Voltammetric behaviour and square-wave voltammetric determination of the potent antioxidant and anticarcinogenic agent ellagic acid in foodstuffs.

The voltammetric behaviour of ellagic acid (EA) is investigated by cyclic, differential pulse and square-wave voltammetry (CV, DPV and SWV, respectively). Based on the anodic oxidation peak at approximately 0.42V in acetic/acetate buffer (pH 5.5) a robust and a highly reliable square-wave voltammetric method is presented for the determination of EA. The oxidation peak current was linearly dependent on the concentration of EA in the range of 1.0×10(-7)-1.5×10(-6)mol/L (r=0.9997), with a detection limit of 1.0×10(-8)mol/L (S/N=3) and a quantification limit of 3.4×10(-8)mol/L (S/N=10), good reproducibility and a satisfactory level of selectivity towards others polyphenols. The proposed method was applied to the determination of free and total EA in fruits, nuts and juices with good analytical results being obtained.

Flow-through bulk optode for the fluorimetric determination of perchlorate.

A flow-through fluorescence bulk optode for the flow-injection determination of perchlorate is described. As the active constituents the optode incorporates the lipophilized pH indicator fluorescein octadecyl ester and methyl tridodecyl ammonium chloride, dissolved in a plasticized poly (vinyl) chloride membrane entrapped in a cellulose support. The optode is applied in conjunction with the flow injection technique for perchlorate determination at pH 4.5 (acetic-acetate). The sensor is readily regenerated with the pH 10.4 (TRIS) carrier solution. The analytical characteristics of this optode with respect to perchlorate response time, dynamic measurement range, reproducibility and selectivity are discussed. The proposed FI method is applied to the determination of perchlorate in waters from different sources.

Determination of zinc (II) in pharmaceuticals based on a flow-through bulk optode.

A method based on flow injection (FI), was applied for the determination of Zn (II) using a flow-through bulk optode membrane that incorporates 1-(2-pyridylazo)-2-naphthol in a plasticized poly (vinyl chloride) membrane entrapped in a cellulose support. The calibration graph plotting the reflectance at 562 nm versus [Zn (II)] was linear in the range 0.16-3.27 mgl(-1) (2.5 x 10(-6)-5 x 10(-5) M) with a detection limit of 0.10 mgl(-1). The variation coefficients of the sensor response for 0.33 mgl(-1) of Zn (II) were +/-0.11% for consecutive measurements (n=10), +/-0.19% between days (n=5) and +/-0.22% between different membranes (n=6). The sensor can be readily regenerated with the same acetic/acetate carrier of pH 3.9. The FI method proposed was applied to the determination of zinc (II) in pharmaceuticals.

Kinetic methods for the determination of cadmium(II) based on a flow-through bulk optode.

Three kinetic methods based on flow injection, flow, and stopped-flow injection were applied for the determination of Cd(II) using a flow-through bulk optode membrane that incorporates 1-(2-pyridylazo)-2-naphtol (PAN) in a plasticized poly(vinyl) chloride membrane entrapped in a cellulose support. The calibration graphs plotting the reflectance at 560 nm versus [Cd(II)](1/2) for the first two methods and versus [Cd(II)] for the third were linear up to 56.2 mg l(-1). The detection limits of the methods were 0.01, 0.06 and 0.8 mg l(-1), respectively. The FI method was selected for application purposes. The variation coefficient of the sensor response for 11.2 mg l(-1) of Cd(II) was +/-0.31 and +/-0.65% between different membranes. The sensor can be readily regenerated with a carrier (acetic-acetate) buffer of pH 4. The FI method was applied to the determination of cadmium in an alloy and in water.

Development of a new flow-through bulk optode for the determination of manganese(III).

A flow-through bulk optode based on the use of 1-(2-pyridylazo)-2-naphthol (PAN) immobilized in a plasticized poly(vinyl chloride) membrane entrapped in a cellulose support, in conjuntion with the flow injection analysis technique, is proposed for the determination of manganese(II). The calibration graph obtained at 570 nm was linear in the range 0.27-27.5 mg L(-1) (5 x 10(-6)-5 x 10(-4) M) Mn(II) with a detection limit of 0.18 mg L(-1). The coefficients of variation of the sensor response for 5.5 mg L(-1) of Mn(II) were +/-0.22% for consecutive measurements (n = 10), +/-0.48% between days (n = 5) and +/-0.38% between different membranes (n = 6). The sensor was readily regenerated with the carrier acetic acid/acetate buffer of pH 4.5. The method was applied to the determination of manganese in steels, waters and lemon tree leaves.

A new procedure for the construction of flow-through optodes. Application to determination of copper (II).

