Comparison of the quantification of caffeine in human plasma by gas chromatography and ELISA

In the present study we evaluated the precision of the ELISA method to quantify caffeine in human plasma and compared the results with those obtained by gas chromatography. A total of 58 samples were analyzed by gas chromatography using a nitrogen-phosphorus detector and routine techniques. For the ELISA test, the samples were diluted to obtain a concentration corresponding to 50% of the absorbance of the standard curve. To determine whether the proximity between the I50 of the standard curve and that of the sample would bring about a more precise result, the samples were divided into three blocks according to the criterion of difference, in modulus, of the I50 of the standard curve and of the I50 of the sample. The samples were classified into three groups. The first was composed of 20 samples with I50 up to 1.5 ng/ml, the second consisted of 21 samples with I50 ranging from 1.51 to 3 ng/ml, and the third of 17 samples with I50 ranging from 3.01 to 13 ng/ml. The determination coefficient (R² = 0.999) showed that the data obtained by gas chromatography represented a reliable basis. The results obtained by ELISA were also reliable, with an estimated Pearson correlation coefficient of 0.82 between the two methods. This coefficient for the different groups (0.88, 0.79 and 0.49 for groups 1, 2 and 3, respectively) showed greater reliability for the test with dilutions closer to I50.

Multiresidue determination of pesticides in honey samples by gas chromatography-mass spectrometry and application in environmental contamination

A simple and fast multiresidue method has been developed to determine 48 pesticides within the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of locally produced honey, in Bauru (State of São Paulo, Brazil) during 2003-2004. The recovery results found ranged from 76% to 95% and the limits of detection were lower than 0.01 mg/kg for gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). The results indicated that most pesticides found in the samples belonged to the organohalogen and organophosphorous groups and lower levels of residues of some organonitrogen and pyretroids were also detected. Malathion residues were detected in all the samples, in a high concentration, owing to its applications to control dengue mosquitoes in the area studied. (c) 2005 Elsevier Ltd. All rights reserved.

Identification of triterpenes and sterols from pterogyne nitens (fabaceae-caesalpinioideae) using high-resolution gas chromatography

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Solid-phase extraction of sugar cane soot extract for analysis by gas chromatography with flame ionisation and mass spectrometric detection

The incomplete combustion of biomass is one of the most important sources of emissions of organic compounds into the atmosphere, like polycyclic aromatic hydrocarbons (PAHs) which show genotoxic activity. Since environmental samples generally contain interferents and trace amounts of PAHs of interest, concentration and clean-up procedures are usually required prior to the final chromatographic analysis. This paper discusses the performance of Sep-Pak cartridges (silica gel and RP18) on clean-up of sugar cane soot extract. The best results were obtained with a silica Sep-Pak cartridge. The recoveries ranged from 79% (benzo[b]fluoranthene) to 113% (benzo[e]pyrene). (C) 2000 Elsevier B.V. B.V. All rights reserved.

Screening Brazilian automotive gasoline quality through quantification of saturated hydrocarbons and anhydrous ethanol by gas chromatography and exploratory data analysis

In this paper a set of Brazilian commercial gasoline representative samples from São Paulo State, selected by HCA, plus six samples obtained directly from refineries were analysed by a high-sensitive gas chromatographic (GC) method ASTM D6733. The levels of saturated hydrocarbons and anhydrous ethanol obtained by GC were correlated with the quality obtained from Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP) specifications through exploratory analysis (HCA and PCA). This correlation showed that the GC method, together with HCA and PCA, could be employed as a screening technique to determine compliance with the prescribed legal standards of Brazilian gasoline.

Determination of buprofezin, pyridaben, and tebufenpyrad residues by gas chromatography mass-selective detection in clementine citrus

A gas chromatography-mass-selective (GC-MS) detection method to determine buprofezin, pyridaben, and tebufenpyrad on the pulp, peel, and whole fruit of clementines is described. The extraction/partition procedure was performed in one step and no cleanup was necessary with the GC-MS in the SIM-mode pesticide determination. Recovery ranged from 75 to 124% with coefficients of variance ranging between 1 and 13%. The limit of determination was 0.01 mg/kg for all pesticides. The field trials showed a similar degradative behavior for all active ingredients (AI), with a great residue decrease during the first week and stability in the second. Just after treatment buprofezin and tebufenpyrad showed lower residues than the maximum residue limit (MRL) fixed in Italy, while pyridaben was below the MRL after a week.

