Determination of carbofuran and 3-hydroxycarbofuran residues in coconut water by solid-phase extraction and liquid chromatography with UV detection

A simple method was developed to determine carbofuran and 3-hydroxycarbofuran in coconut water. The procedure involved solid-phase extraction using C-18 cartridges with acetonitrile for elution. The analysis of these compounds was carried out by liquid chromatography with UV detection at 275 nm using a gradient solvent system. The method was validated with fortified samples at different concentration levels (0.01-2.5 mu g/mL). Average recoveries ranged from 81 to 95% with relative standard deviation between 1.6 and 12.5%. Each recovery analysis was repeated at least five times. Detection limits ranged from 0.008 to 0.01 mu g/mL. The analytical procedure was applied to coconut water samples from palms submitted to treatment with commercial formulation under field conditions.

Tungsten permanent chemical modifier with co-injection of Pd(NO3)(2)+Mg(NO3)(2) for direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry

A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer (THGA((R))) used together with Pd(NO3)(2) + Mg(NO3)(2) as modifier is proposed for the direct determination of lead in vinegar by graphite furnace atomic absorption spectrometry. The optimized heating program (temperature, ramp time, hold time) of atomizer involved drying stage (110 degrees C, 5 s, 30 s; 130 degrees C, 5 s, 30 s), pyrolysis stage (1000 degrees C, 15 s, 30 s), atomization stage (1800 degrees C, 0 s, 5 s) and clean-out stage (2450 degrees C, I s, 3 s). For 10 mu L of vinegar delivered into the atomizer and calibration using working standard solutions (2.5-20.0 mu g L-1 Pb) in 0.2% (v/v) HNO3, analytical curve with good linear correlation (r = 0.9992) was established. The characteristic mass was 40 pg Pb and the lifetime of the tube was around 730 firings. The limit of detection (LOD) was 0.4 mu g L-1 and the relative standard deviations (n = 12) were typically <8% for a sample containing 25 pg L-1 Pb. Accuracy of the proposed method was checked after direct analysis of 23 vinegar samples. A paired t-test showed that results were in agreement at 95% confidence level with those obtained for acid-digested vinegar samples. The Pb levels varied from 2.8 to 32.4 pg L-1. Accuracy was also checked by means of addition/recovery tests and recovered values varied from 90% to 110%. Additionally, two certified reference materials were analyzed and results were in agreement with certified values at a 95% confidence level. (C) 2006 Elsevier Ltd. All rights reserved.

Quantitative determination of anti-fungal and insecticide amides in adult plants, plantlets and callus from Piper tuberculatum by reverse-phase high-performance liquid chromatography

A rapid, sensitive and reliable reverse-phase HPLC method was used for the quantitative determination of the anti-fungal and insecticide amides, dihydropiplartine (1), piplartine (2), Delta(alpha,beta)-dihydropiperine (3) and pellitorine (4) in plants in natura, in plantlets in vitro and ex vitro, and in callus of Piper tuberculatum. Well-resolved peaks were obtained with good detection response and linearity in the range of 15.0-3000 mug/mL. The plants in natura contained compounds 1-4, the plantlets ex vitro and in vitro accumulated compounds 1-2 and 1-4, respectively, while only amide 4 was found in callus. Copyright (C) 2003 John Wiley Sons, Ltd.

On-line extraction and determination of carbofuran in raw milk by direct HPLC injection on an ISRP column

A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-Cs) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5 - acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.

