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.

Comparação de diferentes abordagens para avaliação da incerteza na cromatografia gasosa do gás natural

The evaluation of uncertainty associated with an analytic result is an essential part of the measurement process. Recently, several approaches to evaluate the uncertainty in measurement have been developed. Here, the gas chromatography assay uncertainty for natural gas is compared by some of these approaches: the guide to the expression of uncertainty in measurement (GUM) approach, top-down approach (reproducibility estimate from an inter-laboratory study), Barwick & Ellison (data from validation), study of variability and fuzzy approach. The comparison shows that GUM, Barwick & Ellison and fuzzy approaches lead to comparable uncertainty evaluations, which does not happen with the top-down approach and study of variability by the absence of data normality.

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..

Otimização e validação intralaboratorial de método para análise de resíduos de cloranfenicol em leite caprino por cromatografia gasosa com detecção por captura de elétrons (CG/DCE)

The presence of chloramphenicol residues in goat milk can cause toxic effects in the population. The present work consists of the optimization and validation of analytical methodology for determination of chloramphenicol residues in goat milk by GC/ECD. The extraction was made with ethyl acetate and the clean-up with SPE-C18. The identification was made by comparison of retention time and GC/MS, and the quantification by external standard. The method was selective, linearity (0.998), precise (5.8-13.4%), exact (69.87-73.71%) and robust. The LOD and LOQ of method were 0.030 and 0.10 μg/kg, respectively. The method was efficiently for analysis of chloramphenicol in goat milk.

Evaluation of sample processing methods for the polar contaminant analysis of sewage sludge using liquid chromatography - mass spectrometry (LC/MS)

Monitoring of sewage sludge has proved the presence of many polar anthropogenic pollutants since LC/MS techniques came into routine use. While advanced techniques may improve characterizations, flawed sample processing procedures, however, may disturb or disguise the presence and fate of many target compounds present in this type of complex matrix before analytical process starts. Freeze-drying or oven-drying, in combination with centrifugation or filtration as sample processing techniques were performed followed by visual pattern recognition of target compounds for assessment of pretreatment processes. The results shown that oven-drying affected the sludge characterization, while freeze-drying led to less analytical misinterpretations.

MSPD procedure combined with GC-MS for the determination of procymidone, bifenthrin, malathion and pirimicarb in honey

A method based on matrix solid-phase dispersion and gas chromatography-mass spectrometry to determine procymidone, malathion, bifenthrin and pirimicarb in honey is described. The best results were obtained using 1.0 g of honey, 1.0 g of silica-gel as dispersant sorbent and acetonitrile as eluting solvent. The method was validated by fortified honey samples at three concentration levels (0.2, 0.5 to 1.0 mg kg-1). Average recoveries (n=7) ranged from 54 to 84%, with relative standard deviations between 3.7 and 8.5%. Detection and quantification limits attained by the developed method ranged from 0.02 to 0.08 mg kg-1 and 0.07 to 0.25 mg kg-1 for the honey, respectively.

Interpretação do mecanismo de difusão no processo gás-sólido da reação de dessulfurização

The present paper aims to interpret the SO2 diffusion mechanism process for two different limestones: a calcite and a dolomite. In previous study, the apparent activation energies for sulfation reaction were between 3.03 and 4.45 kJ mol-1 for the calcite, and 11.24 kJ mol-1 for the dolomite. Using nitrogen porosimetry it was possible to observe that the dolomite presents mesopores of 0.03 μm, while the calcite presents mesopores of 0.01 μm. The evaluation of limestones porous structure together with their kinetic parameters, allowed concluding that the diffusion mechanism follows Fick law and Knudsen law for dolomite and calcite, respectively.

Development and validation of a method for the analysis of tetracyclines in chicken-muscle by liquid chromatography-electrospray-mass spectrometry in tandem (LC-ESI-MS/MS)

A LC-ESI-MS/MS method was developed and validated according to the European Union decision 2002/657/EC, for the determination of tetracyclines (TCs) in chicken-muscle since Europe is one of the main markets for Brazilian products. Linearity of r > 0.9979, limits of quantification in the range of 7.0-35.0 ng/g, average recoveries of 89.38 - 106.27%, within-day and between-day precision were adequate for all TCs. The decision limit and the detection capability were 93.00-106.46 ng/g and 95.84-114.38 ng/g, respectively. This method is suitable for application in surveillance programmes of residues of TCs in chicken-muscle samples.