A new procedure for constructing an optical fibre reflectance, bulk optode membrane type, sensor is presented. The optode membrane consists of a plasticized poly (vinyl chloride) membrane in which the ionophore is dissolved, entrapped in a cellulose support. The new optode with the dye indicator 1-(2-pyridylazo)-2-naphthol (PAN) was incorporated in a new flow-through cell and the injection system was optimized to determine Cu (II) at 567 nm in the range 5 x 10(-5)-10(-3) M. The response was reproducible and the optode can be regenerated using 10(-2) M EDTA followed by water. The method was applied to the determination of copper in real samples.

Simultaneous determination of propacetamol and paracetamol by derivative spectrophotometry.

A first-derivative spectrophotometric method for the simultaneous determination of propacetamol hydrochloride (PRO) and paracetamol (PA) is described. Measurements are made at the zero-crossing wavelengths at 242.0 for PRO and 239.0 nm for PA. The calibration graphs were linear up to 20.0 and 15.0 mg l(-1) of PRO and PA, respectively, the limits of quantification were 0.75 and 0.46 mg l(-1). The possible interfering effects of other substances were studied. The method was applied to determining the stability of PRO in ethanolic solutions and in glucose and saline parenteral solutions.

Spectrophotometric methods for determining meloxicam in pharmaceuticals using batch and flow-injection procedures.

Two sensitive and fast spectrophotometric methods using batch and flow-injection procedures for the determination of meloxicam (MX) are proposed. The methods are based on the formation of a green complex between this drug and Fe(III) [2MX/Fe(III)] in a methanolic medium. The calibration graphs resulting from measuring the absorbance at 570 nm are linear over the ranges 2.0-200 and 5.00-250 mg l(-1) with detection limits of 0.47 and 0.72 mg l(-1), respectively. Furthermore, a flow-injection spectrophotometric method involving measurement of the absorbance of the drug at 362 nm in 0.1 M NaOH is presented. The calibration graph is linear over the range 0.5-20 mg l(-1) with a detection limit of 0.04 mg l(-1). The methods are applied to the routine analysis of MX in pharmaceuticals.

Flow-injection spectrophotometric methods for the determination of tenoxicam.

Two sensitive and rapid flow-injection spectrophotometric methods are proposed for the determination of tenoxicam (TX). In the first method, a Fe(III)-tenoxicam complex is formed in a methanolic medium and the absorbance is measured at 540 nm, while the second method involves measurement of the absorbance at 355 nm of a solution containing the drug in hydrochloric acid medium. In both methods, the peak heights were proportional to tenoxicam concentration over the ranges 7.0-320 and 0.5-8.5 mg/l(-1), respectively. The methods have been applied to the routine determination of the drug in dosage forms.

Flow-injection spectrophotometric determination of diclofenac sodium in pharmaceuticals and urine samples.

A sensitive and fast flow-injection spectrophotometric method for the determination of diclofenac sodium based on the formation of coloured compound with Ce(IV)-3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) in H2SO4 3 x 10(-2) M medium is proposed. Using the peak height as a quantitative parameter diclofenac was determined at 580 nm over the range 0.20-8.0 micrograms ml-1. The proposed method was successfully applied to the determination of diclofenac in pharmaceuticals and urine samples.

Simultaneous determination of piroxicam and its major metabolite 5'-hydroxypiroxicam in human plasma by derivative spectrophotometry.

A first-derivative spectrophotometric method for the simultaneous determination of piroxicam (PX) and its major metabolite 5'-hydroxypiroxicam (OH PX) in human plasma is described. The method consists of direct extraction of the two drugs from the plasma samples with hydrochloric and trichloroacetic acid prior to their determination by measuring the first-derivative signals at 337.0 nm for PX and at 327.0 nm for OHPX (zero-crossing wavelength). The calibration graphs were linear up to 10.0 and 8.0 mg l-1 of PX and OH PX, respectively, and the limits of quantification were 0.27 and 0.56 mg l-1. The possible interfering effects of other substances were studied.

Spectrophotometric methods for the determination of cephradine or ceftazidine in human urine using batch and flow-injection procedures.

Sensitive and fast spectrophotometric methods for the determination of cephradine or ceftazidine in human urine, based on the formation of compounds between these drugs and Pd(II), are described. In the batch procedures the calibration graphs resulting from the measurement of the absorbance at 330 nm is linear over the range 5.0-60.0 micrograms. ml-1 for cephradine and 3.0-60.0 micrograms ml-1 for ceftazidine. The methods were successfully adapted to FI-systems, the peak heights being proportional to cephalosporin concentration over the range 5.0-60.0 micrograms ml-1 for cephradine and 3.0-60.0 micrograms ml-1 for ceftazidine. The sampling frequency was 60 h-1 with a sample injection of 72 microliters.

Flow-injection spectrophotometric determination of frusemide or sulphathiazole in pharmaceuticals.

