Construção e avaliação de um eletrodo tubular sensível ao íon hidrogênio como detector em sistemas de análise em fluxo

The construction of a tubular hydrogen ion-selective potentiometric electrode without inner reference solution, based on the tridodecylamine (TDDA) ionophore, and its evaluation in a flow system are described. TDDA was dissolved in 2-nitrophenyl octyl ether, dispersed in a PVC membrane and applied directly to a conducting support which consisted of an epoxy resin and graphite mixture. The electrode was designed with a tubular geometry to effort facilities to be coupled as part of a flow injection network. The main working characteristics such as response time, linear pH range, selectivity and life time were evaluated and compared with those obtained which a conventionally shaped electrode based on the same sensor. The electrode showed a slope of 51-52 mV dec-1 within a linear pH range from 4.0 up to 12.0.

Determinação de traços de Co e Co2 "em linha" por cromatografia em fase gasosa

The present work describes a rapid and sensitive method for the determination of carbon monoxide and carbon dioxide at low concentration levels, on line, in ethylene and hydrogen lines. These gases were separated in a column filled with Porapak Q, converted to methane and quantified by a flame ionization detector. Some modifications were made in the injection system and in the lines of the carrier gas. The detection limits of 2,6 ppbV and 4,85 ppbV for CO and CO2, respectively, were reached after modifications.

Desenvolvimento de um detector piezelétrico para cromatógrafo a gás interfaceado a microcomputador

A piezoelectric detector based on a commercial quartz crystal of 3.57MHz is shown. A PTFE cell attached to the GC-column outlet holds the polymer-coated crystal, whose terminals were removed. Two TTL oscillators (reference and sensor) are used and the beating of their frequencies is monitored through a home-made counter card inserted in a microcomputer. The original thermal conductivity detector was also interfaced, but through a 12-bit analog-to-digital converter. In spite of the well-known fact that QCM has low sensitivity at high temperatures, results show significant peak deformation for low temperatures. In addition, the phenomenon is also dependent on the chemical composition of the absorbent film besides instantaneous partial pressure and chemical composition of the analyte.

Automated flow-injection method for cadmium determination with pre-concentration and reagent preparation on-line

The spectrophotometric determination of Cd(II) using a flow injection system provided with a solid-phase reactor for cadmium preconcentration and on-line reagent preparation, is described. It is based on the formation of a dithizone-Cd complex in basic medium. The calibration curve is linear between 6 and 300 µg L-1 Cd(II), with a detection limit of 5.4 µg L-1, an RSD of 3.7% (10 replicates in duplicate) and a sample frequency of 11.4 h-1. The proposed method was satisfactorily applied to the determination of Cd(II) in surface, well and drinking waters.

Flow analysis by using solenoid valves for As(III) determination in natural waters by an on-line separation and pre-concentration system coupled to a tungsten coil atomizer

A flow system coupled to a tungsten coil atomizer in an atomic absorption spectrometer (TCA-AAS) was developed for As(III) determination in waters, by extraction with sodium diethyldithiocarbamate (NaDDTC) as complexing agent, and by sorption of the As(III)-DDTC complex in a micro-column filled with 5 mg C18 reversed phase (10 µL dry sorbent), followed by elution with ethanol. A complete pre-concentration/elution cycle took 208 s, with 30 s sample load time (1.7 mL) and 4 s elution time (71 µL). The interface and software for the synchronous control of two peristaltic pumps (RUN/ STOP), an autosampler arm, seven solenoid valves, one injection valve, the electrothermal atomizer and the spectrometer Read function were constructed. The system was characterized and validated by analytical recovery studies performed both in synthetic solutions and in natural waters. Using a 30 s pre-concentration period, the working curve was linear between 0.25 and 6.0 µg L-1 (r = 0.9976), the retention efficiency was 94±1% (6.0 µg L-1), and the pre-concentration coefficient was 28.9. The characteristic mass was 58 pg, the mean repeatability (expressed as the variation coefficient) was 3.4% (n=5), the detection limit was 0.058 µg L-1 (4.1 pg in 71 µL of eluate injected into the coil), and the mean analytical recovery in natural waters was 92.6 ± 9.5 % (n=15). The procedure is simple, economic, less prone to sample loss and contamination and the useful lifetime of the micro-column was between 200-300 pre-concentration cycles.

