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1.
Food Chem ; 315: 126158, 2020 Jun 15.
Artículo en Inglés | MEDLINE | ID: mdl-32014672

RESUMEN

Rapid, nondestructive, high-throughput testing and screening of volatile ingredients plays an important role in food flavor analysis. Gas chromatography-ion mobility spectrometry (GC-IMS) is a powerful technique for the separation and sensitive detection of volatile organic compounds. It has a fast response, high sensitivity, easy operation, and low cost. In this article, a brief introduction to the working principle of GC-IMS is presented. A summary of recent studies of different food flavor analysis applications is also provided, including food classification and adulteration, the evaluation of food freshness and spoilage, off-flavor detection, monitoring the processing of food products, and evaluation of aroma changes during food storage. Finally, future directions of GC-IMS are proposed.


Asunto(s)
Cromatografía de Gases/métodos , Análisis de los Alimentos/métodos , Espectrometría de Movilidad Iónica/métodos , Odorantes/análisis , Cromatografía de Gases/estadística & datos numéricos , Aromatizantes/análisis , Aditivos Alimentarios/análisis , Análisis de los Alimentos/estadística & datos numéricos , Espectrometría de Movilidad Iónica/estadística & datos numéricos , Control de Calidad , Gusto , Compuestos Orgánicos Volátiles/análisis
2.
Food Chem ; 275: 143-153, 2019 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-30724180

RESUMEN

The ester aroma profiles of five Chinese cherry wines and the perceptual interaction among esters were investigated in this study. 24 esters were identified by Gas chromatography-olfactometry (GC-O) and Gas Chromatography-Mass Spectrometer (GC-MS). According to addition/omission analysis, seven volatile compounds among them were selected and studied using sensory profiling and multivariate statistic methods such as Principal Component Analysis (PCA). In sensory analysis, a significant reduction of olfactory threshold for total aromatic reconstitution was induced by the addition among each of them in Feller's additive model, which demonstrated their synergistic effects. The σ/τ plot showed that most of them were followed by a partial addition behavior. Furthermore, PCA indicated that the addition among each of them had a significant effect on fruity, floral, sweet and fermentation aroma intensity. Specifically, ethyl decanoate and methyl salicylate at sub-threshold concentrations were also likely to contribute to overall aroma. The results of perceptual interaction were mainly influenced by chemical structure and molecular polarity.


Asunto(s)
Odorantes/análisis , Prunus , Gusto , Vino/análisis , Adulto , Cromatografía de Gases/métodos , Cromatografía de Gases/estadística & datos numéricos , Ésteres/análisis , Femenino , Fermentación , Análisis de los Alimentos/métodos , Análisis de los Alimentos/estadística & datos numéricos , Cromatografía de Gases y Espectrometría de Masas/métodos , Humanos , Masculino , Análisis de Componente Principal , Prunus/química , Compuestos Orgánicos Volátiles/análisis
3.
Forensic Sci Int ; 295: 213-218, 2019 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-30611561

RESUMEN

BACKGROUND: Inter-laboratory proficiency schemes are widely used to control the performance of clinical and forensic toxicology laboratories. In 2016 the Laboratory of Environmental Hygiene and Forensic Toxicology - Venice (Italy) initiated an inter-laboratory proficiency test of blood-alcohol analysis. The number of participating laboratories gradually increased from 26 to 36. Furthermore, a few clinical laboratories were included if gas chromatographic (GC) methods were used for blood alcohol analysis. PROCEDURE: Whole blood was obtained from the Blood Transfusion Centre of the Venice Hospital and a mixture of sodium fluoride and potassium oxalate was added as a preservative and anticoagulant, respectively. Aliquots of the blood were spiked with certified pure ethanol to obtain target blood-alcohol concentrations (BACs) ranging from 0 to 5.0g/L. Two blood samples (4mL each) were included in each shipment to the participating laboratories. The laboratories were asked to provide information about number of replicate BAC determinations they made, the types of ethanol reference standards used, and inherent measurement uncertainty. The aim of the testing was to obtain a mean consensus value for the target BAC and to assess inter-laboratory imprecision. All procedures for registration and submission of results were done on-line. A confidential report and statistical evaluations were returned to the participants one week later. ANALYTICAL METHODS: All participants used head-space GC (HS-GC) for the analysis of ethanol in blood. More than 85% of participants used HS-GC with flame-ionization detection, whereas the others used mass spectrometry (MS) as a detector. More than 40% of the participating laboratories kept the blood samples frozen (-20°C) prior to analysis, whereas the others used refrigeration (+4°C). The preliminary validation tests showed that there were no statistically significant differences between BAC in frozen or refrigerated samples for a period of 20 days. RESULTS AND CONCLUSION: The statistical evaluation of results was done using an iterative procedure known as Algorithm A (ISO 13528:2015, C.3.1). This provides robust estimates for mean and standard deviation between laboratories and these were used as consensus values. More than 85% of participants provided satisfactory results (z-score <1) and 94% of laboratories were within z-score <2, based on five control samples. When a blood sample without any alcohol (blank) was sent for analysis, laboratories reported this as zero, 0.00g/L, below limit of detection (LOD) or not detected. Some type of consensus should be reached for reporting blank samples.


