiol/análise , Estrogênios/análise , Limite de Detecção , Reprodutibilidade dos Testes , Solventes/química , Espectrometria de Massas em Tandem
18.
J Chromatogr A ; 1628: 461486, 2020 Sep 27.
Artigo em Inglês | MEDLINE | ID: mdl-32822970

RESUMO

In this work, an inexpensive, fast, and selective ionic liquid modified graphene oxide (GO-IL) was synthesized and electrochemically deposited on the inner surface of a stainless-steel tube. Then, it was applied for circulated headspace in-tube solid-phase microextraction (CHS-IT-SPME) of naphthalene from honey samples. Next, the coated tube was replaced with the sample loop of a six-port injection valve for on-line desorption and further HPLC-UV analysis of naphthalene. The sorbent was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FT-IR), and energy-dispersive X-ray spectroscopy (EDX). Different parameters affecting the procedure efficiency, including extraction temperature, extraction time, salt concentration, and sample volume were optimized by central composite design and response surface methodology. Under the optimum conditions, the calibration curve was linear within the range of 0.3-200 ng mL-1, with a regression coefficient of 0.9972. The limits of detection (LOD) and quantification (LOQ) were found to be 0.1 ng mL-1 and 0.3 ng mL-1, respectively. Intra-day and inter-day RSDs% for three replicate measurements of naphthalene at the concentration of 10 ng mL-1 were obtained 3.9% and 5.0%, respectively. Also, good tube-to-tube reproducibility of 5.3% was achieved. Finally, the method was successfully applied for measuring trace amounts of naphthalene in honey samples. Relative recoveries were calculated within the range of 90.0-106.5%, indicating excellent efficiency of the proposed method.


Assuntos
Cromatografia Líquida/métodos , Galvanoplastia/métodos , Grafite/química , Mel/análise , Líquidos Iônicos/química , Naftalenos/isolamento & purificação , Sistemas On-Line , Microextração em Fase Sólida/métodos , Cromatografia Líquida de Alta Pressão , Limite de Detecção , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Reprodutibilidade dos Testes
19.
J Chromatogr A ; 1629: 461501, 2020 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-32841768

RESUMO

Metabolic stability tests are one of the fundamental steps at the preclinical stages of new drug development. Microsomes, used as a typical enzymatic model of liver biotransformation, can be a challenging matrix for analytical scientists due to a high concentration of cellular proteins and membrane lipids. In the work, we propose a new procedure integrating biotransformation reaction with SPME-like protocol for sample clean-up. It is beneficial to increase the overall quality of results in contrary to the typical protein precipitation approach. A set of ten arylpiperazine analogs, six of which are considered promising drug candidates (and four are accepted drugs) were used as a probe to assess the goodness of the newly proposed approach. In order to promote an efficient extraction protocol, a new, miniaturized shape of a sorbent, suitable to perform the extraction in 100 µL of the sample has been designed. Termination of the biotransformation process by protein denaturation with hot water was additionally evaluated. A quantitative structure-property relationship (QSPR) study using Orthogonal Partial Least Squares (OPLS) technique to reveal insights to the sorption mechanism was also performed. The obtained results showed the new 3D-printed sorbent can be an attractive basis for the new sample preparation approach for metabolic stability studies and an alternative for commercially available protocols based on solid-phase microextraction (SPME) or solid-phase extraction (SPE) principles.


Assuntos
Preparações Farmacêuticas/química , Impressão Tridimensional , Adsorção , Análise dos Mínimos Quadrados , Preparações Farmacêuticas/isolamento & purificação , Relação Quantitativa Estrutura-Atividade , Microextração em Fase Sólida
20.
J Chromatogr A ; 1629: 461508, 2020 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-32858453

RESUMO

In the present document, we report the development of an analytical method consisting of a sequential direct-immersion/headspace solid-phase microextraction (DI-HS-SPME) followed by gas-phase chromatography and tandem mass spectrometry (GC-MS/MS) for simultaneous analysis of 4-chlorobenzyl alcohol, 2,6-dichlorobenzyl alcohol, 4-methoxybenzyl alcohol, 3,4-dimethoxybenzyl alcohol, pyridine, and 2,3-dimethylpyrazine in oilfield production waters. These compounds are under evaluation for use as phase-partitioning tracers in oil reservoirs. To the best of our knowledge, this is the first time SPME has been applied to the analysis of these compounds in production waters, or any other type of matrix where the compounds targeted are the base for a technical application. Relevant extraction parameters, such as the adsorbent phase of the fiber, direct immersion or headspace, addition of salt, temperature and time of extraction were investigated. The final optimal operation conditions consist on extracting 5 mL of sample at pH 9.0 with 1.8 g of NaCl with constant stirring during 5 minutes of DI-SPME followed by 15 minutes of HS-SPME at 70 °C using a DVB/CAR/PDMS (50/30 µm) fiber. The limits of quantification (LOQ), linearity, precision and accuracy of the method were evaluated. Analyses of the tracer compounds and recovery studies were also performed on production waters from 8 different oilfields of the Norwegian continental shelf. LOQs between 0.080 and 0.35 µg L-1 were obtained. The recovery yields of the method were consistently higher than 85% and RSDs less than 13%. None of the tracer compounds was found in the real samples processed, which is consistent with one of the requirements for an artificial tracer in an oilfield: absence or constant and low background in the traced fluid. The performance of the method developed, combined with its easiness to automate, introduce a new, accurate and cost-efficient technique to process the hundreds of samples required by an inter-well tracer test.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Campos de Petróleo e Gás/química , Álcoois/análise , Álcoois/química , Álcoois/isolamento & purificação , Limite de Detecção , Pirazinas/análise , Pirazinas/química , Pirazinas/isolamento & purificação , Microextração em Fase Sólida , Temperatura
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