Anodic stripping voltammetric determination of aurothiomalate in urine using a screen-printed carbon electrode

This work describes an electroanalytical method for determining gold(I) thiomalate, aurothiomalate, widely used for treatment of reumatoid arthiritis, using a screen-printed carbon electrode (SPCE). Aurothiomalate (AuTM) was determined indirectly at the same electrode by accumulating it first at -1.5 V vs. printed carbon. At this potential in the adsorbed state, the AuTM is reduced to Au(0), which is then oxidized at two steps at -0.22 V and +0.54 V on SPCE. Using optimized conditions of 60 s deposition time, -1.5 V (vs. printed carbon) accumulation potential, 100 mV s(-1) scan rate, linear calibration graphs can be obtained by monitoring the peak at +0.54 V for AuTM in HCl 0.1 mol L-1 from 1.43 x 10(-6) to 1.55 x 10(-4) mol L-1. A limit of detection obtained was 6.50 x 10(-7) mol L-1, and the relative standard deviation from five measurements of 3.0 x 10(-5) mol L-1 AuTM is 4.5%. The method was successfully applied for AuTM determination in human urine sample.

A new potentiometric ibuprofenate ion sensor immobilized in a graphite matrix for determination of ibuprofen in tablets

The characteristics, performance, and application of an electrode, namely, Pt vertical bar Hg vertical bar Hg-2(IBP)(2)vertical bar Graphite, where IBP stands for ibuprofenate ion, are described. This electrode responds to IBP with sensitivity of (58.6 +/- 0.9) mV decade 1 over the range 5.0 x 10(-5)-1.0 x 10(-1) mol L-1 at pH 6.0-9.0 and a detection limit of 3.8 x 10(-5) mol L-1. The electrode is easily constructed at a relatively low cost with fast response time (within 1530 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for ibuprofen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of ibuprofen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure. (c) 2006 Elsevier B.V. All rights reserved.

Analytical procedure for total mercury determination in fishes and shrimps by chronopotentiometric stripping analysis at gold film electrodes after microwave digestion

A method for the total mercury determination in fish and shrimps employing chronopotentiometric stripping analysis on gold film electrodes is described. Fish and shrimp tissues were digested using a microwave oven equipped with closed vessels. We developed a microwave heating program which decomposed all the samples employing diluted nitric acid and hydrogen peroxide. The proposed method was validated by analyzing a certified reference material and then applied for different fish species from fresh water and seawater acquired in local markets of São Paulo city, Brazil. The Brazilian legislation establishes 0.5 and 1 mg per kilogram of fish as upper limit of mercury for omnivorous and predator species, respectively. Except for blue shark tissues, the mercury content was situated below 0.5 mu g g(-1) for all the analyzed samples. The detection limit of the proposed method was calculated as 5 ng g(-1) of sample utilizing 5 minutes of electrodeposition (+300 mV vs. Ag/AgCl) on the gold electrode. (c) 2006 Elsevier Ltd. All rights reserved.

Use of sugar cane bagasse as solid phase extractor for cadmium determination by FAAS

The present paper describes the use of sugar cane bagasse as solid phase extractor for cadmium determination after complexation of the analyte with ammonium diethyldithiophosphate (ADDP) and sorption of the Cd-DDP complexes on the solid support. The concomitants were separated using a flow injection analysis (FIA) system coupled to flame atomic absorption spectrometry (FAAS) for determination. The main parameters such as ADDP concentration, acid medium, flow rate, reaction coil length, and reaction time were investigated.The results obtained with HNO3 showed good accuracy and precision. The enhancement factor was 20.5 times for a 120-second preconcentration time, and the analytical frequency was 25 determinations per hour. The calibration curve was linear over the concentration range of 1-40 mu g L-1 Cd with a LOD of 0.697 mu g L-1 Cd and a relative standard deviation of 0.96% after 12 successive measurements of 30 mu g L-1 Cd.The proposed method was evaluated for the FIA-FAAS analysis of certified reference materials (tomato leaves, spinach leaves, and bovine liver) and Cd-spiked foods (shrimp, sardine, tuna, chicken liver and bovine liver). Good recoveries (80.0-97.1%) for the Cd-spiked samples and certified reference materials were obtained. The results of bagasse-packed minicolumns were compared with Si-C,8 packed minicolumns. The F-test was applied between Si-C-18/Bagasse minicolumns, Si-C-18/certified values, and bagasse/certified values. It was found that the results were in agreement with the certified values at a 95% confidence level.

