Sistema em fluxo para determinação espectrofotométrica de uréia em plasma de sangue animal empregando leguminosa como fonte natural da enzima urease

A spectrophotometric flow injection analysis (FIA) procedure employing natural urease enzyme source for the determination of urea in animal blood plasma was developed. Among leguminous plants used in the Brazilian agriculture, the Cajanus cajan specie was selected as urease source considering its efficiency and availability. A minicolumn was filled with leguminous fragments and coupled to the FIA manifold, where urea was on-line converted to ammonium ions and subsequently it was quantified by spectrophotometry. The system was employed to determine urea in animal plasma samples without any prior treatment. Accuracy was assessed by comparison results with those obtained employing the official procedure and no significant difference at 90 % confidence level was observed. Other profitable features such as an analytical throughput of 30 determinations per hour, a reagent consumption of 19.2 mg sodium salicylate, 0.5 mg sodium hipochloride and a relative standard deviation of 1.4 % (n= 12) were also obtained.

A bench arc-furnace facility for fullerene and single-wall nanotubes synthesis

A metallic-sample arc-furnace was modified to synthesize fullerenes and nanotubes. The (reversible) changes and the process for producing single-wall nanotubes (SWNTs) are described.

Análise de suspensões de argilas por espectrometria de emissão óptica com plasma induzido com configuração axial

The goal of this study was to evaluate the feasibility of direct introduction of clay slurries in an inductively coupled plasma optical emission spectrometer with axial view configuration. Calibration was performed using a certified reference material with a mean particle size of 13 µm (IPT-42) and the analytical curve was applied for quantification of two others reference materials (IPT-28 and IPT-32) and four samples. It was demonstrated that the analytical curve thus obtained was not completely suitable for IPT-28 and samples due to different mineralogical phases determined by X-ray diffraction. After considering this effect, it was possible for most elements to obtain results in agreement with certified values or with values obtained by a conventional technique at a 95% confidence level. It was demonstrated that the ICP-OES with axial view configuration did not present any incompatibility with the direct introduction of a complex inorganic suspension.

Eletroforese capilar acoplada à espectrometria com plasma: uma ferramenta eficiente para a especiação

The most important features of the CE-ICP hyphenation, as well as its advantages and drawbacks as a tool for speciation are discussed. The fundamental principles of capillary electrophoresis and inductively coupled plasma mass spectrometry are also presented. Some applications involving different designs proposed in the literature to couple CE and ICP system for elemental speciation are reviewed.

Ultra-trace monitoring of copper in environmental and biological samples by inductively coupled plasma atomic emission spectrometry after separation and preconcentration by using octadecyl silica membrane disks modified by a new schiff's base

Ultra-trace amounts of Cu(II) were separated and preconcentrated by solid phase extraction on octadecyl-bonded silica membrane disks modified with a new Schiff,s base (Bis- (2-Hydroxyacetophenone) -2,2-dimethyl-1,3-propanediimine) (SBTD) followed by elution and inductively coupled plasma atomic emission spectrometric detection. The method was applied as a separation and detection method for copper(II) in environmental and biological samples. Extraction efficiency and the influence of sample matrix, flow rate, pH, and type and minimum amount of stripping acid were investigated. The concentration factor and detection limit of the proposed method are 500 and 12.5 pg mL-1, respectively.

A importância da análise de especiação do chumbo em plasma para a avaliação dos riscos à saúde

Lead absorption is influenced by the species that are formed and the physicochemical characteristics of lead, among others. Lead plasma concentration is < 5% of total blood lead and represents the biologically active fraction able to cross the cell membranes. Health risks mainly depend on a specific metal and its species. Speciation analysis is the analytical activity of identifying and determining different metal species. Chromatographic methods are very useful in the identification of species and the techniques most used to determine metals in biological fluids are ICP OES/MS and AAS. Lead speciation analysis in blood plasma is fundamental for understanding and evaluating the interaction mechanisms between that analyte and its biological targets.

Identificação de resíduos de disparos de armas de fogo por meio da técnica de espectrometria de massas de alta resolução com fonte de plasma indutivo

The violence derived from crimes involving firearms represents one of the main concerns of society. For this reason modern techniques have emerged in forensic science to identify suspects at crime scenes. This work describes a methodology to identify residues present in the hands of suspect by using a high resolution inductively coupled plasma mass spectrometry and collection procedure based on ethylenediaminetetraacetic acid (EDTA) solution as a complexing agent in moistened swabs. In order to distinguish real gunshot residues from others types of residues present in the hand of suspect, ternary ratio per cent diagrams were developed for antimony (Sb), barium (Ba) and lead (Pb) detected on the hands of volunteers, before and immediately after shooting tests, revealing a remarkable difference in both situations.