Asunto(s)
Nivel de Alcohol en Sangre , Laboratorios/normas , Detección de Abuso de Sustancias/normas , Cromatografía de Gases/métodos , Cromatografía de Gases/estadística & datos numéricos , Frío , Toxicología Forense/normas , Toxicología Forense/estadística & datos numéricos , Humanos , Italia , Laboratorios/estadística & datos numéricos , Espectrometría de Masas/estadística & datos numéricos , Manejo de Especímenes/métodos , Manejo de Especímenes/estadística & datos numéricos
4.
J Chromatogr A ; 1586: 101-105, 2019 Feb 08.
Artículo en Inglés | MEDLINE | ID: mdl-30578027

RESUMEN

Orthogonality can be used as a selection parameter for two-dimensional chromatography column selection (e.g. in GC × GC or LC × LC) or for method optimization purposes, both aiming for maximal orthogonality for a particular analytical application. In order to improve the concurrence of two-dimensional chromatography expert's orthogonality grading, two orthogonality metrics, %FIT and %BIN, were developed, evaluated and compared with the Asterisks orthogonality metric. The %BIN is a bin counting approach where the number of bins is fixed at 25 and deviations from the expected average number of peaks per bin is used as the basis for the orthogonality calculation. The %FIT is based on fitting polynomials of degree two, through the xy and the yx data and calculating the average minimal distance and standard deviation of all data points above and below the fitted polynomials. The orthogonality metrics were evaluated by using 14 different types of computer generated xy datasets and two measured LC × LC datasets. Both %FIT and %BIN, were shown to have a larger discriminative power than the Asterisks equations, and are in good agreement with the orthogonality scores for 2D-chromatograms provided by nine experts.


Asunto(s)
Algoritmos , Técnicas de Química Analítica/métodos , Cromatografía de Gases/estadística & datos numéricos , Cromatografía Liquida/estadística & datos numéricos , Cromatografía de Gases/métodos , Cromatografía Liquida/métodos , Teoría de la Información
5.
J Wound Ostomy Continence Nurs ; 44(3): 269-276, 2017.
Artículo en Inglés | MEDLINE | ID: mdl-28328644

RESUMEN

PURPOSE: The purpose of this study was to identify key odorants in used disposable absorbent incontinence products. DESIGN: Descriptive in vitro study SUBJECTS AND SETTING:: Samples of used incontinence products were collected from 8 residents with urinary incontinence living in geriatric nursing homes in the Gothenburg area of Sweden. Products were chosen from a larger set of products that had previously been characterized by descriptive odor analysis. METHODS: Pieces of the used incontinence products were cut from the wet area, placed in glass bottles, and kept frozen until dynamic headspace sampling of volatile compounds was completed. Gas chromatography-olfactometry was used to identify which compounds contributed most to the odors in the samples. Compounds were identified by gas chromatography-mass spectrometry. RESULTS: Twenty-eight volatiles were found to be key odorants in the used incontinence products. Twenty-six were successfully identified. They belonged to the following classes of chemical compounds: aldehydes (6); amines (1); aromatics (3); isothiocyanates (1); heterocyclics (2); ketones (6); sulfur compounds (6); and terpenes (1). CONCLUSION: Nine of the 28 key odorants were considered to be of particular importance to the odor of the used incontinence products: 3-methylbutanal, trimethylamine, cresol, guaiacol, 4,5-dimethylthiazole-S-oxide, diacetyl, dimethyl trisulfide, 5-methylthio-4-penten-2-ol, and an unidentified compound.


