Chemometric determination of rabeprazole sodium in presence of its acid induced degradation products using spectrophotometry, polarography and anodic voltammetry at a glassy carbon electrode.

Chemometric stability indicating methods are presented for the determination of rabeprazole sodium in presence of its acid induced degradation products using spectrophotometry, differential pulse polarography and differential pulse anodic voltammetry at a glassy carbon electrode. The applied chemometric techniques are multivariate ones including classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). A difference spectrophotometric (DeltaA) method has also been applied. To develop the multivariate calibrations, a training set was used, consisting of 20 mixture solutions of rabeprazole sodium and its degradation products. These mixtures show percentage degradation ranging from 0.5-65%, 0.5-95% and 0.6-75% for the spectrophotometric, polarographic and anodic voltammetric calibrations, respectively. The UV absorbances were recorded in 0.1 M NaOH within the wavelength range 220-340 nm at 2 nm intervals. The polarograms and anodic voltammograms were recorded in Britton-Robinson buffer (pH 8.0) within the potential range -500 to -1508 and 400 to 1192 mV at 6 mV intervals with a pulse amplitude of -100 and 50 mV, sweep rate of 15 and 10 mV s(-1) and pulse interval of 0.4 and 0.6 s for the polarographic and anodic voltammetric methods, respectively. All the studied methods have been validated and successfully applied to the determination of rabeprazole sodium in tablet dosage form. The results were statistically compared to those obtained using a published HPLC method. No significant difference has been found.

A new simple sensitive differential pulse polarographic method for the determination of acrylamide in aqueous solution.

A new simple sensitive differential pulse polarographic (DPP) method was investigated for the determination of acrylamide (AA) directly in a neutral aqueous solution. The AA showed a well-defined and well-resolved peak in pure aqueous LiCl at -1.84V in the potential range from -1.6V to -1.97V at nitrogen pressure of 0.5kgcm(-2). Among the various electrolytes studied, the AA showed good DPP response in the presence of LiCl and tetra methyl ammonium iodide, while it showed poor response in the presence of tetra butyl ammonium hydroxide and tetra butyl ammonium bromide due to their strong adsorption on the surface of electrode which hindered its reduction. The effect of LiCl concentration, the cyclic voltammetric response and the drop time study showed that AA exhibited an irreversible adsorptive electrochemical behavior. The good electrochemical response in pure aqueous medium suggested that hydrogen bonding might be involved which may favor the electrode reaction. Under optimized conditions, the peak current was linear in the entire concentration range from 0.2 mgL(-1) to 20 mgL(-1) with the correlation coefficient of R(2)=0.9998. The method showed good reproducible results with R.S.D. of 0.3% (n=16). The detection limit (LOD) was 27 microgL(-1). The influence of various interfering agents was also studied. The method was applied successfully for the quantification of AA in water samples without any interference effect from alkali metals.

How experimental design can improve the validation process. Studies in pharmaceutical analysis.

A critical discussion about the possibility of improving the method validation process by means of experimental design is presented. The reported multivariate strategies concern the evaluation of the performance parameters robustness and intermediate precision, and the optimisation of bias and repeatability. In particular, accuracy and precision improvement constitutes a special subset of experimental design in which the bias and the relative standard deviation of the assay are optimised. D-optimal design was used in order to plan experiments for this aim. The analytical methods considered were capillary electrophoresis, HPLC, adsorptive stripping voltammetry and differential pulse polarography. All methods were applied to real pharmaceutical analysis problems.

Determination of cadmium, lead, copper and zinc in Yemeni khat by anodic stripping voltammetry.

Trace element concentrations in khat were investigated as they can disturb trace element levels in the body. Cadmium (Cd), lead (Pb), copper (Cu) and zinc (Zn) levels in khat and 6 leafy vegetables commonly consumed in the Republic of Yemen were determined by differential pulse anodic stripping voltammetry after wet digestion of the organic matter. Khat had significantly higher concentrations of Cu and Zn than did the leafy vegetables, but similar amounts of Cd and Pb. The average daily intake of khat consumers of Cd, Pb, Cu and Zn from khat only was estimated to be 2.0-10.2 microg/day, 23.6-118.0 microg/day, 530-2654 microg/day and 662-3311 microg/day respectively. Although high, these values were within Food and Agriculture Organization/World Health Organization tolerance limits.

