Multivariate calibrations in gas chromatographic profiles for prediction of several physicochemical parameters of Brazilian commercial gasoline

Several Brazilian commercial gasoline physicochemical parameters, such as relative density, distillation curve (temperatures related to 10%, 50% and 90% of distilled volume, final boiling point and residue), octane numbers (motor and research octane number and anti-knock index), hydrocarbon compositions (olefins, aromatics and saturates) and anhydrous ethanol and benzene content was predicted from chromatographic profiles obtained by flame ionization detection (GC-FID) and using partial least square regression (PLS). GC-FID is a technique intensively used for fuel quality control due to its convenience, speed, accuracy and simplicity and its profiles are much easier to interpret and understand than results produced by other techniques. Another advantage is that it permits association with multivariate methods of analysis, such as PLS. The chromatogram profiles were recorded and used to deploy PLS models for each property. The standard error of prediction (SEP) has been the main parameter considered to select the "best model". Most of GC-FID-PLS results, when compared to those obtained by the Brazilian Government Petroleum, Natural Gas and Biofuels Agency - ANP Regulation 309 specification methods, were very good. In general, all PLS models developed in these work provide unbiased predictions with lows standard error of prediction and percentage average relative error (below 11.5 and 5.0, respectively). (C) 2007 Elsevier B.V. All rights reserved.

(1)H NMR Fingerprinting of Brazilian Commercial Gasoline: Pattern-Recognition Analyses for Origin Authentication Purposes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Identification of Mycobacteria by Thin Layer Chromatographic Analysis of Mycolic Acids and Conventional Biochemical Method: Four Years of Experience

Mycolic acids analysis by thin-layer chromatography (TLC) has been employed by several laboratories worldwide as a method for fast identification of mycobacteria. This method was introduced in Brazil by our laboratory in 1992 as a routine identification technique. Up to the present, 861 strains isolated were identified by mycolic acids TLC and by standard biochemical tests; 61% out of these strains came as clinical samples, 4% isolated from frogs and 35% as environmental samples. Mycobacterium tuberculosis strains identified by classical methods were confirmed by their mycolic acids contents (I, III and IV). The method allowed earlier differentiation of M. avium complex - MAC (mycolic acids I, IV and VI) from M. simiae (acids I, II and IV), both with similar biochemical properties. The method also permitted to distinguish M. fortuitum (acids I and V) from M. chelonae (acids I and II) , and to detect mixed mycobacterial infections cases as M. tuberculosis with MAC and M. fortuitum with MAC. Concluding, four years experience shows that mycolic acids TLC is an easy, reliable, fast and inexpensive method, an important tool to put together conventional mycobacteria identification methods.

Metabolic fingerprinting using direct flow injection electrospray ionization tandem mass spectrometry for the characterization of proanthocyanidins from the barks of Hancornia speciosa

Direct flow injection electrospray ionization ion trap tandem mass spectrometry (ESI-IT-MS/MS) was used to investigate the polyphenolic compounds present in an infusion from the barks of Hancornia speciosa Gom. (Apocynaceae), a native Brazilian plant popularly known as 'mangabeira', used as a source of nutrition and against gastric disorders. After a simple sample filtration pretreatment the characteristic fingerprint of the infusion was performed in negative ion ESI mode in a few minutes. At low capillary-voltage activation, the deprotonated molecules ([M-H](-)) were observed and using collision-induced dissociation the product ion spectra showed the presence of a homologous series of B-type proanthocyanidins, as well as another series containing their respective C-glycosylated derivatives, with a degree of polymerization from 1 up to 6 units of interlinked catechins. Therefore, direct flow injection allowed us to identify the key compounds without preparative isolation of the components. Copyright (C) 2007 John Wiley & Sons, Ltd.