Asunto(s)
Pañales para la Incontinencia/normas , Odorantes/análisis , Orina/química , Almohadillas Absorbentes/efectos adversos , Almohadillas Absorbentes/normas , Anciano , Anciano de 80 o más Años , Cromatografía de Gases/métodos , Cromatografía de Gases/estadística & datos numéricos , Femenino , Humanos , Pañales para la Incontinencia/efectos adversos , Masculino , Persona de Mediana Edad , Olfatometría/métodos , Olfatometría/estadística & datos numéricos , Suecia , Incontinencia Urinaria/enfermería
6.
J Chromatogr A ; 1449: 89-99, 2016 Jun 03.
Artículo en Inglés | MEDLINE | ID: mdl-27139215

RESUMEN

Chromatographic background drift correction, which influences peak detection and time shift alignment results, is a critical stage in chromatographic data analysis. In this study, an automatic background drift correction methodology was developed. Local minimum values in a chromatogram were initially detected and organized as a new baseline vector. Iterative optimization was then employed to recognize outliers, which belong to the chromatographic peaks, in this vector, and update the outliers in the baseline until convergence. The optimized baseline vector was finally expanded into the original chromatogram, and linear interpolation was employed to estimate background drift in the chromatogram. The principle underlying the proposed method was confirmed using a complex gas chromatographic dataset. Finally, the proposed approach was applied to eliminate background drift in liquid chromatography quadrupole time-of-flight samples used in the metabolic study of Escherichia coli samples. The proposed method was comparable with three classical techniques: morphological weighted penalized least squares, moving window minimum value strategy and background drift correction by orthogonal subspace projection. The proposed method allows almost automatic implementation of background drift correction, which is convenient for practical use.


Asunto(s)
Cromatografía de Gases/estadística & datos numéricos , Cromatografía de Gases/métodos , Escherichia coli/metabolismo , Análisis de los Mínimos Cuadrados , Metaboloma
7.
J Anal Toxicol ; 35(7): 402-10, 2011 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-21871148

RESUMEN

An estimate was made of the measurement uncertainty for blood ethanol testing by headspace gas chromatography. While uncertainty often focuses on compliance to a single threshold level (0.08 g/100 mL), the existence of multiple thresholds, related to enhanced sentencing, subject age, or commercial vehicle licensure, necessitate the use of an estimate with validity across multiple specification levels. The uncertainty sources, in order of decreasing magnitude, were method reproducibility, linear calibration, recovery, calibrator preparation, reference material, and sample preparation. A large set of reproducibility data was evaluated (n = 15,433) in order to encompass measurement variability across multiple conditions, operators, instruments, concentrations and timeframes. The relative, combined standard uncertainty was calculated as ±2.7%, with an expanded uncertainty of ±8.2% (99.7% level of confidence, k = 3). Bias was separately evaluated through a recovery study using standard reference material from a national metrology institute. The uncertainty estimate was verified through the use of proficiency test (PT) results. Assigned values for PT results and their associated uncertainties were calculated as robust means (x*) and standard deviations (s*) of participant values. Performance scores demonstrated that the uncertainty estimate was appropriate across the full range of PT concentrations (0.010-0.370 g/100 mL). The use of PT data as an empirical estimate of uncertainty was not examined. Until providers of blood ethanol PT samples include details on how an assigned value is obtained along with its uncertainty and traceability, the use of PT data should be restricted to the role of verification of uncertainty estimates.


Asunto(s)
Cromatografía de Gases/métodos , Cromatografía de Gases/estadística & datos numéricos , Etanol/sangre , Toxicología Forense/métodos , Toxicología Forense/estadística & datos numéricos , Calibración , Cromatografía de Gases/instrumentación , Interpretación Estadística de Datos , Toxicología Forense/instrumentación , Humanos , Cómputos Matemáticos , Estándares de Referencia , Reproducibilidad de los Resultados , Incertidumbre
8.
J AOAC Int ; 94(1): 232-42, 2011.
Artículo en Inglés | MEDLINE | ID: mdl-21391500