Determinação de bifenilos policlorados em soro de cordão umbilical através de extração por hidrólise ácida seguida de cromatografia a gás acoplada a um microdetector de captura de elétrons

The present work describes the determination of polychlorinated biphenyls in 123 umbilical cord serum samples by liquid-liquid extraction method with acid hydrolyze step and analysis by GC-mECD. The analytical method was evaluated with following figures of merit for all PCBs: linearity (>0.997); precision (<12.55%); recoveries (73-119%); limit of detection (0.1 ng mL-1); limit of quantification (0.25-0.5 ng mL-1). The results showed high contamination in the analyzed samples. PCB more frequent was 138 (66.7%), followed by 180 (55.3%) and 52 (51.3%).

Uso da técnica HRICP-MS na avaliação dos isótopos de boro em eucalipto

The 10B isotope tracer technique is essential to study the B mobility in plants. Factors that can influence the quality of measured B isotope ratios were optimized experimentally using High Resolution Inductively Coupled Plasma Mass Spectrometry (HRICP-MS). An isotopically certified standard (NIST SRM-951) was used. The best combination was obtained using a resolution of 400, a RF power of 1250 W, followed by 15 measurements over a 10-s integration period each (15*10). Utilizing this approach it was possible to obtain a precision of 0.3 % in standard material and 2z % in the experimental samples. The results show the importance of establishing optimized work conditions before carrying out the analytical series.

Otimização e validação de método empregando quechers modificado e lc-esi-ms/ms para determinação de agrotóxicos em cebola

An evaluation of the pesticides extraction from onion using a modern sample preparation method (QuEChERS) and determination by liquid chromatography tandem mass spectrometry was carried out. All the calibration curves showed r>0.99. The recoveries ranged between 61.8 and 120.0% with relative standard deviation lower than 20% for all compounds. Due to the occurrence of matrix effect, the quantification was performed using matrix-matched calibration. The limits of quantification of the method were between 0.0005 and 0.05 mg kg-1. The method shows the advantages of not require the clean-up step and consume low volume of organic solvents, decreasing time, costs and residues.

Construção de uma célula de gás de baixo custo para análise no infravermelho

Infrared spectroscopy is a versatile technique used for qualitative and quantitative determination of all types of molecular species. As far as analysis of confined or flowing gases is concerned, different types of cell can be found in the market, but they are often very expensive. This study describes the construction of a very efficient gas cell with good reproducibility for qualitative infrared analysis of confined or flowing gases, using easily available and low-cost materials.

A sensitive and robust lc-ms/ms method with monolithic column and electrospray ionization for the quantitation of efavirenz in human plasma: application to a bioequivalence study

An LC-MS/MS method has been developed for the determination of efavirenz (EFZ) in human plasma using hydrochlorothiazide as internal standard (I.S.). An ESI negative mode with multiple reaction-monitoring was used monitoring the transitions m/z 313.88→69.24 (EFZ) and 296.02→204.76 (I.S.). Samples were extracted using liquid-liquid extraction. The total run time was 2.0 min. The separation was achieved with HPLC-RP using a monolithic column. The assay was linear in the concentration range of 100 - 5000 ng mL-1. The mean recovery was 83%. Intra- and inter-day precision were < 9.5% and < 8.9%, respectively and accuracy was in the range ± 8.33%. The method was successfully applied to a bioequivalence study.

Avaliação da eficiência das técnicas ESI-MS e ATR/FTIR na determinação de adulteração de BX com querosene e óleo residual

Direct infusion electrospray ionization mass spectrometry in the negative ion mode, ESI(-)-MS and Fourier transform infrared spectroscopy (FTIR) were used together with partial least squares (PLS) as a tool to determine B3 adulteration (B3 - mixture of 3% v/v of biodiesel in diesel) with kerosene and residual oil.

Produção de gás de síntese por plasma térmico via pirólise de metano e dióxido de carbono

In this work the production of synthesis gas from a mixture of methane (CH4) and carbon dioxide (CO2) by thermal plasma was studied. The best relation found for the gas mixture [CO2]/[CH4] was 1.3. Under the excess of CH4 in the gas mixture soot was formed and also benzene, indene and naphthalene were identified. The disulfides compounds in the gas mixture were degraded causing no interference in the synthesis gas production, suggesting no needs of pretreatment step for sulfurorganic compounds removal in the process