Kinetic study and analytical applications of micellar catalyzed reactions of 1-fluoro-2,4-dinitrobenzene with inorganic thioanions using a fluoride-selective electrode.

A kinetic study and analytical applications of the CPC micellar catalyzed reactions of 1-fluoro-2,4-dinitrobenzene (FDNB) with inorganic thioanions (sulfide, sulfite and thiosulfafte) using a fluoride-selective electrode is described. Reaction orders (unity for both FDNB and thioanion) and experimental stoichiometric reaction-rate constants were calculated from initial slope measurements (DeltaE/Deltat) at various pH values (4-9). Calibration graphs for quantitative determinations (4.5-45 muM for sulfide, 2.4-75 muM for thiosulfate and 6.6-75 muM for sulfite) are constructed using the initial rate approach. The proposed method has been applied to the determination of sulfide in spiked seawater samples using the multiple standard addition approach with a mean relative error of 5.5%. The application of this micellar catalyzed reaction in the differential kinetic analysis of binary mixtures of sulfide-thiosulfate and sulfite-thiosulfate, using the proportional equations approach at pH 5.5 and 8.0, was unsuccessful due to the interactions of the two analytes, which can be explained using the ion-exchange/pseudophase model of micellar catalysis. However, the use of multiple linear regression approach on a sufficient number of standard binary mixtures can confront this drawback.

Flow-injection stopped-flow kinetic spectrophotometric determination of drugs, based on micellar-catalysed reaction with 1-fluoro-2,4-dinitrobenzene.

A flow-injection stopped-flow kinetic spectrophotometric method for the determination of hydrazines, hydrazides, amines and amino-acids, based on the cetyltrimethylammonium bromide catalysed reaction with 1-fluoro-2,4-dinitrobenzene is described. With the proposed method dihydralazine, isoniazid, levodopa and aspartame can be determined at concentrations of 0.1-6 x 10(-4)M. The calibration ranges can be varied by adjusting the pH and surfactant concentration. The determination of amphetamine, cysteine, s-carboxymethylcysteine, cephalexin, tobramycin and gentamicin is also feasible. The method has been applied to the determination of levodopa, isoniazid and aspartame in commercial pharmaceutical formulations. The determination of isoniazid in formulations containing the highly coloured antibiotic rifamycin, and of aspartame in coloured beverages was also accomplished. The results were in good agreement with those obtained by reference methods and the throughput was 40 measurements per hour with 0.4-3.9% RSD.

Kinetic determination of EDTA and citrate by the displacement of fluoride from Al(3+)F(-) complexes and use of a fluoride ion-selective electrode.

The displacement of fluoride from its aluminium complexes by the action of EDTA, citrate and other ligands is a relatively slow process which can be monitored potentiometrically with a fluoride ion-selective electrode. Some characteristics of these reactions are presented. There is evidence that [AlF](2+) reacts with the competitive ligand faster than the simple free (hydrated) Al(3+) species does. The relative rates of release of fluoride by the action of various aminopolycarboxylic acids have been determined. Potentiometric reaction-rate methods have been developed for the determination of 0.2-1.5 mumole of EDTA and 0.1-1.0 mumole of citric acid, with average relative errors of approximately 3%.

Determination of thiamine using continuous flow molecular emission cavity analysis.

A continuous flow method for the determination of thiamine hydrochloride (20.0-240.0 microgram ml(-1), 5.9 x 10(-5)-7.1 x 10(-4)m) is described. The sample was mixed with an excess of sodium hydroxide and remained in the delay coil for 20 min at 90 degrees C. The solution was then mixed with an excess of orthophosphoric acid and the hydrogen sulphide evolved was transferred continuously into the cavity to generate a molecular++ emission of S2. The analysis is completely automated, requires no sample pre-treatment and samples can be analysed at a rate of 30 samples h(-1) with a relative error of 1-2%. The method was evaluated by carrying out an interference study with common excipients and other water-soluble vitamins, a recovery study and by the analysis of commercial formulations. Results compared well with those obtained using the official method. The method was also applied to content uniformity tests.

Ion-selective electrodes for the H2-receptor antagonists cimetidine and ranitidine.

