Use of palladium(II) chloride as a colour-forming reagent for the determination of N-acetyl-L-cysteine in water and fluimukan injections

The formation of the complex between N-acetyl-L-cysteine and palladium(II) chloride in Britton-Robinson buffer solution in the pH range 2.08-8.00 was studied. The optimum conditions for this reaction were ascertained and a spectrophotometric method was developed for the determination of N-acetyl-L-cysteine in the concentration range 4.0-65.3 micrograms ml-1, using PdCl2 as the reagent. The detection limit was 1.63 micrograms ml-1 and the relative standard deviation varied from 0.63 to 1.92%. The method was applied to the determination of N-acetyl-L-cysteine in water and in injection solutions.     

Spectrophtometric determination of tungsten(VI) with rutin and cetyltrimethylammonium bromide

Tungsten-(VI) reacts with rutin in the presence of cetyltrimethylammonium bromide to form a soluble yellow complex having maximum absorbance at 416 nm. The molar ratio of tungsten to rutin in the complex is 1:2. The molar absorptivity is 5.01 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed over the range 1 x 10(-7)(-1) x 10(-5)M tungsten (VI). Optimum solution conditions for the determination of tungsten in various sample matrices have been found and the interference of diverse ions has been examined.     

Indirect atomic absorption spectrometric determination of sulfate in human blood serum.

An indirect method for the determination of sulfate by atomic absorption spectrometry (AAS) is described. Sulfate forms a stable ion-association complex, [Cu(neocuproine)2]2+(SO4(2-)), in neutral medium, which can be extracted into isobutyl methyl ketone in the presence of a polar medium (methanol) with an efficiency higher than 98.0% and the extract can be analysed directly for copper (and hence indirectly for sulfate) by AAS. Measurement of the copper atomic absorption signal from the organic phase allows the indirect determination of 0.14-1.12 micrograms ml-1 of sulfate, giving a 450-fold increase in sensitivity over the conventional method of precipitation with barium. The limit of detection (3 sigma) is 3.2 ng ml-1 which is better than that of ion chromatography (0.15 micrograms ml-1). Indirect AAS allows the accurate assay of inorganic sulfate anion in biological fluids and tissues. The sulfate concentration determined by the proposed method in human blood serum (n = 6 in each instance) was 35.4-43.3 micrograms ml-1 in normal persons, 50.3-62.5 micrograms ml-1 in jaundice patients and 83.3-155.6 micrograms ml-1 in diabetic patients. A good correlation between measured sulfate and the sulfate added to blood serum was obtained.     

Column preconcentration of trace manganese with the ion pair of 2-nitroso-1-naphthol-4-sulfonic acid tetradecyldimethylbenzyl-ammonium chloride supported on naphthalene and determination by derivative spectrophotometry

A column preconcentration method has been developed for the determination of trace amounts of manganese by preconcentration on 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-S)-tetradecyldimethylbenzylammonium (TDBA) naphthalene as an adsorbent using a simple funnel tipped glass tube. Manganese reacts with nitroso-S to form a water soluble brown colored chelate anion. The chelate anion forms a water insoluble Mn-Nitroso-S-TDBA ion pair on naphthalene packed in a column in the pH range 9.6-10.5 at a flow rate of 1-2 ml/min. The solid mass consisting of manganese complex and naphthalene is dissolved in 5 ml of dimethylformamide (DMF) and the metal determined by second derivative spectrophotometry. The calibration curve is linear in the concentration range 0.25-35.0 micrograms of Mn in 5 ml of the final DMF solution. Eight replicate determinations of 25 micrograms of standard manganese solution give a mean peak height of 4.0 with a correlation coefficient of 0.9995 and relative standard deviation of +/- 1.1%. The sensitivity was calculated to be 0.502(d2 A/d lambda 2)/microgram ml-1 from the slope of the calibration curve. The detection limit was 0.020 microgram ml-1 for manganese at the minimum instrumental settings (signal to noise ratio = 2). Various parameters effecting the method such as the effect of pH, volume of aqueous phase and interference of a number of metal ions on the determination of manganese have been evaluated to optimize the conditions for its determination in standard alloys and biological samples.     

