Flow analysis-hydride generation-gas phase derivative molecular absorption spectrophotometric determination of antimony in antileishmanial drugs

In the present work, the development of a method based on the coupling of flow analysis (FA), hydride generation (HG), and derivative molecular absorption spectrophotometry (D-EAM) in gas phase (GP), is described in order to determine total antimony in antileishmanial products. Second derivative order (D²224nm) of the absorption spectrum (190 - 300 nm) is utilized as measurement criterion. Each one of the parameters involved in the development of the proposed method was examined and optimized. The utilization of the EAM in GP as detection system in a continuous mode instead of atomic absorption spectrometry represents the great potential of the analytic proposal.

Spectrophotometric flow injection procedure to indirect determination of paracetamol in pharmaceutical formulations using o-tolidine as reagent

A spectrophotometric flow injection method for the determination of paracetamol in pharmaceutical formulations is proposed. The procedure was based on the oxidation of paracetamol by sodium hypochloride and the determination of the excess of this oxidant using o-tolidine dichloride as chromogenic reagent at 430 nm. The analytical curve was linear in the paracetamol concentration range from 8.50 x 10-6 to 2.51 x 10-4 mol L-1 with a detection limit of 5.0 x 10-6 mol L-1. The relative standard deviation was smaller than 1.2% for 1.20 x 10-4 mol L-1 paracetamol solution (n = 10). The results obtained for paracetamol in pharmaceutical formulations using the proposed flow injection method and those obtained using a USP Pharmacopoeia method are in agreement at the 95% confidence level.

Spectrophotometric flow injection system for determination of Zn2+ in ophthalmic formulations using Alizarin red S

A spectrophotometric flow injection method for the determination of Zn(II) in ophthalmic formulations was developed. In this work, Zn(II) ion was complexed with Alizarin red S in borate buffer solution (pH 9.0) and the chromophore produced was monitored at 520 nm. The analytical curve was linear in the Zn(II) concentration range from 6.05 x 10-6 to 1.50 x 10-4 mol L-1 with a detection limit of 3.60 x 10-6 mol L-1. Recoveries ranged from 96.3 to 105 % and a relative standard deviation of 1.2 % (n = 10) for 5.5x10-5 mol L-1 Zn(II) reference solution were obtained. The sampling rate was 60 h-1 and the results obtained of Zn(II) in ophthalmic products using this procedure are in close agreement with those obtained using a comparative spectrophotometric procedure at 95 % confidence level.

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.

Multicomutação e amostragem binária em análise química em fluxo: determinação espectrofotométrica de ortofosfato em águas naturais

A flow system based on multicommutation and binary sampling process was developed to implement the sample zone trapping technique in order to increase the spectrophotometric analytical range and to improve sensitivity. The flow network was designed with active devices in order to provide facilities to determine sequentialy analyte with a wide concentration range, employing a single pumping channel to propel sample and reagents solutions. The procedure was employed to determine ortophosphate ions in water samples of river and waste. Profitable features such as an analytical throughput of 60 samples determination per hour, relative standard deviation (r.s.d.) of 2% (n = 6) for a typical sample with concentration of 2.78 mg/L were achieved. By applying the paired t-test no significant difference at 95% confidence level was observed between the results obtained with the proposed system and those of the usual flow injection system.

Determinação espectrofotométrica de ácido ascórbico em fármacos empregando amostragem binária em fluxo

A flow system procedure for spectrophotometric determination of ascorbic acid in drugs based on [Fe3+(SCN-)n]+3-n complex decomposition by reduction is described. The flow network was constituted by a set of three-way solenoid valves, controlled by a microcomputer running a software wrote in QuickBasic 4.5 language. The feasibility of the procedure was ascertained by determining ascorbic acid in drug samples with mass ranging from 0.0018 up to 0.0180 g. The results showed an agreement of about 7% when compared with recommended method. Other profitable features such as a standard deviation of 1.5% (n = 7) and a throughput of 120 determinations per hour was also achieved.

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.

Construção e aplicação de uma cela espectrofotométrica de camada delgada para análises em fluxo

A low cost spectrophotometric cell for use in flow analysis was manufactured in acrylic and adapted to a commercial spectrophotometer. The application of this cell was performed in the determination of chromium (VI) in steel samples using the reaction with the alkaloid brucine in presence of oxalic acid and 0.6 mol L-1 sulfuric acid. The cell allows an enlarged analytical range, diminishing the extension of dilutions, which is useful for on-line monitoring of industrial processes.

Determinação enzimática de dopamina em formulações farmacêuticas utilizando sistema de análise por injeção em fluxo com extrato bruto de abacate (Persea americana)

In this work, a spectrophotometric flow injection analysis system using a crude extract of avocado (Persea americana) as a source of polyphenol oxidase to dopamine determination was developed. The substrates and enzyme concentrations from 2.4x10-7 to 5.3x10-4 mol L-1 and 28 to 332 units mL-1 were evaluated, respectively. In addition, the FIA parameters such as sample loop (50 to 500 µL), flow rate (1.4 to 4.3 mL min-1) and reactor length (100 to 500 cm) were also evaluated in a 0.1 mol L-1 phosphate buffer solution (pH 7.0). Dopamine solution concentrations were determined using 277 units mL-1 enzyme solution, 400 mL enzyme loop, 375 µL sample loop, 2.2 mL min-1 flow rate and a reactor of 350 cm. The analytical curve showed a linearity from 5.3x10-5 to 5.3x10-4 mol L-1 dopamine with a detection limit of 1.3x10-5 mol L-1. The analytical frequency was 46 h-1 and the RSD lower than 0.5% for 5.3x10-4 mol L-1 dopamine solution (n=10). A paired t-test showed that all results obtained for dopamine in commercial formulations using the proposed flow injection procedure and a spectrophotometric procedure agree at the 95% confidence level.

