Detecção eletroquímica em eletroforese capilar

This review focuses the development of electrochemical detection systems coupled to capillary electrophoresis. Conductometric, amperometric, voltametric, and potentiometric modes of detection are reviewed. The positioning of the electrodes, interferences of high electric field, and the materials employed in the fabrication and modification of the electrodes are discussed. The advantages of the use of electrochemical detection with capillary electrophoresis, regarding to the sensitivity and selectivity, is exemplified with a large number of applications. Also, the use of electrochemical detection systems in microchip technology is addressed.

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.

Análise de ácidos graxos por eletroforese capilar utilizando detecção condutométrica sem contato

This article describes a novel approach to the separation of fatty acids ranging from 8 to 20 carbons using capillary electrophoresis with contactless conductivity detection. Complete separation of nine linear chain fatty acids (from C8:0 to C20:0) was achieved in 15 min under normal polarity operation. Limits of detection ranged from 35 to 319 µmol L-1 for C20:0 to C8:0, respectively. The optimized running electrolyte composition was 5.0 mmol L-1 phosphate buffer at pH 7, 4.0 mmol L-1 dimethyl-b-cyclodextrin, 2.0 mmol L-1 trimethyl-b-cyclodextrin, acetonitrile 50% (v/v), and methanol 20% (v/v). The applicability of the separation system was demonstrated by the analysis of coconut vegetable oil.

Análise enantiosseletiva de fármacos: contribuições da cromatografia líquida de alta eficiência e eletroforese capilar

The demand for analytical methods suitable for accurate and reproducible determination of drug enantiomers has increased significantly in the last years. High-performance liquid chromatography (HPLC) using chiral stationary phases and capillary electrophoresis (CE) are the most important techniques used for this purpose. In this paper, the fundamental aspects of chiral separations using both techniques are presented. Some important aspects for the development of enantioselective methods, particularly for the analysis of drugs and metabolites in biological samples, are also discussed.

Um equipamento de eletroforese capilar com detecção condutométrica construído em laboratório

A new construction of a capillary electrophoresis instrument with a universal conductivity detector (oscillometric detector) is described. The performance of the electrophoresis equipment was evaluated through the separation and detection of inorganic anions and cations in aqueous solutions. The results reproduced those found in the literature for the investigated probe ions, showing an efficient separation and good repeatability.

Avaliação de contaminantes inorgânicos e orgânicos em álcool combustível utilizando eletroforese capilar

This work reports the analysis of inorganic and organic contaminants in alcohol fuel samples using capillary electrophoresis. Chloride and sulfate were analyzed in nitrate/ monochloroacetic acid at 10 mmol L-1 concentration each under indirect UV detection (210 nm). The analysis of aldehydes is based on the 216 nm detection of 3-methyl-2-benzothiazoline hydrazone adducts. The running buffer consisted of 20 mmol L-1 tetraborate , 40 mmol L-1 sodium dodecyl sufate and 12 mmol L-1 beta-ciclodextrin. Both methodologies were applied to real samples indicating inorganic ion concentrations from 0.15 to 6.64 mg kg-1 and aldehydes from 32.0 to 91.3 mg L-1.

Espectroscopia de correlação bidimensional: fundamentos, aplicações e perspectivas

This paper presents the basic theory of generalized two-dimensional correlation spectroscopy. This method is applicable to various types of spectroscopy, including Infrared, Near Infrared and Raman Spectroscopy and it emphasizes spectral features not readily observable in conventional one-dimensional spectra. Some applications are cited, including work developed in Brazil.

Caracterização de amostras petroquímicas e derivados utilizando cromatografia gasosa bidimensional abrangente (GCxGC)

The goal of this article is to discuss the application of comprehensive two-dimensional gas chromatography (GCxGC) to petrochemical samples. The use of GCxGC for petroleum and petroleum derivatives characterization, through group type analysis, or BTEX (benzene, toluene, ethylbenzene, xylenes), total aromatic hydrocarbons, polyaromatic hydrocarbons, sulfur-containing, oxygen-containing, and nitrogen-containing compounds is presented. The capability of GCxGC to provide additional specific chemical information regarding petroleum processing steps, such as dehydrogenation of linear alkanes, the Fischer-Tropsch process, hydrogenation and oligomerization is also described. In addition, GCxGC analyses of petrochemical biomarkers and environmental pollutants derived from petrochemicals are reported.