Liquid-membrane and polyvinyl chloride (PVC)-matrix ion-selective electrodes (ISE) that respond to the cationic forms of cimetidine and ranitidine are described. The ion-exchangers were the salts of cimetidine and ranitidine with tetrakis(m-chlorophenyl)borate dissolved in p-nitrocumene or entrapped in PVC polymer in the presence of 2-nitrophenyl octyl ether as plasticizer. The electrodes exhibited a near-Nernstian response in the range 10(-2)-10(-6)M (working pH range 2-7) for ranitidine, and 10(-2)-2 X 10(-5)M (pH 2-6) for cimetidine. Very small PVC-matrix ISE with internal diameters as small as 0.035 inches were constructed and used in combination with small cuvettes, so that measurements could be carried out in 250 muL of stirred solution. The electrodes were applied successfully for the determination of the pKa of the protonated bases and for the determination of the drugs in pharmaceutical preparations. New selective and effective solid-state extraction procedures are described for the extraction of ranitidine from urine and serum samples. Potentiometric methods were developed for the determination of ranitidine in urine and serum samples during a pharmacokinetic experiment.

Flow-injection analysis with the iron-induced perbromate-iodide reaction: spectrophotometric determination of iron.

Total iron is determined by a flow-injection spectrophotometric technique. The production of I(-)(3) from the iron(II)- or iron(III)-induced perbromate-iodide reaction is monitored at 353 nm. Calibration graphs are linear from 10 to 100 ng/ml with correlations up to 0.9998 and can be extended up to 10 microg/ml by appropriate adjustment of conditions. The average sampling rate is 30 samples/hr. Detection limits and relative standard deviations compare well with those of other FIA methods.

Kinetic detection of the end-point in titrations involving slow reactions Direct titration of polyhydroxy-compounds with periodate.

A new titration technique is described in which the end-point is determined by measuring the relative reaction rate of the titration reaction. This technique is adequate for rather slow reactions where conventional direct titrations are not applicable. The titrations are done automatically under microcomputer control. The efficiency of this technique is demonstrated with direct titrations of certain polyhydroxy-compounds with standard periodate solution. Ethylene glycol and propylene glycol (0.05-0.3 mmole), glycerol (0.06-0.17 mmole) and mannitol (0.01-0.03 mmole) were determined with average relative errors of 0.1-0.3%.

Potentiometric determination of certain alpha-aminohydroxy compounds by using an ammonia gas-sensing electrode.

A simple method is described for the determination of certain alpha-aminohydroxy compounds, based on the potentiometric measurement of ammonia released after oxidation with an excess of periodate. Ammonia is measured directly in the reaction mixture, with an ammonia gas-sensing electrode. Ethanolamine, diethanolamine, triethanolamine, serine, threonine, and glucosamine (0.3-6 mumole) can be determined with average errors of about 1-2%.

Continuous-flow serum albumin determination by reaction with picrate ions, with use of a flow-through picrate ion electrode.

An automated potentiometric method for serum albumin determination by use of the picrate/albumin reaction is described. A continuous-flow system and a specially designed flow-through picrate ion electrode were used in making the measurements. Various factors affecting the reaction, such as pH, picrate ion concentration, and reaction time, were studied. Peak height in millivolts and albumin concentration were linearly related in the range 10-70 g/L. Both within-run and day-to-day, the CV for the method was about 2%. Analytical recovery of albumin added to serum samples ranged from 97.0 to 110.3%, averaging 102.2%. Results compare favorably with those by the established bromcresol green method. The proposed method is suitable for routine use and for screening tests.

Kinetic potentiometric determination of creatinine in serum with a picrate ion-selective membrane electrode.

We describe a new kinetic method for potentiometric determination of creatinine in serum, based on the creatinine--picrate reaction in alkaline medium (Jaffé reaction). The reaction is monitored with a picrate-selective electrode, and the increase in electrode potential during 270 s is measured and related directly to the creatinine concentration. Small cation-exchange columns are used to separate creatinine from interfering substances. Analytical recovery of creatinine added to serum was 100.7%. Results for a series of samples compared well with results obtained with a spectrophotometric method (r = 0.994).

Indirect potentiometric determination of hydrazine, isoniazid, sulphide and thiosulphate with a chloramine-T ion-selective electrode.

