Eletroforese capilar acoplada à espectrometria de massas (CE-MS): vinte anos de desenvolvimento

CE-MS has been increasingly used for analysis of a vast array of compounds. This article reviews the different electrophoretic modes, interfaces and mass analyzers that are commonly used in the CE-MS coupling, as well as the technique advantages and performance characteristics. A large compilation of CE-MS applications is also presented. Therefore, this review is both a guide for beginners and a collection of key references for people who are familiar to the technique. Furthermore, this is the first CE-MS review published in a Brazilian journal and marks the installation of the first two commercial CE-MS units in Sao Paulo State.

QuEChERS: um método moderno de preparo de amostra para determinação multirresíduo de pesticidas em alimentos por métodos cromatográficos acoplados à espectrometria de massas

This review attempts to provide an updated overview of the Quick, Easy, Cheap, Effective, Ruged and Safe (QuEChERS) multiresidue extraction method, that involves initial extraction in acetonitrile, an extraction/partition step after the addition of salt, and a cleanup step utilizing dispersive solid phase extraction. QuEChERS method is nowadays the most applied extraction method for the determination of pesticide residues in food samples, providing acceptable recoveries for acidic, neutral and basic pesticides. Several applications for various food matrices (fruits, vegetables, cereals and others) in combination with chromatographic mass spectrometry analysis were presented.

Determinação de resíduos de pesticidas em plasma bovino por cromatografia gasosa-espectrometria de massas

An analytical method for the isolation based on matrix solid-phase dispersion technique and gas chromatographic determination of pesticides in cattle plasma is presented. It was fortified 0.25 g of plasma with pesticides and blended with 1 g each C18 and Na2SO4. The homogenized matter was transferred to a SPE cartridge, which contained 1 g of activated florisil with 5 mL acetonitrile. The analites were eluted under vaccum with 15 mL acetonitrile, the extract was analyzed by gas chromatography-mass spectrometry. The limit of quantification of the method was 0.04 mg L-1 for chlorphenvinfos and fipronil and 0.02 mg L-1 for cypermethrin..

Hidrólise do óleo de Azadirachta indica em água subcrítica e determinação da composição dos triacilglicerídeos e ácidos graxos por cromatografia gasosa de alta resolução a alta temperatura e cromatografia gasosa de alta resolução acoplada à espectrometria de massas

The development of modern analytical tools plays an important role in quality control. The main purpose of this study was to explore the use of subcritical water as a versatile analytical tool, employed simultaneously as a reagent and solvent, as well as the application of high temperature-high resolution gas chromatography (HT-HRGC) to develop a procedure for the analysis of triacylglycerides and fatty acids in Azadirachta indica A. Juss. (Neem) oil without the need for solvents, chemical reagents, or catalytic agents. The developed method presented satisfactory results and is in agreement with the concepts of Green Analytical Chemistry (GAC).

Caracterização de contaminantes presentes em sistemas de tratamento de esgotos, por cromatografia líquida acoplada à espectrometria de massas tandem em alta resolução

This work shows results on the characterization, by liquid chromatography coupled to high resolution tandem mass spectrometry (LC-IT-TOF-MS) with electrospray ionization, of organic compounds present in raw and treated effluents from a combined sewage treatment systems (upflow anaerobic sludge blanket-trickling filter). The sewage samples were prepared by C18 solid phase extraction and the spectra obtained from the various extracts were submitted to principal component analysis to evaluate their pattern and identify the major deprotonated species. Some target compounds were submitted to semiquantitative analysis, using phenolphtalein as internal standard. The results showed the anaerobic step had little impact on the removal of anionic surfactants (LAS), fatty acids, and some contaminantes such as bisphenol A and bezafibrate, whereas the aerobic post-treatment was very efficient in removing these organics.

Projeto e construção de um picnômetro a ar para caracterização de insumos e produtos farmacêuticos

This paper describes a project, construction and test of a low cost air pycnometer, developed to be used preferentially in pharmaceutical research. A complete discussion of the construction, test and calibration of this equipment is presented and some measurements are made using pharmaceutical powders and dry granulations. The equipment performance has been estimated through its calibration curve, and the obtained value to its volume resolution is about 1%. This equipment is accomplished at the Applied Nuclear Physics Laboratory of University of Sorocaba (LAFINAU) in Sorocaba, SP, Brazil and it was denominated "Picnômetro a Ar Uniso - PICNAU".

Aplicação de métodos quimiométricos na caracterização de charutos utilizando extração por dispersão da matriz em fase sólida e análise por cromatografia gasosa acoplada à espectrometria de massas

In this work, the organic compounds of cigar samples from different brands were analyzed. The compound extraction was made using the matrix solid-phase dispersion (MSPD) technique, followed by gas chromatography and identification by mass spectrometry (GC-MS) and standards, when available. Thirty eight organic compounds were found in seven different brands. Finally, with the objective of characterizing and discriminating the cigar samples, multivariate statistical analyses were applied to data, e.g.; principal component analysis (PCA) and hierarchical cluster analysis (HCA). With such analyses, it was possible to discriminate three main groups of three quality levels.