Desenvolvimento de um micro-aquecedor para sistemas de análise química em fluxo: determinação espectrofotométrica de manganês em plantas

In this work a micro-heater device to be used as an integral part of the flow analysis manifold is described. The usefulness of the device was demonstrated using it in the development of a multicommutated flow analysis procedure for the spectrophotometric determination of manganese in plant digest. The method was based on the manganese oxidation by periodate in phosphoric acid medium to form the permanganate anion. The reaction development is dependent on the temperature and it was observed that at 25 °C a time interval of ca. 15 min was necessary for the reaction to attain equilibrium. Setting the temperature to 70 ºC, this time interval could be decreased to ca. 30 s. This condition was easily attained employing the proposed micro-heater device coupled to the manifold. The procedure was applied to manganese determination in soybean digests and results compared with those obtained by inductively coupled argon plasma optical emission spectrometry (ICP-OES). No significant difference at 90% confidence level was observed. A linear response for sample concentrations ranging from 5.0 to 30.00 mg L-1 Mn2+; a relative standard deviation of 1.3% (n = 6) for a typical sample containing 6.3 mg L-1 Mn2+; a sampling rate of 22 determinations per hour; a low reagent consumption, of 12.0 mg NaIO4 per determination; and a detection limit of 1.2 mg L-1 were achieved.

Multímetro interfaceado de baixo custo para aquisição de dados

A digital multimeter (~U$ 240.00 on the national market) connected to a microcomputer by a RS-232 serial interface is proposed for data acquisition in equipment with analog output. Data are measured at the rate of 2 points per second and stored in text files by the software that accompanies the device, running in a Windows environment. The performance of the multimeter was verified by monitoring the transient signals generated in flow injection systems associated with fluorimetric, spectrophotometric and flame photometric detection. In addition, the performance of the proposed device was similar to that attained by employing an interface card with a 12-bit analog-to-digital converter for acquisition of the signals generated by a capillary electrophoresis equipment with oscillometric detection.

Estratégias para aumento de sensibilidade em espectrofotometria UV-VIS

Spectrophotometry is one of the most widespread analytical techniques due to its simplicity, reliability, and low-cost instrumentation for both direct measurements and coupled to other techniques or processes such as chromatography, electrophoresis and flow analysis. However, the application is often limited by sensitivity. This article describes some advances that greatly improve the performance of spectrophotometric measurements, especially in order to increase sensitivity, including the employment of liquid-core waveguides and solid-phase spectrophotometry.

Construção de uma cela de fluxo de longo caminho óptico para medidas espectrofotométricas

A simple and low-cost flow cell with 30 cm optical path for spectrophotometric measurements is described. It presents desirable characteristics such as low attenuation of the radiation beam and internal volume (75 µL) comparable to that of a 1-cm conventional cell (80 µL). Despite the increase in optical path, the effect on sample dispersion was also similar to that attained in the commercial cell. The performance of the cell was assessed by the determination of phosphate based on the molybdenum blue method, yielding a linear response range between 0.05 and 0.8 mg L-1 phosphorus (r=0.999). The increase in sensitivity (30.4-fold) in comparison with that obtained with a conventional 1-cm flow cell agreed with that estimated by the Lambert-Beer law.

Sistema de análises em fluxo polivalente para a determinação espectrofotométrica de fármacos

A flow system based on the sandwich technique is proposed for the sequential determination of ascorbic acid, dipyrone, acetylcysteine, captopril and paracetamol. The procedure is based on the reduction of Cu(II) by the analytes followed by the spectrophotometric measurement of the complex of Cu(I) with 2,2'-biquinoline 4,4'-dicarboxylic acid. Linear responses were achieved in the µmol L-1 range, with coefficients of variation better than 1.7%. Sampling rate was estimated as 60 determinations per hour, consuming 230 µg of BQA and generating 2.5 mL of waste per determination. Results for commercial samples agreed with those obtained by procedures recommended by the American and European pharmacopeias at the 95% confidence level.

Uso de hardware de código fonte aberto "Arduino" para acionamento de dispositivo solenoide em sistemas de análises em fluxo

This paper describes the use of the open source hardware platform, denominated "Arduino", for controlling solenoid valves for solutions handling in flow analysis systems. System assessment was carried out by spectrophotometric determination of iron (II) in natural water. The sampling rate was estimated as 45 determinations per hour and the coefficient of variation was lower than 3%. Per determination, 208 µg of 1-10-phenanthroline and ascorbic acid were consumed, generating 1.3 mL of waste. "Arduino" proved a reliable microcontroller with low cost and simple interfacing, allowing USB communication for solenoid device switching in flow systems.