Indirect potentiometric procedures with chloramine-T (CAT) as the oxidant and a chloramine-T ion-selective electrode are described for the determination of hydrazine and isonicotinic acid hydrazide (isoniazid) in the 1-100 mumole range and of sulphide and thiosulphate in the 0.5-50 mumole range. The reductants react stoichiometrically with a known and excessive volume of added CAT and the unconsumed excess of CAT is measured with the CAT-selective electrode. Aqueous solutions of the reductants were analysed with an error and precision of about 1-2%. Analytical recovery of isoniazid added to tablet diluents was 97-101% (average 98.9%). Results were comparable with those obtained with a titrimetric method for the determination of isoniazid in injection solutions and tablets.

Use of a periodate-sensitive perchlorate ion-selective electrode in the kinetic ultramicrodetermination of manganese(II) by means of its catalytic effect on the periodate-acetylacetone reaction.

A kinetic method for the ultramicrodetermination of maganese, based on its catalytic effect on the periodate-acetylacetone reaction, is described. A perchlorate electrode is used as a periodate sensor to monitor the reaction. The time required for the potential to change by a preselected amount (10 mv) is measured automatically and related directly to the manganese concentration. Amounts of manganese in the range 40-240 ng were determined with relative errors of about 2-4%.

Automated enzymatic determination of L-lactate in serum, with use of a miniature centrifugal analyzer.

We describe an automated enzymatic reaction-rate method for spectrophotometric determination of lactate in serum with a miniature centrifugal analyzer. The L(+) -lactate is selectively oxidized in the presence of lactate dehydrogenase (EC 1.1.1.27) and NAD+ to form NADH, which is measured from its absorption. Reaction rates are determined automatically, and unknown concentrations are calculated from a computer-generated calibration curve with aqueous lithium lactate standards. Lactate concentrations in the range 0.32-1.6 mug/4 mul (80-400 mg/liter) of sample were determined with relative errors and coefficient of variation of 4.8%. Analytical recovery of lactate added to pooled serum was 89-112% (average, 101%). Comparison with a kit ("Rapid Lactate") method gave a correlation coefficient squared of 0.979 over a concentration range of 39-779 mg/liter.

Adaptation of "EMIT" technique for serum phenobarbital and diphenylhydantoin assays to the miniature centrifugal analyzer.

We used a miniature centrifugal analyzer in a spectrophotometric rate-measurement mode to determine the anticonvulsant drugs phenobarbital and diphenylhydantoin in serum, by use of a modified enzyme immunoassay ("EMIT", Syva Corp.) We decreased reagent cost per determination by at least sixfold by means of microscale techniques. Also, the analysis rate is increased by measuring multiple samples simultaneously. Our method requires only 3 mul of serum for duplicate determinations. Replicate analyses of sera containing phenobarbital and diphenylhydantoin gave reaction rates with a CV of 1.5%. Run-to-run CV was 15%. Analytical recovery for drug-supplemented serum samples was 98%, and results for a series of samples compared well with results obtained by gas chromatography (for phenobarbital, r = 0.95; for diphenylhydantoin, r = 0.91).

Automated enzymic determination of ethanol in blood, serum, and urine with a miniature centrifugal analyzer.

We describe an automated spectrophotometric reaction-rate method for determination of ethanol in serum and urine with a miniature centrifugal analyzer. The theanol is selectively oxidized in the presence of alcochol dehydrogenase and NAD+ to form NADH, which is measured by the rate of change of its absorbance. Reaction rates are determined automatically, and unknown concentrations are calculated from a computer-generated working curve based on aqueous ethanol standards. Blood, serum, or urine specimens need not be deproteinized. The method permits duplicate analysis of at least 30 samples per hour. Coefficients of variation and relative errors are about 2-3% for ethanol concentrations of 0.3-3.0 mug per 2 mul of sample. Analytical recovery of ethanol added to serum is 92-103% (average, 98.5%). Comparisons with distillation-oxidation, gas-chromatographic, and conventional enzymic procedures give satisfactory agreement.

EDTA titration of calcium and magnesium with a calcium-selective electrode.

Direct semi-automatic and automatic derivative potentiometric EDTA procedures for the determination of calcium and/or magnesium with a calcium-selective electrode are described. Calcium is titrated in the presence of magnesium at pH 12.0 and the total calcium and magnesium is determined at pH 9.7. Calcium in the range 1-8 mg and magnesium in the range 0.7-5 mg are determined semi-automatically with average errors of about 0.2 and 0.3% respectively and automatically with average errors of 0.4 and 0.7%. Titration times vary from a few seconds to a few minutes.