Análise de ácidos graxos não-esterificados de plasma humano por cromatografia gasosa capilar com injeção sem divisão de fluxo

The aim of the present work was to test the combination of non-esterified fatty acid (NEFA) isolation using fumed silicon dioxide with capillary gas-chromatography (C-GC) with splitless injection for the analysis of NEFAs in human plasma. Injection volume, solvent re-condensation and split purge flow-rate were the parameters evaluated for the analysis of fatty acid methyl esters by C-GC. The use of a solvent re-condensation technique, associated with 1.0 µL injection and a split purge flow rate of 80 mL/min resulted in satisfactory analysis of NEFAs. Fourteen fatty acids were identified in plasma samples, ranging from 2.03 to 184.0 µmol/L. The combination of both techniques proved useful for routine analyses of plasma NEFAs.

Decomposição de argilas em forno de microondas e determinação simultânea dos seus constituintes principais por espectrometria de emissão óptica em plasma indutivamente acoplado

In this work a closed-vessel microwave-assisted acid decomposition procedure for clays was developed. Aluminum, Ca, Fe, K, Mg, Na, Si, and Ti were determined in clay digestates by inductively coupled plasma optical emission spectrometry. The most critical parameter for total decomposition of clays was the composition of the reagent mixture. The applied power and the heating time exerted a less critical influence. Best decomposition conditions were attained using a reagent mixture containing 4 mL aqua regia plus 3 mL HF and the heating program was implemented in 12 min. The accuracy of the results was demonstrated using two standard reference materials and a paired t-test showed a good agreement between determined and certified values at a 95% confidence level.

Diazepam e nordiazepam em plasma: métodos de extração líquido-líquido e em fase sólida no pré-tratamento de amostras para análise cromatográfica em fase líquida

Analysis of diazepam (DZP) and its active metabolite nordiazepam (NDZP) in plasma is commonly performed in clinical medicine to ensure proper therapeutic effects while minimizing the incidence of toxicity. This study aimed to optimize analytical parameters and compare two pre-treatment techniques, liquid-liquid (LLE) and solid phase extraction (SPE), as well as liquid chromatographic conditions to analyze simultaneously DZP and NDZP in plasma from 20 patients treated with a daily dose of 10 mg. Both techniques showed to be well in line with the international criteria for analytical validation, which permitted to quantify DZP (66.2 - 1148.6 ng mL-1) and NDZP (138.5 - 808.6 ng mL -1) in all samples. The correlation coefficients between SPE and LLE were respectively 0.9729 for DZP and 0.9643 for NDZP.

PARAFAC: uma ferramenta quimiométrica para tratamento de dados multidimensionais. Aplicações na determinação direta de fármacos em plasma humano por espectrofluorimetria

Since the last decade, the combined use of chemometrics and molecular spectroscopic techniques has become a new alternative for direct drug determination, without the need of physical separation. Among the new methodologies developed, the application of PARAFAC in the decomposition of spectrofluorimetric data should be highlighted. The first objective of this article is to describe the theoretical basis of PARAFAC. For this purpose, a discussion about the order of chemometric methods used in multivariate calibration and the development of multi-dimensional methods is presented first. The other objective of this article is to divulge for the Brazilian chemical community the potential of the combination PARAFAC/spectrofluorimetry for the determination of drugs in complex biological matrices. For this purpose, two applications aiming at determining, respectively, doxorrubicine and salicylate in human plasma are presented.

Use of thin films obtained by plasma polymerization for grain protection and germination enhancement

In this work, preliminary results of the use of hydrophobic thin films obtained by plasma deposition to protect grains and seeds are presented: grains coated by the films did not present biological degradation when stored in a saturated water vapor environment, but had their germination accelerated in the presence of water. A model that explains the difference of behavior of the films when exposed to water in vapor form or in liquid form, based on the formation of microchannels within the film that lead to water uptake in seeds, is presented. The model was successfully tested using quartz crystal measurements, which showed that the microchannels within the films can favor the adsorption and permeation of water when the films are immersed in water.

Desenvolvimento de colunas cromatográficas de meios de acesso restrito proteína-imobilizada e suas avaliações para análise de fármacos com injeção direta de plasma humano

A series of bovine serum albumin-immobilized supports have been prepared and used as restricted access media (RAM) columns. Restricted-access supports combine size-exclusion of proteins and other high-molar-mass matrix components with the simultaneous enrichment of low-molar mass analytes. These characteristics were chromatographically evaluated for the columns. The RAM-BSA (Bovine Serum Albumin) columns showed excellent performance for exclusion of human plasma protein with good retention capacity for a series of acidic, basic, and neutral drugs.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Pré-concentração de cádmio com Saccharomyces cerevisiae e determinação em águas fluviais usando espectrometria de emissão óptica com plasma indutivamente acoplado

A preconcentration method based on the use of Saccharomyces cerevisiae as sorbent material is proposed for the determination of Cd(II) in river water. The solid phase extraction was performed in batch mode and the determination of the analyte in the solid phase was easily carried out by introducing a slurry of the yeast (0.0625 g / 2.5 mL) directly into the ICP OES. A limit of detection of 0.11 µg L-1 and a sample throughput in the range of 4 - 54 sample h-1 were obtained. Determinations of cadmium in a certified sample and in real river water samples were in excellent agreement with the expected values.