RESUMEN

A gas chromatograph with electron capture detection method for estimation of selected metabolites--amino acids (free and bound), gamma-aminobutyric acid (GABA), salicylic acid (SA), and acetyl salicylic acid (ASA) from tomato--is reported. The method is based on nitrophenylation of the metabolites by 1-fluoro-2, 4-dinitrobenzene under aqueous alkaline conditions to form dinitophenyl derivatives. The derivatives were stable under the operating conditions of GC. Analysis of bound amino acids comprised perchloric acid precipitation of protein, alkylation (carboxymethylation) with iodoacetic acid, vapor-phase hydrolysis, and derivatization with 1-fluoro-2,4-dinitrobenzene in that order. The metabolites were resolved in 35 min, using a temperature-programmed run. The method is rapid, sensitive, and precise. It easily measured the typical amino acids (aspartate, asparagine, glutamate, glutamine, alanine, leucine, lysine, and phenylalanine) used for identification and quantification of a protein, resolved amino acids of the same mass (leucine and isoleucine), satisfactorily measured sulfur amino acid (methionine, cystine, and cysteine), and quantified GABA, SA, and ASA, as well. The developed method was validated for specificity, linearity, and precision. It has been applied and recommended for estimation of 25 metabolites from Solanum lycopersicum (L.).


Asunto(s)
Cromatografía de Gases/métodos , Análisis de los Alimentos/métodos , Solanum lycopersicum/química , Aminoácidos/análisis , Aspirina/análisis , Cromatografía de Gases/estadística & datos numéricos , Análisis de los Alimentos/estadística & datos numéricos , Frutas/química , Hidrólisis , Solanum lycopersicum/metabolismo , Hojas de la Planta/química , Proteínas de Vegetales Comestibles/química , Ácido Salicílico/análisis , Ácido gamma-Aminobutírico/análisis
9.
J Clin Periodontol ; 36(11): 964-9, 2009 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-19843192

RESUMEN

AIM: Measurement of volatile sulphur compounds (VSC) by portable sulphur monitors (Halimeter, OralChroma) is a common practice for diagnosis of oral malodour. In this study, the clinical value of these devices was examined. MATERIALS AND METHODS: Two hundred and eighty patients with bad breath complaints attending a halitosis consultation were enrolled. Organoleptic scores were given by a trained and calibrated judge, before measurement of the VSC levels (Halimeter, OralChroma), to avoid any bias. RESULTS: Significant correlations were found between the organoleptic assessment, the Halimeter, and the OralChroma (R=0.74 for organoleptic versus Halimeter; 0.66 for organoleptic versus OralChroma; 0.63 for Halimeterversus OralChroma). The sensitivity and specificity (with regard to the organoleptic score) to detect patients with/without oral malodour for the Halimeter were 63% and 98%, respectively, and for the OralChroma 69% and 100% when using the cutoffs suggested by the manufacturer. By lowering these values, sensitivity could be improved without a significant decrease in specificity (both devices). CONCLUSIONS: We concluded that the measurement of the VSC levels can be used as an adjunct to the organoleptic assessment. Thresholds should be revisited in order to improve their clinical utility. These devices can prove the absence of malodour in case of pseudo-halitosis.


Asunto(s)
Pruebas Respiratorias/instrumentación , Halitosis/diagnóstico , Compuestos de Azufre/análisis , Adulto , Cromatografía de Gases/instrumentación , Cromatografía de Gases/estadística & datos numéricos , Femenino , Humanos , Sulfuro de Hidrógeno/análisis , Masculino , Índice de Higiene Oral , Índice Periodontal , Reproducibilidad de los Resultados , Sensibilidad y Especificidad , Olfato/fisiología , Compuestos de Sulfhidrilo/análisis , Lengua/patología , Compuestos Orgánicos Volátiles/análisis , Xerostomía/clasificación
10.
J Chromatogr A ; 1216(27): 5302-12, 2009 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-19486989