Gas chromatographic-olfactometric characterization of aroma compounds in two types of cashew apple nectar

Cashew apple nectar is a secondary product from the production of cashew nuts and possesses an exotic tropical aroma. Aroma volatiles in pasteurized and reconstituted (from concentrate) Brazilian cashew apple nectars were determined using GC-MS and split, time-intensity GC-olfactometry (GC-O/GC-FID. Methional, (2)-1,5-octadien-3-one, (2)-2-nonenal, (E,Z)-2,4-decadienal, (E,E)-2,4-decadienal, beta-damascenone, and delta-decalactone were identified for the first time in cashew apple products. These compounds plus butyric acid, ethyl 3-methylbutyrate, 2-methylbutyric acid, acetic acid, benzaldehyde, homofuraneol, (E)-2-nonenal, gamma-dodecalactone, and an unknown were the most intense aroma volatiles. Thirty-six aroma volatiles were detected in the reconstituted sample and 41 in the pasteurized sample. Thirty-four aroma active components were common to both samples. Ethyl 3-methylbutyrate and 2-methylbutyric acid were character impact compounds of cashew apple (warm, fruity, tropical, sweaty). Using GC-pFPD, 2-methyl-3-furanthiol and bis(2-methyl-3-furyl) disulfide were identified for the first time in cashew apple. Both were aroma active (meaty).

Molecular fingerprinting methods for the discrimination between C-albicans and C-dubliniensis

Opportunistic fungal pathogens are becoming increasingly important causes of both community-acquired and nosocomial infections. The most important fungal pathogens are yeast species belonging to the genus Candida. These species show differences in levels of resistance to antifungal agents and mortality. Consequently, it is important to correctly identify the causative organism to the species level. Identification of Candida dubliniensis in particular remains problematic because of the high degree of phenotypic similarity between this species and Candida albicans. However, as the differences between both are most pronounced at the genetic level, several studies have been conducted in order to provide a specific and rapid identification fingerprinting molecular test. In most candidal infectious, no single DNA fingerprinting technique has evolved as a dominant method, and each method has its advantages, disadvantages and limitations. Moreover, the current challenge of these techniques is to compile standardized patterns in a database for interlaboratory use and future reference. This review provides an overview of most common molecular fingerprinting techniques currently available for discrimination of C. albicans and C. dubliniensis.

A high-performance liquid chromatographic assay for sparfloxacin

A specific and sensitive high-performance liquid chromatographic procedure was developed for the assay of sparfloxacin in raw material and tablets. It was also found that the excipients in the commercial tablet preparation did not interfere with the assay. The method validation yielded good results and included the range, linearity, precision, accuracy, specificity and recovery. This method can also be applied to stability studies. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Analysis of aromatic amines in surface waters receiving wastewater from a textile industry by liquid chromatographic with electrochemical detection

A high performance liquid chromatography ( HPLC) method with electrochemical detection (ED) was developed for the determination of benzidine, 3,3-dimethylbenzidine, o-toluidine and 3,3-dichlorobenzidine in the wastewater of the textile industry. The aromatic amines were eluted on a reversed phase column Shimadzu Shimpack C-18 using acetonitrile + ammonium acetate (1 x 10(-4) mol L-1) at a ratio 46: 54 v/v as mobile phase, pumped at a flow rate of 1.0 mL min(-1). The electrochemical oxidation of the aromatic amines exhibits well-defined peaks at a potential range of +0.45 to +0.78 V on a glassy carbon electrode. Optimum working potentials for amperometric detection were from 0.70 V to +1.0 V vs. Ag/AgCl. Analytical curves for all the aromatic amines studied using the best experimental conditions present linear relationship from 1 x 10(-8) mol L-1 to 1.5 x 10(-5) mol L-1, r = 0.99965, n = 15. Detection limits of 4.5 nM (benzidine), 1.94 nM (o-toluidine), 7.69 nM (3,3-dimethylbenzidine), and 5.15 nM (3,3-dichlorobenzidine) were achieved, respectively. The detection limits were around 10 times lower than that verified for HPLC with ultra violet detection. The applicability of the method was demonstrated by the determination of benzidine in wastewater from the textile industry dealing with an azo dye processing plant.