Phosphite determination in fertilizers after online sequential sample preparation in a flow injection system

A flow injection spectrophotometric system is proposed for phosphite determination in fertilizers by the molybdenum blue method after the processing of each sample two times on-line without and with an oxidizing step. The flow system was designed to add sulfuric acid or permanganate solutions alternately into the system by simply displacing the injector-commutator from one resting position to another, allowing the determination of phosphate and total phosphate, respectively. The concentration of phosphite is obtained then by difference between the two measurents. The influence of flow rates, sample volume, and dimension of flow line connecting the injector-commutator to the main analytical channel was evaluated. The proposed method was applied to phosphite determination in commercial liquid fertilizers. Results obtained with the proposed FIA system were not statistically different from those obtained by titrimetry at the 95% confidence level. In addition, recoveries within 94 and 100% of spiked fertilizers were found. The relative standard deviation (n = 12) related to the phosphite-converted-phosphate peak alone was <= 3.5% for 800 mg L-1 P (phoshite) solution. Precision due to the differences of total phosphate and phosphate was 1.1% for 10 mg L-1 P (phosphate) + 3000 mg L-1 P (phosphite) solution. The sampling rate was calculated as 15 determinations per hour, and the reagent consumption was about 6.3 mg of KMnO4, 200 mg of (NH4)(6)Mo7O24 center dot 4H(2)O, and 40 mg of ascorbic acid per measurement.

Spectrophotometric determination of dipyrone in pharmaceutical preparations by using chromotropic acid

A spectrophotometric method for the determination of dipyrone in pharmaceutical preparations is proposed. This method is based on selective oxidation of dipyrone, in the presence of sulphuric acid, splitting off formaldehyde which reacts with chromotropic acid, also in a sulphuric acid medium, producing a violet-red compound (lambda(max) 575 nm). Beer's law is obeyed in a concentration range of 0.57-5.7 ppm dipyrone with an excellent correlation coefficient (r = 0.9997). The results show a simple, accurate, selective and readily applied method to the determination of dipyrone in pharmaceutical products. The analytical results obtained for these products by the proposed method are in agreement with those of the Brazilian Pharmacopoeia procedure. No interference was observed from common excipients in formulations. Recoveries were within 98.7-101.2%, with standard deviations ranging from 0.2 to 1.7%. (C) 1999 Elsevier B.V. S.A. All rights reserved.

Benzoate ion determination in beverages by using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely. Pt\Hg\Hg-2(Bzt)(2)\graphite, where Bzt stands for benzoate ion. are described. This electrode responds to Bzt with sensitivity of 57.7 +/- 1.0 mV/decade over the range 5 x 10(-4)-1 x 10(-1) mol l(-1) at pH 6.0-8.0 with a detection limit of 1.6 x 10(-4) mol l(-1). The electrode shows easy construction, fast response rime (between 10-30 s), low-cost, acid excellent response stability (lifetime > 6 months, in continuous use), the proposed sensor displayed good selectivity for benzoate in the presence of several carboxylate and inorganic anions. It was used to determine benzoate in various beverages by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by the official AOAC spectrophotometric method and by a HPLC procedure as well. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GRAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect back- ground correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier, With 5 mug Pd + 3 mug Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400degreesC and 2100degreesC, respectively, and 20 muL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 - 50.0 mug L-1 for As, Sb, Se; 10.0 - 100 mug L-1 for Cu; and 20.0 - 200 mug L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 mug L-1 As, 0.2 mug L-1 Cu, 0.6 mug L-1 Mn, 0.3 mug L-1 Sb, 0.9 mug L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 mug L-1, 1000 mug L-1, 2000 mug L-1, 5 mug L-1, and 50 mug L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mu Sb and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by GFAAS