Determination of nucleic acids with crystal violet by a resonance light-scattering technique

For the first time, Crystal Violet (CV) was used to determine nucleic acid concentrations using the resonance light-scattering (RLS) technique. Based on the enhancement of the RLS of CV by nucleic acids, a new quantitative determination method for nucleic acids in aqueous solutions has been developed. At pH 5.03 and ionic strength 0.005 mol kg-1, the interaction of CV with nucleic acids results in three characteristic RLS peaks at 344.0, 483.0 and 666.0 nm. With 4.0 x 10(-5) mol l-1 of CV, linear relationships were found between the enhanced intensity of RLS at 666.0 nm and the concentration of nucleic acids in the range 0-2.5 micrograms ml-1 for herring sperm DNA, 0-4.0 micrograms ml-1 for calf thymus DNA and 0-4.5 micrograms ml-1 for yeast RNA. The limits of determination were 13.8 ng ml-1 for herring sperm DNA, 36.8 ng ml-1 for calf thymus DNA and 69.0 ng ml-1 for yeast RNA. The assay is convenient, rapid, inexpensive and simple.     

Simultaneous determination of acetylsalicylic and salicylic acids in human serum and aspirin formulations by second-derivative synchronous fluorescence spectrometry

A second-derivative synchronous scanning spectrofluorimetric method for the simultaneous determination of acetylsalicylic acid (ASA) and salicylic acid (SA) is described. The method is based on the native fluorescence of both acids in a 1% acetic acid-chloroform solution. Both ASA and SA can be determined within the concentration ranges 0.2-70 and 0.03-10 micrograms ml-1, respectively. The effect of each acid on the signal of the other has been studied in detail. Empirical equations have been used to overcome this effect, thus allowing the accurate determination of both acids in binary mixtures, without a separation step. The method has been applied to the determination of ASA and SA in blood serum and to the determination of SA impurities in aspirin formulations. Recoveries from sera spiked with both ASA (2.5-50 micrograms ml-1) and SA (100-160 micrograms ml-1) varied from 99.5 to 106.7% (mean = 102.6%) and from 93.0 to 98.0% (mean = 95.8%), respectively. Recoveries of SA from spiked aspirin solutions (0.25-1.5 mg g-1 of aspirin) varied from 98.0 to 102.0% (mean = 100.3%).     

Fluorimetric determination of aluminium in serum

A convenient fluorimetric method for the routine determination of aluminium in serum has been developed using lumogallion [4-chloro-3-(2,4-dihydroxyphenylazo)-2-hydroxybenzene-1-sulphonic acid]. Losses of aluminium during deproteinisation of the serum were prevented by treatment with a combination of 20 or 30% m/V trichloroacetic acid (TCA) and 5% m/VTCA. Iron(III) was removed by extraction into chloroform with capriquat (methyltrioctylammonium chloride) as an Fe3+-lumogallion-capriquat ternary complex. The interference from Cu2+ was eliminated by using thiosulphate as a masking agent. The detection limit was 3.6 ng ml-1 and the calibration graph was linear up to 1.4 micrograms ml-1 of aluminium. Using the proposed method, the average concentration of aluminium in the serum of healthy subjects was found to be 6.8 ng ml-1, in agreement with values reported in the literature.     

A new sensitive method for the spectrophotometric determination of molybdenum using 3-hydroxy-2-(2'-thienyl)-4H-chromen-4-one

A spectrophotometric method has been developed for the determination of Molybdenum (VI) using 3-hydroxy-2-(2'-thienyl)-4H-chromen-4-one as a complexing agent. The complex formed was dissolved in water in the presence of Triton X-100 and exhibits an absorption maximum at 410 nm. A large number of metal ions like Co(II), Ni(II), Mn(II), Cr(III), Zn(II), Cu(II), Hg(II), Bi(III), Fe(II), Fe(III), Zr(IV), V(V) can be tolerated at an appreciable concentrations. Molar absorptivity and Sandell's sensitivity of the method is 2.80 x 10(5) l mol-1cm-1 and 3.42 x 10(-4) micrograms cm-2, respectively. Beer's law is obeyed in the concentration range of 0.01-0.4 ppm Mo(VI). Aliquots containing 0.2 ppm of Mo(VI) give a mean absorbance of 0.56 with a relative standard deviation of 1.3%.     

Determination of molybdenum in steel by adsorptive stripping voltammetry in a homogeneous ternary solvent system.