Optimización de la determinación porpolarografía diferencial de impulsos de ácidoascórbico en fórmulas para lactantes / Optimization of a differential pulse polarography determination of ascorbic acid in infant formulas

El objeto del estudio es la selección de las condiciones adecuadas para la preparación de la muestra y las instrumentales para la determinación de ácido ascórbico en fórmulas de base láctea para lactantes por polarografía diferencial de impulsos. La bondad del método se estima determinando los parámetros analíticos. Se obtiene un límite de detección equivalente a 15 mg de ácido ascórbico por 100 g de fórmula, una respuesta lineal en el intervalo de 15 a 550 mg de ácido ascórbico por 100g de muestra, una precisión interdía del 4,33 por ciento y una recuperación del 95 por ciento, valores que indican la bondad del método para el fin propuesto (AU)

Padronizaçäo do método polarográfico no tumor de Walker em ratos Wistar / Standardization of polarography in Walker tumor inoculated in Wistar rats

Estudo polarográfico foi realizado em 15 ratos Wistar inoculados com tumor de Walker 256, implantando-se eletrodos de platina no tumor e no músculo, com o objetivo de padronizaçäo da polarografia no tumor de Walker 256. Os níveis de oxigênio foram sempre menores no tumor do que no músculo, tanto em condiçöes basais como após a oxigenaçäo. A resposta à oxigenaçäo foi mais lenta no tumor do que no músculo

Oil-in-water emulsions as suitable working media for the direct polarographic determination of aziprotryne and desmetryne from its organic extracts in water samples.

The electroanalytical behavior of the reduction of the herbicides aziprotryne (2-azido-4-isopropylamino-6-methylthio-1,3,5-triazine) and desmetryne (4-isopropylamino-6-methylamino-2-methylthio-1,3,5-triazine) in oil-in-water emulsions is reported. This medium allows the differential pulse polarographic determination of these s-triazines directly from their sample extracts in an appropriate organic solvent. Sodium pentanesulfonate was chosen as the most suitable surfactant to be used as emulsifying agent, whereas ethyl acetate was selected as the organic solvent to form the emulsions. The peak current was maximum in a 0.3 mol L(-1) HClO4 medium of the continuous aqueous phase for aziprotryne, and at pH 3.0 for desmetryne, and the potential became more negative as the pH increased for both herbicides. The limiting current is diffusion controlled and the electrode process is irreversible. Four electrons are involved in the overall electrochemical reduction process as determined by controlled potential coulometry, whereas the alpha n(a) values suggested that two electrons are involved in the rate-determining step. Using differential pulse polarography, aziprotryne and desmetryne can be determined in the emulsified medium over the concentration ranges 1.0 x 10(-7)-1.0 x 10(-4) mol L(-1), with limits of detection of 4.5 x 10(-8) mol L(-1) and 6.6 x 10(-8) mol L(-1), respectively. The method was applied to the determination of aziprotryne and desmetryne in spiked irrigation water. At concentration levels of 6.0 x 10(-7) mol L(-1) aziprotryne and 4.0 x 10(-7) mol L(-1) desmetryne, recoveries of 94 +/- 3% and 94 +/- 4%, respectively, were obtained after preconcentration on Sep-Pack C18 cartridges. Finally, partial least-squares regression (PLSR) has been used for treatment of the polarographic data obtained from mixtures of aziprotryne, desmetryne and simazine in oil-in-water emulsions. The size of the calibration set was of 29 samples by ninety two current measurements at different potentials. Prediction of the herbicides concentration within the range 1.0 x 10(-6)-1.0 x 10(-5) mol L(-1) was possible.

Determination of nicotinamide (NA) using its polarographic catalytic wave in the presence of KIO3.

Nicotinamide (NA) yields a polarographic catalytic wave with a peak potential -1.38 V (vs. SCE) in 0.1 mol/L HAc-NaAc (pH 4.7)/4 x 10(-3) mol/L KIO3 buffer solution. The sensitivity of the catalytic wave increased in one order of magnitude as compared to that of the responding reduction wave without KIO3. Based on this observation, a new method for the determination of NA was recommended. The second order derivative peak current was proportional to the NA concentration in the range of 5 x 10(-8)- 6 x 10(-7) mol/L. 0.11-fold vitamin B1, 0.13-fold B2, 0.14-fold B6 and 8-fold nicotinic acid amounts do not interfere the determination of 1 x 10(-6) mol/L NA. The proposed method was used to determine the NA content in multivitamin tablets, with good agreement to the declared amount.

Electrochemical study on the determination of tinidazole in tablets.