Efeito da temperatura do ar de secagem sobre o teor e a composição química do óleo essencial de Pectis brevipedunculata

Leaves and flower heads of P. brevipedunculata were submitted to four drying-air temperatures (room temperature, 40, 50 and 60 ºC). Room temperature (approximately 30 ºC) and higher temperature drying (50 and 60 ºC) had a deleterious effect on the essential oil content. The recommended drying-air temperature for the species is 40 ºC for it results in the same amount of essential oil observed in fresh cut plants. Overall, 13 components accounting for more than 92% of the total composition were identified. Citral was the major component, followed by α-pinene and limonene. The essential oil showed high toxicity against Artemia salina larvae.

Análise de pesticidas organoclorados em água usando a microextração em fase sólida por headspace com cromatografia gasosa e espectrometria de massas

A method based on headspace - solid phase microextraction coupled with gas chromatography - mass spectrometry was validated for the quantitative determination of 18 organochlorine pesticides in water. For the extraction conditioning some parameters as the best type of coating fiber, time and temperature of extraction, pH and ionic strength were evaluated. The method HS-SPME/GC-MS/MS showed linear coefficient above 0.9948. The repeatability of the measurements were lower than 7.6%. Relative recoveries were between 88 and 110%. Limits of detection from 0.5 x 10-3 to 1.0 mg L-1 were obtained. A total of 31 samples were analyzed and 16 presented from 1 to 5 pesticides.

Principais técnicas de preparo de amostra para a determinação de resíduos de agrotóxicos em água por cromatografia líquida com detecção por arranjo de diodos e por espectrometria de massas

The determination of pesticide residues in water samples by Liquid Chromatography require sample preparation for extraction and enrichment of the analytes with the minimization of interferences to achieve adequate detection limits. The Solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), Stir Bar Sorptive Extraction (SBSE) and Dispersive Liquid-Liquid Microextraction (DLLME) techniques have been widely used for extraction of pesticides in water. In this review, the principles of these sample preparation techniques associated with the analysis by Liquid Chromatography with Diode Array Detection (LC-DAD) or Mass Spectrometry (LC-MS) are described and an overview of several applications were presented and discussed.

Nomenclaturas de espectrometria de massas em língua portuguesa

In commemoration of the International Year of Chemistry this article presents the normalization and standardization of key terms used in mass spectrometry in Portuguese Language.

Atribuição absoluta e geral de isômeros constitucionais por espectrometria de massas: o caso das metilpiperidinas

An absolute method is described via mass spectrometry (MS) for the structural assignment of isomers within the class of methylpiperidines. The method explores both the unimolecular and bimolecular gas phase behavior of structurally diagnostic fragment ions (SDFI). For the methylpiperidnes, the isomeric 2-methyl, 3-methyl and 4-methyl 2-azabutadienyl cations are found to function as SDFI. These fragment ions are expected to be formed from all members within the class, to be stable and to retain the structural information of the precursor molecule, and to not interconvert into one another. To characterize these SDFI, both the collision induced dissociation (CID) in argon and bimolecular ion/molecule chemistry with ethyl vinyl ether were compared.

Determinação de bifenilos policlorados em milho através de extração em fase sólida seguida de cromatografia a gás acoplada à espectrometria de massas

This paper describes an analytical method for analyzing polychlorinated biphenyls in corn samples using solid phase extraction (SPE) followed by determination by GC-MS. All calibration curves proved linear (r> 0.99). Recoveries ranged between 74.1 and 110.6% with relative standard deviation lower than 20% for all compounds. The limits of quantitation for the method were between 0.025 and 0.1 ng g-1. Of the 51 samples analyzed, PCB 180 showed the highest frequency, being detected in more than 39%, followed by PCB 138, detected in more than 33% of samples.

Determinação de plastificantes em água potável utilizando cromatografia gasosa e espectrometria de massas

This study investigated the levels of plasticizer endocrine disruptors (diethyl phthalate, dibutyl phthalate, and bisphenol A) in drinking water at Paraíba do Sul River region and release of these compounds from bottled water. An analytical method employing solid phase extraction and GC/MS was optimized and validated. The results showed that the method is selective, linear (r² > 0.99), precise (RSD <12%), accurate (recoveries between 62 and 105%), sensitive and robust. Applying the method, the presence of all studied pollutants in drinking water was observed for the three sampled plasticizers. These plasticizers were not found in mineral bottled water, before or after storage.

Extração de ácido trans-trans mucônico urinário com polímeros de impressão molecular e análise por cromatografia gasosa: espectrometria de massas

This paper describes selective molecularly imprinted solid-phase extraction of ttMA from urine samples followed by derivatization and analysis by gas chromatography/mass spectrometry (GC/MS). The analytical calibration curve ranged from 0.3 to 7.0 mg L-1 (r = 0.999) and the limit of quantitation (LOQ) was 0.3 mg L-1. The method was applied for the determination of ttMA in urine samples from smokers and concentrations detected ranged from < LOQ to 1.64 mg L-1. Thus, the proposed method proved adequate for the determination of urinary ttMA in the biomonitoring of occupational exposure to low levels of benzene.