RESUMEN

Quantitative structure-retention relationships (QSRR) models were built for a data set consisting of 96 essential oils and used to predict their gas chromatographic (GC) retention times (t(R)). Multiple linear regression (MLR), principal component regression (PCR), and partial least squares (PLS) have been applied to build different QSRR models by using 13 nonzero E-state indexes and 56 descriptors calculated from TSAR software. The three chemometric methods (MLR, PCR, and PLS) for evaluation of GC t(R) values of essential oils have been compared. The best model based on the whole data set derived from MLR model (model M2) appears to be the best predictive power (r(2)=0.9689 and q(2)=0.9631) for this data set. The whole data set was splitted into a training set consisting of 72 compounds and a test set consisting of 24 compounds. The model based on the training set derived from MLR offered the highest r(2) of 0.9756 and q(2) of 0.9693. The best model base on the training set obtained from PLS not only showed a good internal predictive power (r(2)=0.9703 and q(2)=0.9633) but also offered the highest external predictive power (R(2)=0.9588 and q(2)(ext)=0.9572). The results showed that two E-state indexes (sssCH and sOH) and five molecular connective indices ((1)chi(B), (2)chi(p), (3)chi(C), (4)chi(C), and (6)chi(p)) closely relate to the GC t(R) values of essential oils. The applicability domain of the QSRR models were defined by control leverage values (h*) and the models can be used to predict the unknown compounds falling in this domain.


Asunto(s)
Cromatografía de Gases/instrumentación , Cromatografía de Gases/estadística & datos numéricos , Modelos Estadísticos , Aceites Volátiles/química , Análisis de los Mínimos Cuadrados , Modelos Lineales , Modelos Químicos , Análisis de Componente Principal
11.
J Hazard Mater ; 166(2-3): 853-9, 2009 Jul 30.
Artículo en Inglés | MEDLINE | ID: mdl-19144466

RESUMEN

The quantitative structure-retention relationship (QSRR) of the essential oil components against the gas chromatography retention index (RI) was studied. The genetic algorithm (GA) was employed to select the variables that resulted in the best-fitted models. After the variables were selected, the linear multivariate regressions [e.g. the multiple linear regression (MLR), the partial least squares (PLS)] as well as the nonlinear regressions [e.g. the polynomial PLS (poly-PLS), the support vector machine (SVM)] were utilized to construct the linear and nonlinear QSRR models. The obtained results using SVM were compared with those of MLR, PLS and poly-PLS, exhibiting that the SVM model demonstrated a better performance than that of the other models. The relative standard error SE (%) of the training set and the test set for the SVM model was 1.96 and 4.25, and the square correlation coefficients were 0.987 and 0.962 respectively, while the square correlation coefficient of the cross validation (Q(2)) on the SVM model was 0.963, revealing the reliability of this model. The resulting data indicated that SVM could be used as a powerful modeling tool for the QSRR studies. This is the first research on the QSRR of the essential oil compounds against the retention index using the SVM.


Asunto(s)
Inteligencia Artificial , Cromatografía de Gases/métodos , Aceites Volátiles/aislamiento & purificación , Algoritmos , Cromatografía de Gases/estadística & datos numéricos , Modelos Lineales
12.
J Chromatogr A ; 1216(14): 2866-72, 2009 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-18834592

RESUMEN

Comprehensive two-dimensional gas chromatography (GC x GC) is now recognized as the preferred technique for the detailed analysis and characterization of complex mixtures of volatile compounds. However, for comparison purposes, taking into account all the information contained in the chromatogram is far from trivial. In this paper, it is shown that the combination of peak alignment by dynamic time warping and multivariate analysis facilitated the comparison of complex chromatograms of tobacco extracts. The comparison is shown to be efficient enough to provide a clear discrimination among three types of tobacco. A tentative interpretation of loadings is presented in order to give access to the compounds which differ from one sample to another. Once located, mass spectrometry was used to identify markers of tobacco type.


Asunto(s)
Cromatografía de Gases/estadística & datos numéricos , Cómputos Matemáticos , Nicotiana/química , Extractos Vegetales/química , Algoritmos , Análisis Multivariante
13.
J Chromatogr A ; 1216(14): 2923-7, 2009 Apr 03.
Artículo en Inglés | MEDLINE | ID: mdl-19054522

RESUMEN

User-friendly and easy-to-use laboratory-written programs for visualisation and interpretation of comprehensive two-dimensional chromatographic data were developed. The programs that are not tied to any particular commercial instrument, and data obtained either by comprehensive two-dimensional liquid (LC x LC) or gas (GC x GC) chromatography can be analysed. Operations of the programs allow visualisation of 2D and 3D plots, comparison of two 2D plots at a time, as well as determination of retention times and peak heights and volumes.