Gas chromatographic analysis of indole alkaloids from Tabernaemontana hilariana

A fast and efficient procedure was elaborated to identify the alkaloid constituents from Tabernaemontana hilariana (Apocynaceae). The strategy based on fractioning of the crude alkaloid fraction in small silica cartridges followed by thin-layer chromatography (TLC), capillary gas chromatography-flame ionization detection as well as high-resolution gas chromatography-mass spectrometry afforded voacangine, coronaridine, ibogamine, voacangine pseudoindoxyl, voacangine hydroxyindolenine, 3-hydroxycoronaridine and 3-(2-oxopropyl)coronaridine. (C) 1997 Elsevier B.V. B.V.

Fast chromatographic determination of polycyclic aromatic hydrocarbons in aerosol samples from sugar cane burning

Sugar cane burning in Brazil causes remarkable amounts of organic compounds to be emitted amongst which the polycyclic aromatic hydrocarbons (PAHs) represent serious health hazards. Therefore, 24-h aerosol samples (< 10 mum aerodynamic diameter) were collected in Araraquara city (São Paulo state) during the harvest season using a Hi-Vol sampler. PAHs were recovered using an Accelerated Solvent Extractor and analyzed by low-pressure gas chromatography-ion trap mass spectrometry (LP-GC-IT-MS). The fully automated extraction process was performed in less than 25 min with a solvent consumption of approximately 20 ml. The use of a deactivated 0.6 m x 0. 10 mm i.d. restrictor coupled to a 10 m wide-bore analytical column allowed most of the 16 PAHs in EPA's priority list to be identified and quantified in only 13 min. Concentrations of PAHs in Nraraquara aerosols ranged between 0.5 and 8.6 ng m(-3). (C) 2003 Elsevier B.V. All rights reserved.

Determination of carbamate residues in crop samples by cholinesterase-based biosensors and chromatographic techniques

An amperometric biosensor based on cholinesterase (ChE) has been used for the determination of selected carbamate insecticides in vegetable samples. The linear range of the biosensor for the N-methylcarbamates (aldicarb, carbaryl, carbofuran, methomyl and propoxur) varied from 5 x 10(-5) to 50 mg kg(-1). Limits of detection were calculated on the basis that the ChE enzymes were 10% inhibited and varied, depending of the combination ChE (as acetyl- or butyrylcholinesterase) vs. inhibitor (pesticide), from 1 x 10(-4) to 3.5 mg kg(-1). The biosensor-based carbamate determination was compared to liquid chromatography/UV methods. Three vegetable samples were spiked with carbofuran and propoxur at 125 mu g kg(-1) followed by conventional procedures. Good correlations were observed for carbofuran in the vegetable extracts (79, 96 and 91% recoveries for potato, carrot and sweet pepper, respectively), whereas for propoxur unsatisfactory results were obtained. Potato and carrot samples were spiked with 10, 50 and 125 mu g kg(-1) carbofuran, followed by direct determination by the amperometric biosensor. The fortified sampler; resulted in very high inhibition values, and recoveries were: 28, 34 and 99% for potato, and 140, 90 and 101% for carrot, respectively, at these three fortification levels. (C) 1998 Elsevier B.V. B.V.

Screening Brazilian C gasoline quality: Application of the SIMCA chemometric method to gas chromatographic data

A total of 2400 samples of commercial Brazilian C gasoline were collected over a 6-month period from different gas stations in the São Paulo state, Brazil, and analysed with respect to 12 physicochemical parameters according to regulation 309 of the Brazilian Government Petroleum, Natural Gas and Biofuels Agency (ANP). The percentages (v/v) of hydrocarbons (olefins, aromatics and saturated) were also determined. Hierarchical cluster analysis (HCA) was employed to select 150 representative samples that exhibited least similarity on the basis of their physicochemical parameters and hydrocarbon compositions. The chromatographic profiles of the selected samples were measured by gas chromatography with flame ionisation detection and analysed using soft independent modelling of class analogy (SIMCA) method in order to create a classification scheme to identify conform gasolines according to ANP 309 regulation. Following the optimisation of the SIMCA algorithm, it was possible to classify correctly 96% of the commercial gasoline samples present in the training set of 100. In order to check the quality of the model, an external group of 50 gasoline samples (the prediction set) were analysed and the developed SIMCA model classified 94% of these correctly. The developed chemometric method is recommended for screening commercial gasoline quality and detection of potential adulteration. (c) 2007 Elsevier B.V. All rights reserved.