Utilização de um monitor de vídeo como fonte de alta tensão para eletroforese capilar

This article describes the use of a conventional CRT monitor as a high voltage power supply for capillary electrophoresis. With this monitor, a 23-kV high voltage with a ripple of 1.32% was observed. The reproducibility of the applied high voltage was evaluated by measuring the standard deviations of peak area and migration time for five consecutive injections of a test mixture containing potassium, sodium, and lithium cations at 50 mmol L-1. The errors were about 2.5% and 0.6% for peak area and migration time, respectively. The maximum current tested was about 180 mA, which covers most capillary electrophoresis applications. This system has been successfully used for several months, maintaining the desired level of performance.

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.

Cromatografia gasosa bidimensional abrangente (GC × GC)

This paper presents the fundamental principles, instrumentation and selected applications of comprehensive two-dimensional gas chromatography (GC × GC). In this technique, introduced in 1991, two capillary columns are coupled and proper modulating interfaces continuously collect the eluate from the first column, transferring it to the second column. The result is a geometric increment in the chromatographic resolution, ensuring separation of extremely complex mixtures in time periods shorter or comparable to those of analysis using conventional gas chromatography and with better detectabilities and sensitivities.

Estratégias de pré-concentração em eletroforese capilar (CE): parte 1. Manipulação da velocidade eletroforética do analito

Capillary electrophoresis has become a well-established and routine-based separation technique. It is based on the differences between charged analyte mobility in aqueous or organic electrolytes. Its major limitation is the sensitivity due to small sample injection volumes and the narrow diameter of the capillaries, especially when UV detection is used. There are a number of ways to increase the concentration sensitivity. This report shows some on-line preconcentration strategies to perform it in free solution capillary electrophoresis that are based on manipulation of the analyte electrophoretic velocity during the sample introduction (stacking, field amplification and transient isotachophoresis).

Determinação simultânea de cátions empregando eletroforese capilar com detecção condutométrica sem contato em equipamento construído em laboratório

This work describes the development of a home-made capillary electrophoresis (CE) system based on the capacitively coupled contactless conductivity detection (C4D) for the separation of the metallic species Zn2+, Cr3+, Pb2+, Cd2+, Co2+, Cu2+, Ni2+ e Tl+. A background electrolyte composed of MES/Histidine 0,02 mol L-1 (pH 5.0) was optimized for the separation of the metallic species by using organic solvents and complexing agents as additives. The system allowed the determination of the metallic species using MES/Histidine 0,02 mol L-1 and methanol 5% (pH 5.0) as a background electrolyte, 15 kV separation voltage and hydrodynamic injection by gravity.

Estratégias de pré-concentração em eletroforese capilar: parte 2. Manipulação da velocidade da fase dispersa/secundária

This work describes CE preconcentration strategies based on the effect of manipulation of the disperse/secondary velocity. Introduced by Terabe et al. in 1984, micellar electrokinetic chromatography is a powerful separation approach that increases the usage of electrokinetic phenomena for the separation of nonionic compounds. The main disadvantage of MEKC is the low concentration sensitivity associated with the limited optical path length for on-capillary photometric detection and the limited volume of sample solution that can be injected. This paper compiles on-line concentration strategies for neutral analytes by sample stacking and sweeping in micellar electrokinetic chromatography.

Desenvolvimento de métodos analíticos para determinação de agrotóxicos em sedimentos por cromatografia gasosa monodimensional e bidimensional abrangente com micro detector de captura de elétrons

The development of analytical methods for determination of eight pesticides of different chemical classes (trichlorfon, propanil, fipronil, propiconazole, trifloxystrobin, permethrin, difenoconazole and azoxystrobin) in sediments with gas chromatography-micro-electron capture detector (GC/µECD) and comprehensive two-dimensional gas chromatography with micro-electron capture detector (GCxGC/µECD) is described. These methods were applied to real sediment samples, and the best results were obtained using a 5% diphenyl-methylpolysiloxane column for 1D-GC. For GCxGC the same column was employed in the first dimension and a 50%-phenyl-methylpolysiloxane stationary phase was placed in the second dimension. Due to the superior peak capacity and selectivity of GCxGC, interfering matrix peaks were separated from analytes, showing a better performance of GCxGC.