Asunto(s)
Cromatografía de Gases/estadística & datos numéricos , Cromatografía Liquida/estadística & datos numéricos , Programas Informáticos , Estadística como Asunto/métodos
14.
RBCF, Rev. bras. ciênc. farm. (Impr.) ; 44(4): 773-781, out.-dez. 2008. graf, tab
Artículo en Portugués | LILACS | ID: lil-507928

RESUMEN

O caju (Anacardium occidentale L.) apresenta substâncias fenólicas, as quais são atribuídas propriedades antioxidantes. Sendo assim, o presente trabalho objetivou verificar a capacidade antioxidante em subproduto, ou seja, no bagaço do pedúnculo do caju. O potencial antioxidante do extrato hidroalcoólico (EHAlc) do bagaço do pedúnculo de caju foi avaliado em sistema de varredura do radical 2,2'-difenil-1-picrilhidrazilo (DPPHò) e em ensaio in vivo. No sistema DPPH, o extrato demonstrou atividade antioxidante de cerca de 95% em sua maior concentração (1000 µg/mL). Para o estudo in vivo, foram utilizados ratos Wistar administrando oralmente EHAlc (200 e 400 mg/kg de peso corpóreo) por 30 dias e analisados os tecidos plasmático, hepático e cerebral. Não houve alterações na peroxidação lipídica no plasma e no fígado dos animais tratados comparados ao grupo controle. Contudo, foi observada redução da lipoperoxidação no cérebro dos grupos tratados. Além do mais, neste tecido, os animais tratados apresentaram maior quantidade de ácidos graxos poliinsaturados (AGPI), destacando-se o ácido docosahexaenóico (DHA). Estes resultados indicam que o EHAlc contém antioxidantes naturais efetivos e que podem contribuir na redução da lipoperoxidação e preservação dos AGPICL no tecido cerebral de ratos, dando indícios da capacidade antioxidante do bagaço do pedúnculo de caju CCP-76.


The cashew apple (Anacardium occidentale L.) contains phenolic compounds usually related with antioxidant properties. Then, the aim of this study was to investigate its antioxidant capacity. The antioxidant capacity of the hydroalcoholic extract of the cashew apple pulp (EHAlc.) was assessed for the scavenging of the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) by in vitro method and by an in vivo essay. For this essay a 30-day oral (gavage, EHAlc. 200 and 400 mg/kg) study was conducted in Wistar male rats, evaluating hepatic, plasma and brain tissues. In DPPH model, the extract demonstrated antioxidant activity of 95% (largest concentration, 1000 µg/ mL). There were found no relevant peroxidation comparing the treated animals with the control group. However, the treated group presented a lower level of brain lipoperoxidation. Also in the treated animals brain tissue was found the largest amount of polyunsaturated fatty acids (PUFA), mainly docosahexaenoic (DHA). Therefore, the analyzed extract from cashew apple pulp clone CCP-76 contains effective natural antioxidants, responsible for free radical scavenging in vitro and also for decreasing the brain lipoperoxidation and keeping the PUFAS levels in Wistar rats.


Asunto(s)
Animales , Masculino , Ratas , Anacardium/análisis , Antioxidantes/farmacología , Cromatografía de Gases/estadística & datos numéricos , Fenómenos Químicos , Radicales Libres
15.
J Sep Sci ; 31(13): 2434-43, 2008 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-18646271

RESUMEN

In the present study, Lu index and distance-based atom type topological index (DAI) previously developed in our team, were introduced and combined with molecular electronegativity chi ep to characterize quantitative structure-property relationship of GC relative retention time (RRT) for several types of structurally diverse organic pesticides on the four kinds of chromatographic columns. Using multiple linear regression technique, four several-variable models are obtained with the estimations correlation coefficient (R(2)) being between 0.9655 and 0.9285, and the correlation coefficient (R(2)cv) in the leave-one-out cross-validation procedure are between 0.9560 and 0.9143, respectively. The results in this study indicate that the three topological indices Lu index, DAI, and molecular electronegativity chi ep can predict the gas chromatographic RRT of organic pesticides with diverse hetero-atoms.