A new alternative approach for the determination of molybdenum in steel is proposed, using adsorptive stripping voltammetry (AdSV). The determinations are performed in a homogeneous ternary solvent system (HTSS) composed of N,N-dimethylformamide, ethanol and water, with alpha-benzoinoxime (alpha BO) as the complexing agent and a sodium acetate-acetic acid buffer as the support electrolyte. The HTSS composition was optimized by mixture design modelling. The AdSV measurements were performed in the differential pulse mode using an accumulation potential of -1050 mV. Under these optimized experimental conditions, the Mo(VI)-alpha BO reduction current peak potential is observed at potentials near -1250 mV, much lower than those usually reported, and the calibration plot follows the polynomial equation I = 0.359 + 0.265 [CMo(VI)] - 0.015 [CMo(IV)]2 (r2 = 0.997), for Mo concentrations up to 10.0 micrograms L-1. There is a linear range in this calibration plot for Mo(VI) concentrations up to 0.20 microgram L-1, defined by the equation I = 0.353 + 0.385 [CMo(VI)] (r2 = 0.980). In both cases, I is the absolute value for the current in microA and CMo(VI) is the concentration of Mo in microgram L-1. The detection limit for this linear concentration range was estimated as 20 pg L-1. A RSD of 0.43% is associated with the signals at a Mo(VI) level of 0.72 microgram L-1. From the common method-interfering species tested, only iron at Fe/Mo(VI) ratios above 500 and vanadium and tungsten at M/Mo(VI) ratios above 100 appear to affect the analytical response significantly. Phosphorous may also reduce the analytical signal at P/Mo(VI) ratios above 100, due to the formation of the competitive P-Mo complex. The suggested routine procedure was tested by analyzing four stainless steel samples and the results compared well with the ICP-AES measurements. The higher sensitivity of this method permits direct determination of Mo(VI) in steels, eliminating the need of analyte concentration or separation steps in the sample processing procedure.     

Poly(vinyl chloride) matrix membrane electrode for the selective determination of heroin (diamorphine) in illicit powders

The potentiometric response characteristics of a poly(vinyl chloride) membrane electrode for heroin based on its ion-pair complex with tetraphenylborate were examined. The influence of pH, temperature and time on the performance of the electrode system was investigated. The electrode shows a near-Nernstian response over the heroin concentration range 10(-2)-10(-4) M with good precision. The mean relative standard deviation for the determination of heroin in 40 micrograms ml-1(-1) mg ml-1 aqueous heroin hydrochloride solutions is 1.2%. The electrode exhibits good selectivity for heroin in the presence of a number of adulterants and basic organic compounds commonly present in illicit heroin powders. The method was applied to the direct potentiometric determination of heroin in illicit powders (10-36% heroin) and the results agreed fairly well with those obtained by gas - liquid chromatography.     

Spectrophotometric determination of vanadium(V) in minerals, steels, soil and biological samples using phenothiazine derivatives.

Two simple, rapid and sensitive spectrophotometric methods have been proposed for the determination of vanadium(V) using butaperazine dimaleate (BPD) and propionyl promazine phosphate (PPP). These methods are based on the formation of red-colored radical cations on reaction with vanadium(V) in phosphoric acid medium, with their absorbance maxima at 513 nm. Beer's law is valid over the concentration range of 0.25-5.0 micrograms ml-1 and 0.2-4.0 micrograms ml-1, with Sandell's sensitivity values of 6.1 ng cm-2 and 6.0 ng cm-2 for BPD and PPP respectively. The proposed methods have been successfully applied to the analysis of vanadium steels, minerals, biological samples and soil samples.     

Atomic absorption spectrometric determination of trace zinc in alloys and biological samples after preconcentration with [1-(2-pyridylazo)-2-naphthol] on microcrystalline naphthalene

An atomic absorption spectrometric method for the determination of trace amounts of zinc after adsorption of its [1-(2-pyridylazo)-2-naphthol] complex on microcrystalline naphthalene has been developed. This complex is adsorbed on microcrystalline naphthalene in the pH range 3.5-7.5 from large volumes of aqueous solutions of various alloys and biological samples with a preconcentration factor of 40. After filtration, the solid mass consisting of the zinc complex and naphthalene was dissolved with 5 ml of dimethylformamide and the metal was determined by flame atomic absorption spectrometry. Zinc can alternatively be quantitatively adsorbed on [1-(2-pyridylazo)-2-naphthol]-naphthalene adsorbent packed in a column and determined similarly. About 0.5 ng of zinc can be concentrated in a column from 200 ml of aqueous sample, where its concentration is as low as 2.5 pg ml-1. The calibration curve is linear in the range 0.1-6.5 ng ml-1 in dimethylformamide solution. Eight replicate determinations of 2 ng ml-1 of zinc gave a mean absorbance of 0.145 with a relative standard deviation of 1.5%. The sensitivity for 1% absorption was 0.061 ng ml-1. Various parameters, such as the effect of pH and the interference of a number of metal ions on the determination of zinc, have been studied in detail to optimize the conditions for the determination of zinc in various standard complex materials.     