Two sensitive and fast flow-injection spectrophotometric methods are proposed for the determination of frusemide or sulphathiazole based on the formation of coloured complexes between these compounds and Pd(II) at pH 5.0 and 55 degrees C. Using the peak height as a quantitative parameter, frusemide or sulphathiazole was determined at 410 nm over the range 2.0 x 10(-5)-4.0 x 10(-4) M or 5.0 x 10(-5)-3 x 10(-4) M, respectively. The methods were applied to the determination of these sulphonamides in pharmaceuticals.

Flow-injection spectrofluorimetric determination of flufenamic and mefenamic acid in pharmaceuticals.

Two sensitive and rapid flow-injection (FI) spectrofluorimetric methods are proposed for the determination of flufenamic acid (FF) and mefenamic acid (MF), based on the formation of complexes of these compounds with A1(III) in an ethanolic medium. The calibration graphs resulting from the measurements of the fluorescence at lambda exc = 351 nm and lambda em = 440 nm, and lambdaexc = 355 nm and lambda em = 454 nm for the complexes with FF and MF, respectively, are linear over the range 0.030-1.20 micrograms ml-1 for FF and 0.30-16.1 micrograms ml-1 for MF. The methods have been applied to the determination of these drugs in pharmaceutical preparations.

Kinetic determination of carbimazole, methimazole and propylthiouracil in pharmaceuticals, animal feed and animal livers.

Kinetic methods are proposed for the determination of carbimazole(CBZ), methimazole(MMI) and propylthiouracil(PTU) based on their inhibitory effects on the palladium(II)-catalysed reaction between the pyronine G and hypophosphite ions. The reactions are monitored spectrophotometrically at 548 nm. The influence of reaction variables and the interfering effect of other substances were studied. Under the selected experimental conditions (CBZ: 3.6 x 10(-5) mol l-1 pyronine G; pH 3.0; 0.7 microgram ml-1 PdII and 0.2 mol l-1 H2PO2-; MMI: 6 x 10(-5) mol l-1 pyronine G, pH 3.0; 0.7 microgram ml-1 PdII, 0.4 mol l-1 H2PO2-; PTU: 3.6 x 10(-5) mol l-1 pyronine G; pH 3.0; 0.7 microgram ml-1 PdII and 0.3 mol l-1 H2PO2-), these three antithyroids were determined in the following ranges: CBZ, 0.04-0.70 microgram ml-1; MMI, 0.04-0.50 microgram ml-1; PTU 0.08-1.00 microgram ml-1. The methods were applied to the determination of CBZ, MMI and PTU, in pharmaceuticals, animal feed and animal livers.

Flow-injection spectrophotometric determination of piroxicam.

Two flow-injection analysis (FIA) methods are proposed for the determination of piroxicam. The first involves measurement of the UV absorbance of a solution containing the drug, methanol and hydrochloric acid at 332 nm; in the second method a Fe(III)-piroxicam complex is formed in a methanolic medium and the absorbance is measured at 520 nm. In both methods, the peak height is used as a quantitative parameter and piroxicam is determined over the ranges 0.5-15 and 30-500 microgram ml-1, respectively. The methods have been applied to the routine determination of the drug in dosage forms.

Determination of captopril in pharmaceutical samples by flow injection analysis.

A flow injection spectrophotometric method for the determination of captopril involving measurement of the absorbance of the captopril complex with palladium(II) in a 0.12 M HCl medium at 400 nm is presented. The calibration graph was linear over the range 2 x 10(-5)-6 x 10(-4) M. The sampling frequency was 90 h-1 with sample injections of 70 microliters. The proposed method was applied to the determination of captopril in pharmaceutical samples.

Determination of penicillamine or tiopronin in pharmaceutical preparations by flow injection analysis.

Two flow injection analysis (FIA) methods, using spectrophotometric detection, are proposed for the determination of penicillamine or tiopronin [N-(2-mercaptopropionylglycine)]. The procedures are based on the formation of yellow complexes between these thiol-containing drugs and Pd(II), in a 1 M or 0.25 M HCl medium, respectively. With peak height as a quantitative parameter, penicillamine is determined over the range 1.0 x 10(-5)-7.0 x 10(-4) M; for tiopronin the range is 1.0 x 10(-5)-6.0 x 10(-4) M. The methods have been applied to the routine determination of the drugs in pharmaceutical preparations.

Determination of ascorbic acid in pharmaceuticals and urine by reverse flow injection.

Two reverse flow injection (FI) methods, using spectrophotometric detection, are proposed for the determination of ascorbic acid. Both methods are based on its reaction with the ethylenediaminetetraacetic acid-CoIII complex in a medium of 5% diethylamine. In the first method, using the peak-height FI technique, ascorbic acid is determined over the range from 2 x 10(-4) to 5 x 10(-3) mol dm-3 and in the second, using the peak-width FI method, the working range is extended (2 x 10(-3)-5 x 10(-2) mol dm-3). Both FI methods were applied to the determination of ascorbic acid in pharmaceuticals while the peak-height FI technique was also used to determine ascorbic acid in urine.