Asunto(s)
Cromatografía de Gases/métodos , Plaguicidas/aislamiento & purificación , Cromatografía de Gases/estadística & datos numéricos , Electroquímica , Contaminantes Ambientales/análisis , Modelos Lineales , Estructura Molecular , Plaguicidas/análisis , Plaguicidas/química , Análisis de Regresión
16.
J Sep Sci ; 31(13): 2444-50, 2008 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-18646272

RESUMEN

The presence of cocaine on US paper currency has been known for a long time. Banknotes become contaminated during the exchange, storage, and abuse of cocaine. The analysis of cocaine on various denominations of US banknotes in the general circulation can provide law enforcement circles and forensic epidemiologists objective and timely information on epidemiology of illicit drug use and on how to differentiate money contaminated in the general circulation from banknotes used in drug transaction. A simple, nondestructive, and accurate capillary gas chromatographic method has been developed for the determination of cocaine on various denominations of US banknotes in this study. The method comprises a fast ultrasonic extraction using water as a solvent followed by a SPE cleanup process with a C(18) cartridge and capillary GC separation, identification, and quantification. This nondestructive analytical method has been successfully applied to determine the cocaine contamination in US paper currency of all denominations. Standard calibration curve was linear over the concentration range from the LOQ (2.00 ng/mL) to 100 microg/mL and the RSD less than 2.0%. Cocaine was detected in 67% of the circulated banknotes collected in Southeastern Massachusetts in amounts ranging from approximately 2 ng to 49.4 microg per note. On average, $5, 10, 20, and 50 denominations contain higher amounts of cocaine than $1 and 100 denominations of US banknotes.


Asunto(s)
Cromatografía de Gases/métodos , Cocaína/análisis , Drogas Ilícitas/análisis , Papel , Cromatografía de Gases/normas , Cromatografía de Gases/estadística & datos numéricos , Cocaína/normas , Espectrometría de Masas/métodos , Estándares de Referencia , Reproducibilidad de los Resultados , Ultrasonido , Estados Unidos
17.
J AOAC Int ; 91(3): 653-9, 2008.
Artículo en Inglés | MEDLINE | ID: mdl-18567313

RESUMEN

A method based on gas chromatography (GC)-pulsed flame photometric detection (PFPD) was developed to determine the levels of organotins in aquatic food. After being purified by gel-permeation chromatography in ethyl actate-tetrahydrofuran, the organotin compounds were derivatized by pentylmagnesium bromide. The derivative products were injected into the GC system and detected by PFPD (sulfur mode). The method was validated by analysis of the certified reference material and spiked samples. Recoveries of organotins ranged from 84.1 to 116.6% with relative standard deviation between 1.3 and 16.0% when spiked at levels of 2, 10, and 40 microg/kg. The limits of detection varied from 0.1 to 1.2 microg/kg for shellfish and 0.1 to 0.5 microg/kg for fish. The proposed method was suitable for determining organotins in aquatic foods.


Asunto(s)
Cromatografía de Gases/métodos , Contaminación de Alimentos/análisis , Compuestos Organometálicos/análisis , Compuestos de Estaño/análisis , Alimentación Animal/análisis , Alimentación Animal/normas , Alimentación Animal/toxicidad , Animales , Cromatografía de Gases/normas , Cromatografía de Gases/estadística & datos numéricos , Ionización de Llama/métodos , Ionización de Llama/normas , Ionización de Llama/estadística & datos numéricos , Cadena Alimentaria , Contaminación de Alimentos/estadística & datos numéricos , Compuestos Organometálicos/normas , Compuestos Organometálicos/toxicidad , Fotometría/métodos , Estándares de Referencia , Reproducibilidad de los Resultados , Compuestos de Estaño/normas , Compuestos de Estaño/toxicidad
18.
J Chromatogr A ; 1167(1): 102-8, 2007 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-17765907

RESUMEN

Gas mixtures of trace amounts of carbon dioxide (CO(2)), dioxygen (O(2)), and carbon monoxide (CO) in dinitrogen (N(2)) were separated and quantified using parallel dual capillary columns and pulsed discharge helium ionisation detection (PDHID). The detection limits (9 x 10(-9) mol mol(-1) for CO(2), 7 x 10(-9) mol mol(-1) for O(2) and 37 x 10(-9) mol mol(-1) for CO) were lower than those reported previously for similar methods. Uncertainties were calculated and results were validated by comparison of the CO and CO(2) results with those obtained using conventional methods. The method was also used to analyse nitrogen, carbon dioxide and carbon monoxide in oxygen.