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

Determination of disease biomarkers in Eucalyptus by comprehensive two-dimensional gas chromatography and multivariate data analysis

In this paper is reported the use of the chromatographic profiles of volatiles to determine disease markers in plants - in this case, leaves of Eucalyptus globulus contaminated by the necrotroph fungus Teratosphaeria nubilosa. The volatile fraction was isolated by headspace solid phase microextraction (HS-SPME) and analyzed by comprehensive two-dimensional gas chromatography-fast quadrupole mass spectrometry (GC. ×. GC-qMS). For the correlation between the metabolic profile described by the chromatograms and the presence of the infection, unfolded-partial least squares discriminant analysis (U-PLS-DA) with orthogonal signal correction (OSC) were employed. The proposed method was checked to be independent of factors such as the age of the harvested plants. The manipulation of the mathematical model obtained also resulted in graphic representations similar to real chromatograms, which allowed the tentative identification of more than 40 compounds potentially useful as disease biomarkers for this plant/pathogen pair. The proposed methodology can be considered as highly reliable, since the diagnosis is based on the whole chromatographic profile rather than in the detection of a single analyte. © 2013 Elsevier B.V..

Leishmanicidal activity of Brosimum glaziovii (Moraceae) and chemical composition of the bioactive fractions by using high-resolution gas chromatography and GC-MS

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Pyrolysis-Gas Chromatography-Mass Spectometry and Chemometric Analysis for the Characterization of Complex Matrices

The present PhD thesis was focused on the development and application of chemical methodology (Py-GC-MS) and data-processing method by multivariate data analysis (chemometrics). The chromatographic and mass spectrometric data obtained with this technique are particularly suitable to be interpreted by chemometric methods such as PCA (Principal Component Analysis) as regards data exploration and SIMCA (Soft Independent Models of Class Analogy) for the classification. As a first approach, some issues related to the field of cultural heritage were discussed with a particular attention to the differentiation of binders used in pictorial field. A marker of egg tempera the phosphoric acid esterified, a pyrolysis product of lecithin, was determined using HMDS (hexamethyldisilazane) rather than the TMAH (tetramethylammonium hydroxide) as a derivatizing reagent. The validity of analytical pyrolysis as tool to characterize and classify different types of bacteria was verified. The FAMEs chromatographic profiles represent an important tool for the bacterial identification. Because of the complexity of the chromatograms, it was possible to characterize the bacteria only according to their genus, while the differentiation at the species level has been achieved by means of chemometric analysis. To perform this study, normalized areas peaks relevant to fatty acids were taken into account. Chemometric methods were applied to experimental datasets. The obtained results demonstrate the effectiveness of analytical pyrolysis and chemometric analysis for the rapid characterization of bacterial species. Application to a samples of bacterial (Pseudomonas Mendocina), fungal (Pleorotus ostreatus) and mixed- biofilms was also performed. A comparison with the chromatographic profiles established the possibility to: • Differentiate the bacterial and fungal biofilms according to the (FAMEs) profile. • Characterize the fungal biofilm by means the typical pattern of pyrolytic fragments derived from saccharides present in the cell wall. • Individuate the markers of bacterial and fungal biofilm in the same mixed-biofilm sample.

Informatics for cross-sample analysis with comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry (GCxGC-HRMS)

This paper describes informatics for cross-sample analysis with comprehensive two-dimensional gas chromatography (GCxGC) and high-resolution mass spectrometry (HRMS). GCxGC-HRMS analysis produces large data sets that are rich with information, but highly complex. The size of the data and volume of information requires automated processing for comprehensive cross-sample analysis, but the complexity poses a challenge for developing robust methods. The approach developed here analyzes GCxGC-HRMS data from multiple samples to extract a feature template that comprehensively captures the pattern of peaks detected in the retention-times plane. Then, for each sample chromatogram, the template is geometrically transformed to align with the detected peak pattern and generate a set of feature measurements for cross-sample analyses such as sample classification and biomarker discovery. The approach avoids the intractable problem of comprehensive peak matching by using a few reliable peaks for alignment and peak-based retention-plane windows to define comprehensive features that can be reliably matched for cross-sample analysis. The informatics are demonstrated with a set of 18 samples from breast-cancer tumors, each from different individuals, six each for Grades 1-3. The features allow classification that matches grading by a cancer pathologist with 78% success in leave-one-out cross-validation experiments. The HRMS signatures of the features of interest can be examined for determining elemental compositions and identifying compounds.