Determination of etoricoxib in human plasma using automated on-line solid-phase extraction coupled with LC-APCI/MS/MS

A liquid chromatography-tandem mass spectrometry method with atmospheric pressure chemical ionization (LC-APCI/MS/MS) was validated for the determination of etoricoxib in human plasma using antipyrin as internal standard, followed by on-line solid-phase extraction. The method was performed on a Luna C18 column and the mobile phase consisted of acetonitrile:water (95:5, v/v)/ammonium acetate (pH 4.0; 10 mM), run at a flow rate of 0.6 mL/min. The method was linear in the range of 1-5000 ng/mL (r²>0.99). The lower limit of quantitation was 1 ng/mL. The recoveries were within 93.72-96.18%. Moreover, method validation demonstrated acceptable results for the precision, accuracy and stability studies.

Demonstrando os fundamentos, potencialidades e limitações da análise por injeção seqüencial

The sensitivity and accuracy of sequential injection methods are dependent on efficient overlapping of reagent and sample zones as they are propelled toward the detector cell. The formation of the reduced phosphomolybdic acid is used to demonstrate that the overlapping efficiency in a fixed reaction coil relies on a suitable choice of reagent to sample volume ratio. Additionally, under poor mixing conditions or highly concentrated samples, the reaction extension is strongly dependent on the reagent concentration. The zone-sampling concept is exploited to determine phosphate in cola-based soft drinks after in-line dilution in an auxiliary coil.

Determinação de metil-etil-cetona em amostras de urina com amostragem por micro extração em fase sólida (MEFS) em headspace associada à cromatografia gasosa com detector de ionização de chama (CG-DIC)

Methyl ethyl ketone (MEK) is a solvent commonly used in chemical, paint and shoe industry. The aim of this study was to develop and validate a method for urinary quantification of MEK, employing headspace solid phase micro extraction sampling (SPME) coupled to gas chromatography with flame ionization detection (GC-FID). The calibration curve (y=4.6851x-0.0011) presented good linearity with r²=0.9993. Accuracy (94-109%), intra-assay precision (4.07-5.91%) and inter-assay precision (3.03-5.62%) were acceptable. The quantification limit was 0.19 mg/L. This low cost method can be used routinely in the biological monitoring of occupational exposure to MEK, according to the requirements of the Brazilian legislation.

On-line preconcentration system using a microcolumn packed with Alizarin Red S-modified alumina for zinc determination by flame atomic absorption spectrometry

A simple and sensitive on-line flow injection system for determination of zinc with FAAS has been described. The method is based on the separation and preconcentration of zinc on a microcolumn of immobilized Alizarin Red S on alumina. The adsorbed analyte is then eluted with 250 µL of nitric acid (1 mol L-1) and is transported to flame atomic absorption spectrometer for quantification. The effect of pH, sample and eluent flow rates and presence of various cations and anions on the retention of zinc was investigated. The sorption of zinc was quantitative in the pH range of 5.5-8.5. For a sample volume of 25 mL an enrichment factor of 144 and a detection limit (3S) of 0.2 µg L-1 was obtained. The precision (RSD, n=7) was 3.0% at the 20 µg L-1 level. The developed system was successfully applied to the determination of zinc in water samples, hair, urine and saliva.