RAPD genomic fingerprinting differentiates Thiobacillus ferrooxidans strains

The PCR-based technique, involving the random amplification of polymorphic DNA (RAPD), was optimized and used for assessing genomic variability among eight Thiobacillus ferrooxidans strains. RAPD fingerprints presented variation for the thirty primers used, giving a total of 269 polymorphic bands. Similarity coefficients between the strains were calculated, and UPGMA cluster analysis was used to generate a dendrogram showing relationships among them. Most primers divided T. ferrooxidans strains in two distinct groups - Group 1: S, SSP, V3, AMF and Group 2: CMV, FG-460, I-35, LR. We observed that the T. ferrooxidans strains used in this work have a high degree of genomic diversity and that RAPD is a powerful method to differentiate them.

Determination of 2,4-dichlorophenoxyacetic acid and its major transformation product in soil samples by liquid chromatographic analysis

The 2,4-dichlorophenoxyacetic acid (2,4-D) is one of the most applied herbicides around the world to control broad leave herbs in many crops: In this study, a method was developed for simultaneous extraction and determination of 2,4D and its major transformation product, i.e., the 2,4-dichlorophenol (2,4-DCP), in soil samples. The herbicide and its degradation product were extracted twice from soil samples, after acidification, by dichloromethane on ultrasound system for 1 h. Both extracts were combined and filtrated in qualitative filter paper and Celitee. The total extract was concentrated in rotatory evaporator, dried under N-2 and finally dissolved in 1 ml of methanol. High Performance Liquid Chromatography with UV detection at 230 nm was used for analysis. Recoveries were obtained from soil samples fortified at 0.1, 1.0, 2.0, 3.0 and 4.0 mg kg(-1) levels and the results varied from 85 to 111% (for 2,4-D) and from 95 to 98% (for 2,4-DCP). For both compounds, the limits of quantification were 0.1 mg kg(-1), which were the loss level at which the accuracy and the precision were studied. Nevertheless, the limits of detection, calculated by considering the blank standard deviation and the minimum concentration level, were 0.03 and 0.02 mg kg for 2,4-D and 2,4-DCP, respectively. This proposed method was applied to soil samples of eucalyptus crops, which was previously treated with the herbicide. Despite that, neither 2,4-D nor its degradation product were detected 30 days after the herbicide application. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Electrophoretic and chromatographic profile for S-like hemoglobin

Hemoglobin variants originate mainly by simple amino acid substitutions, the result of nucleotide sequence changes. Recently, the number of known abnormal hemoglobins has increased due to improvement in analysis methodologies; however, many laboratories are not prepared to correctly identify mutants. Hb S is a very well-characterized hemoglobin variant that varies in prevalence in different regions of Brazil. However, there is a type of Hb that presents electrophoretic migration in alkaline pH similar to Hb S, named S-like Hb, which can be incorrectly diagnosed; therefore, its frequency is underestimated. We obtained reference ranges for Hb S by HPLC, and we examined the electrophoretic and chromatographic profiles of S-like Hb. Hb Hasharon, Hb D-Los Angeles, Hb Korle-Bu, Hb Lepore, Hb D-Iran, Hb G-like, Hb Queens, Hb Montgomery, and Hb Q-India were found. Cases of association between two beta chain mutants were also found. Electrophoresis in alkaline and acid pH was utilized to initially screen these Hb variants, and globin chain electrophoresis at both high and low pH was performed to identify the globin chain mutant. Chromatographic analysis permitted the identification of the hemoglobin variant and also facilitated the quantification of these variants. Therefore, an association of classical laboratory diagnostic methodologies is fundamental for the correct identification of suspect Hb variants. The S and S-like hemoglobin profiles determined in this study will help in the diagnosis of these variants in health care services.