The electrochemical reduction of tinidazole has been carried out in aqueous solution in the pH range 1.8-11.3 by differential-pulse (DP) polarography. Tinidazole exhibits one or two reduction peaks depending on pH. In strongly acidic solution (pH < 4.5), one reduction peak was obtained and it was suitable for analytical purposes. A method for the determination of tinidazole by DP polarography in Britton-Robinson buffer of pH 3.0, which allows quantification over the range 0.03-7.30 microg/ml, was proposed. The method was successfully applied to the determination of tinidazole in tablets with mean recovery and relative standard deviation of 98.7 and 3%, respectively. Excipients did not interfere in the determination.

Applications of chiroptical spectroscopy for the characterization of pharmaceutical compounds.

Many pharmaceutical compounds contain one or more centers of dissymmetry, thus presenting a unique series of regulatory and compendial requirements. Although most often characterized using chiral chromatography, these molecules can be effectively studied using the various techniques of chiroptical spectroscopy. Techniques which have been found to be very useful for such work include polarimetry, optical rotatory dispersion, circular dichroism, and circularly polarized luminescence. The principles underlying each effect will be briefly outlined, and the application of each illustrated through the inclusion of appropriate examples.

The influence of different levels of PEEP on peripheral tissue perfusion measured by subcutaneous and transcutaneous oxygen tension.

OBJECTIVE: To compare subcutaneous (PscO2) and transcutaneous (PtcO2) oxygen tension measurements in relation to hemodynamic variables at different levels of PEEP, and to evaluate the usefulness of these measurements as monitors of peripheral tissue perfusion. DESIGN: Prospective trial. SETTING: Intensive care unit in a university hospital. PATIENTS: Seven patients with gastric cancer who where undergoing total gastrectomy. INTERVENTIONS: Silicone catheter was placed in the upper arm and transcutaneous oxygen monitor was placed on the upper part of the chest. A pulmonary artery catheter was placed in the right pulmonary artery. MEASUREMENTS AND RESULTS: PscO2 and PtcO2 together with hemodynamic variables were measured at different levels of PEEP. Progressive increase of PEEP reduced cardiac index (CI) (p < 0.05) with a concomitant decrease of PscO2 (p < 0.05) and oxygen delivery (DO2) (p < 0.05). Changes in PtcO2 paralleled changes in arterial oxygen tension (PaO2), but no correlation was found between PtcO2, CI and DO2. CONCLUSION: PscO2 is a sensitive indicator of subcutaneous tissue perfusion, which can be used to identify the PEEP level, with optimum peripheral perfusion. PscO2 seems to be a more reliable indicator of tissue perfusion than PtcO2.

Polarographic determination of sorbic acid in fruit juices and soft drinks.

A simple differential-pulse polarographic method using a laboratory-built hanging mercury drop electrode as the working electrode was developed for the determination of sorbic acid in fruit juices and soft drinks. Sorbic acid was extracted from the samples with diethyl ether. After reduction of the ethereal solution to a small volume by direct evaporation, the residual ether was dissolved in the supporting electrolyte (25 ml of acetonitrile + 1 ml of 0.06 M acetic acid + 0.8 g of tetraethylammonium bromide). Peak current was measured at -1.7 V. The working range of the method, without dilution or pre-concentration of the samples, was from 4 to 229 p.p.m. for the original juice and drink samples. The validity of the method was confirmed by parallel determinations using the method of the Association of Official Analytical Chemists and by recovery tests on a large variety of juice samples. Satisfactory recoveries and agreement in results from the two methods were obtained. The recovery and precision (relative standard deviation) of the method were 97 +/- 4 and 100 +/- 3%, respectively, for blackcurrant juice for five determinations.

Halothane mimics oxygen in oxygen microelectrodes.

The effects of halothane and enflurane on the polarographic measurement of oxygen with five platinum and three gold microelectrodes were examined. Oxygen microelectrodes were calibrated in saline solution equilibrated with either nitrogen (N2) or air, then either halothane, 1.0 per cent, or enflurane, 2.0 per cent, was added to the gas mixture. For each electrode, polarographic curves were determined during exposure to five equilibrating gas mixtures: N2, air, N2 plus halothane, air plus halothane, and N2 plus enflurane. Halothane variably increased the current produced (and therefore the estimated oxygen tension) at all polarizing voltages in saline solution equilibrated with either N2 or air. The effect was present in both conical platinum electrodes and recessed-tip gold electrodes and was not prevented by membrane coatings of polystyrol, Rhoplex or collodion. Enflurane did not alter the polarographic measurement of oxygen. It is concluded that tissue oxygen tension measurements, made with these microelectrodes and membranes, may be unreliable in the presence of halothane.