Asunto(s)
Dióxido de Carbono/análisis , Monóxido de Carbono/análisis , Cromatografía de Gases/métodos , Electroforesis Capilar/métodos , Helio/química , Nitrógeno/química , Oxígeno/análisis , Cromatografía de Gases/estadística & datos numéricos , Cromatografía en Gel , Nitrógeno/análisis , Terapia por Inhalación de Oxígeno/normas , Sensibilidad y Especificidad , Temperatura
19.
J Clin Monit Comput ; 21(4): 257-64, 2007 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-17597416

RESUMEN

OBJECTIVES: There is a continuing risk of production of toxic levels of carbon monoxide (CO) as a result of interaction of volatile anesthetics and desiccated strong base carbon dioxide absorbents like soda lime. The aim of this study is to establish the reliability of detection of CO levels by an electrochemical carbon monoxide sensor compared to gas chromatography. METHODS: Completely desiccated sodalime was conducted through a circle anesthesia system connected to an artificial lung. For different rates of CO production, a low flow anesthesia with a oxygen/nitrous oxide mixture was maintained using five volatile anesthetics. For quantification of CO production, a portable gas chromatograph (GC) was connected to this setup, as well as a Bedfont EC40 electrochemical carbon monoxide sensor (ES) with a claimed reliable sensitivity of 0-200 parts per million (ppm) and a maximum detection range of more than 5500 ppm. To assess the agreement between the GC and ES measurements the intra class correlation coefficient (ICC) and the 95% limits of agreement were calculated. Bland and Altman scatterplots were made to visualize the difference between measurements. RESULTS: For concentrations up to 200 ppm, no significant differences between the GC and ES mean CO measurements were found in the halothane experiments. However CO was not accurately measured at every moment during these experiments by the ES. For concentrations above 200 ppm the results of the two instruments differed significantly. The ES malfunctioned when exposed to sevoflurane and desiccated sodalime. CONCLUSIONS: From these data we conclude that the ES can only be used as an indicator of CO production. When this sensor is used with sevoflurane and desiccated sodalime it is not capable of normal operation. The use of a strong base free carbon dioxide absorbent is therefore recommended.


Asunto(s)
Anestésicos por Inhalación/efectos adversos , Compuestos de Calcio/efectos adversos , Monóxido de Carbono/análisis , Cromatografía de Gases/métodos , Electroquímica/métodos , Óxidos/efectos adversos , Hidróxido de Sodio/efectos adversos , Adsorción , Anestesia por Inhalación/efectos adversos , Órganos Artificiales , Dióxido de Carbono/aislamiento & purificación , Monóxido de Carbono/metabolismo , Cromatografía de Gases/estadística & datos numéricos , Desflurano , Desecación , Interacciones Farmacológicas , Electroquímica/estadística & datos numéricos , Humanos , Técnicas In Vitro , Isoflurano/efectos adversos , Isoflurano/análogos & derivados , Pulmón , Monitoreo Intraoperatorio/métodos , Monitoreo Intraoperatorio/estadística & datos numéricos , Sensibilidad y Especificidad
20.
Chirality ; 19(5): 401-14, 2007 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-17385662

RESUMEN

Whereas the determination of high enantiomeric fractions (EF) of chiral compounds is very well established, the accurate determination of small deviations from racemic compositions has not yet received much attention despite its relevance to studies dealing with the origin of homochirality, where only small initial enantiomeric bias is expected. Racemic samples of representative alpha-amino acids were derivatized as N-(O,S)-trifluoroacetyl/ethylesters and analyzed by enantioselective gas chromatography (GC) on fused silica capillaries coated with the chiral stationary phases (CSPs) Chirasil-D-Val, Chirasil-L-Val, and Lipodex E with GC/FID and GC/MS detection. The validation (accuracy and precision) of the determination of the enantiomeric fraction EF of the D-enantiomer in racemic or near-racemic compositions for 10 DL-alpha-amino acids obtained from commercial sources has been carried out. Emphasis is given to DL-tyrosine, the enantiomers of which have recently been claimed to show different crystallization properties. Values of EF obtained from GC measurements using CSPs were compared with those from CE using chiral mobile phase additives. While the precision of the GC method is generally better than 0.08% for all DL-alpha-amino acids studied, accuracy (trueness) of determination of amino acids with polar side chains is poorer than expected from the precision as a result of systematic errors. The accuracy determined relied on measurements on two oppositely configurated CSPs.


Asunto(s)
Aminoácidos/química , Aminoácidos/aislamiento & purificación , Cromatografía de Gases/métodos , Tirosina/química , Tirosina/aislamiento & purificación , Cromatografía de Gases/estadística & datos numéricos , Estereoisomerismo
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