A method has been developed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by graphite furnace atomic absorption spectrometry (GFAAS) using a transversely heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages using the mixture Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3, and diluted ethanol (1 + 1, v/v) containing different nitric acid concentrations. With 5 rhog Pd + 3 mug Mg as the modifiers, pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1200 C and 2200degreesC respectively. For 20 muL of diluted sample (10 muL ethanol + 10 muL of 0.28 mol L-1 HNO3) dispensed into the graphite tube, analytical curves in the 2.0 - 50 mug L-1 Al, As, Cu, Fe, Mn, Ni ranges were established. The calculated characteristic masses were - 37 pg Al, 73 pg As, 31 pg Cu, 16 pg Fe, 9 pg Mn, and 44 pg Ni, and the lifetime of the tube was around 2 50 firings. The limits of detection (LOD) based on integrated absorbance were 1.2 mug L-1 Al, 2.5 mug L-1 As. 0.22 mug L-1 Cu, 1.6 L-1 Fe 0.20 mug L-1 Mn 1.1 mug L-1 Ni. The relatively standard deviations (n = 12) were less than or equal to 3%, less than or equal to 6%, less than or equal to 2%, less than or equal to 3.4%, less than or equal to 1.3%, and less than or equal to 2% for Al, As, Cu, Fe, Mn, and Ni, respectively, the recoveries of Al, As, Cu, Fe, Mn and Ni added to fuel ethanol samples varied from 77% to 112%, 92% to 114%, 104% to 113%, 73% to 116%, 91% to 122% and 93% to 116%, respectively. Accuracy was checked for Al, As, Cu, Fe, Mn, and Ni determination in 20 samples purchased at local gas stations in Araraquara city, Brazil. A paired t-test showed that the results were in agreement at the 95% confidence level with those obtained by single-element GFAAS.

p-Aminobenzoate ion determination in pharmaceutical formulations by using a potentiometric sensor immobilized in a graphite matrix

The characteristics, performance, and application of an electrode, namely, Pt\Hg\Hg-2(PABzt)(2)\ graphite, where PABzt stands for p-aminobenzoate ion, are described. This electrode responds to PABzt with sensivity of (58.1 +/- 1.0) mV per decade over the range 1.0 x 10(-4) to 1.0 x 10(-1) mol l(-1) at pH 6.5-8.0 and a detection limit of 3.2 x 10(-5) mol l(-1). The electrode shows easy construction, fast response time (within 10-30 s), low-cost, and excellent response stability (lifetime greater than 6 months, in continuous use). The proposed sensor displayed good selectivity for p-aminobenzoate in the presence of several substances, especially, concerning carboxylate and inorganic anions. It was used to determine p-aminobenzoate in pharmaceutical formulations by means of the standard additions method. The results obtained by using this electrode compared very favorably with those given by an HPLC procedure. (C) 2004 Elsevier B.V. All rights reserved.

Determination of furosemide in pharmaceutical formulations by diffuse reflectance spectroscopy

In this report an analytical method to determine furosemide by using diffuse reflectance spectroscopy is presented. This study shows that this technique can give quantitative results using spot test analysis, particularly in the case of pharmaceuticals containing furosemide. The color spot test could be obtained by reaction between furosemide with p-dimethylaminocinnamaldehyde, in acid medium. This reaction produced a stable complex on filter paper after heating to 80degreesC for 5 min. All reflectance measurements were carried out at 585 nm and the linear range was from 7.56 x 10(-3) to 6.05 x 10(-2) mol l(-1), with a correlation coefficient of 0.999. The limit of detection was estimated to be 2.49 x 10(-3) mol l(-1) (R.S.D. = 1.7%) and the effect of common excipients on the reflectance measurements was evaluated. The method was applied to determine furosemide in commercial brands of pharmaceuticals. The results obtained by the proposed method were favorably compared with those of the official method, showing for the first time ever that quantitative spot test analysis by diffuse reflectance could be successfully used to determine furosemide in tablets. (C) 2004 Elsevier B.V. All rights reserved.