Determinação de ácido valpróico em soro por cromatografia líquida de alta eficiência com detector de arranjo de diodos (CLAE-DAD), após derivatização com brometo de fenacila

Valproic acid (VA) is a drug used to control seizures in several epileptic conditions. In VA pharmacotherapy, therapeutic drug monitoring is recommended to obtain adequate seizure control and avoid toxicity. The aim of this study was to validate a method for the determination of valproic acid in serum, employing high performance liquid chromatography with diode array detection (HPLC-DAD), after derivatization with phenacyl bromide. The calibration curve (y=0.0133x-0.0025) presented good linearity with r²=0.9999. Accuracy (101-115%), intra-assay precision (4.53-8.15%) and inter-assay precision (3.15-6.77%) were acceptable. The quantification limit was 2.0 µg/mL. The method presented similar results to enzyme immunoassay.

Determinação de etanol e voláteis relacionados em sangue e fluido oral por microextração em fase sólida em headspace associada à cromatografia gasosa com detector de ionização em chama

The aim of this study was to validate a method for the determination of acethaldehyde, methanol, ethanol, acetone and isopropanol employing solid-phase microextraction associated to gas chromatography with flame ionization detection. The operational conditions of SPME were optimized by response surface analysis. The calibration curves for all compounds were linear with r² > 0.9973. Accuracy (89.1-109.0%), intra-assay precision (1.8-8.5%) and inter-assay precision (2.2-8.2%) were acceptable. The quantification limit was 50 µg/mL. The method was applied to the meaurement of ethanol in blood and oral fluid of a group of volunteers. Oral fluid ethanol concentrations were not directly correlated with blood concentrations.

Construção e caracterização de um detector eletroquímico para análises em fluxo

The present work describes a low-cost electrochemical "wall-jet" detector for flow analysis. The electrolytic solution enters into the cell through a tube of stainless steel (200 to 300 µm i.d), reaching to the center of the working electrode perpendicularly and then being mixed to the remaining solution in the cell, which flows under atmospheric pressure into a waste reservoir. The proposed electrochemical detector can be used with any type of working electrode, from commercial to home-made, such as glassy carbon and metallic electrodes (modified or unmodified), which enlarge the applications of the electrochemical detector.

Photometric procedure for quantitative analysis of Aflatoxin B1 in peanuts by thin-layer chromatography using charge coupled device detector

A photometric procedure was developed for determination of aflatoxin B1 in peanuts by TLC-CCD technique. The quantification and detection limit were 1.2 μg kg-1 and 0.4 ng per spot, respectively, with mean recovery of 98%. The CCD camera is sufficiently sensitive to detect small changes in spots fluorescence intensity and the results for performance confirmed the efficiency of the method. Another important property of CCD detector is its linearity for a wide range of luminous stimulus determined by analysis of five-point calibration curves using the intensity of AFB1 fluorescence versus AFB1 concentration (0.8 to 4.8 ng per spot). The method was applied to the analysis of thirty nine peanut samples and aflatoxin B1 levels ranged from 16 to 115 μg kg-1. The TLC-CCD and the photometric procedure developed in this study demonstrated to be a simple and efficient tool for quantitative analyses of AFB1 in peanut samples.

Emprego de sílica gel organicamente modificada e impressa ionicamente para pré-concentração seletiva on-line de íons cobre

The present work purposes the preparation of a silica gel sorbent organically modified with 2-aminoethyl-3-aminobutylmethyldimethoxysilane (AAMDMS) and imprinted with Cu2+ ions by means surface imprinting technique and its use for selective on-line sorbent preconcentration of Cu2+ ions with further UV-VIS spectrophotometric determination by flow injection analysis. The Cu2+-imprinted silica gel, when compared with non imprinted silica gel and silica gel, showed from the binary mixture of Cu2+/Ni2+ relative selectivity coefficient (k') of 6.84 and 5.43 and 6.64 and 19.83 for the mixture Cu2+/Pb2+, thus demonstrating higher selectivity of Cu2+-imprinted silica gel towards Cu2+ ions. Under optimized condition, the on-line preconcentration method provided detection limit of 3.4 μg L-1 and linear range ranging from 30.0 up to 300.0 μg L-1 (r = 0.995). The accuracy of method was successfully assessed by analyzing different kind of spiked water samples with recovery values ranging from 92.2 up to 103.0%.