The simple and rapid spectrophotometric determination of trace chromium(VI) after preconcentration as its colored complex on chitin

Preconcentration method with collection of metal complexes on a chitin has been applied to the spectrophotometric determination of chromium(VI) in water. The chromium(VI) is collected as its 1,5-diphenylcarbazide(DPC) complex on a column of chitin in the presence of dodecyl sulfate as counter-ion. The Cr-DPC complex retained on the chitin is eluted with a methanol-1 M acetic acid mixture (7:3, v/v), and the absorbance of the eluent is measured at 541 nm. Beer's law is obeyed over the concentration range of 0.05-0.6 mug of chromium(VI) in 1 ml of the eluent. The apparent molar absorptivity is 3.5x10(4) dm(3) mol(-1) cm(-1). The tolerance limits for Fe(III) is low, i.e. ten times that of chromium(VI), but some metal ions and common inorganic anions do not interfere in concentration range of 100-10 000 times that of chromium(VI). The present method can be applied to the determination of chromium(VI) in natural water samples.     

Spectrophotometric method for the determination of sorbic acid in various food samples with iron(III) and 2-thiobarbituric acid as reagents

A simple, rapid and accurate spectrophotometric method has been developed for the determination of sorbic acid in various food samples based on the oxidation of sorbic acid by iron(III) at 100 degrees C to malonaldehyde, which then reacts with 2-thiobarbituric acid to form a reddish brown product. The optimum experimental conditions for colour development have been assessed. Absorbance measurements were made at 529 nm in the presence of 0.4% m/V citric acid. The calibration graph was linear for 0-6 micrograms ml-1 of sorbic acid with a slope of 0.131 A micrograms-1 ml. The recoveries of sorbic acid at concentrations of 164-557 micrograms ml-1 ranged from 96 to 103%. The relative standard deviations of ten replicate determinations of sorbic acid in a synthetic cream soda sample spiked with 573 micrograms ml-1 of sorbic acid and in an onion juice sample containing 82 micrograms ml-1 of sorbic acid were 1.6 and 1.9%, respectively. Interferences from several common food additives can be minimised by extracting sorbic acid with diethyl ether and then back-extracting the acid with sodium hydrogen carbonate. The method has been applied successfully to the determination of sorbic acid in a wide range of food samples including beverages, cake, cake mate, garlic bread sprinkle, onion juice, oyster flavoured sauce and grenadine syrup.     

Extraction--spectrophotometric determination of oxalate in urine and blood serum

An extraction--spectrophotometric method is described for the determination of oxalate, based on the formation of a mixed ligand vanadium (V)--mandelohydroxamic acid--oxalate complex. The complex was extracted into a solution of trioctylmethylammonium chloride (Adogen 446) in toluene and the absorbance measured at 535 nm. The experimental variables and interferences in this determination were studied. The detection limit is 0.5 microgram ml-1 and the range of application is between 2 and 8 micrograms ml-1. The method was applied to the determination of oxalate in urine and blood serum.     

Novel spectrophotometric method for the determination of molybdenum in a PVA medium.

A novel spectrophotometric method for the determination of trace molybdenum in the presence of a large amount of tungsten was developed. This proposed method was based on the formation of a green charge-transfer polyoxometalate, molybdo-11-tungstophosphate-3,3',5,5'-tetramethylbenzidine-N-propanesulfonic, which was solubilized and stabilized in a PVA medium; the wavelength of the maximum absorption was at 660 nm. Beer's law was obeyed in the Mo concentration range of 0.04-1.6 microg ml(-1). The molar absorptivity was 1.35 x 10(4) l mol(-1) cm(-1). The developed method avoided the interference of W(VI), and was conveniently applied to analyses of some tungsten ores containing Mo(VI) with satisfactory results.     

N,N-diethyl-N'-benzoylthiourea--a new spectrophotometric reagent for rhenium determination

The reagent N,N-diethyl-N'-benzoylthiourea produces a green complex with rhenium in hydrochloric acid medium in the presence of tin(II) chloride. The complex extracted into toluene shows an absorption maximum at 383 nm, obeys Beer's law from 1.5 to 22 micrograms ml-1 of rhenium while its molar absorptivity and Sandell sensitivity are 6.66 x 10(3) L mol-1 cm-1 and 0.028 microgram cm-2, respectively. It tolerates the presence of a large number of ions, including Mo(VI), W(VI) and some platinum metals. Job's and the mole ratio methods indicate that the rhenium metal and the chelating agent ratio of 1:2 in solution. The system has been applied to the determination of rhenium on synthetic samples and alumina based catalysts.     

Determination of nickel in biological samples spectrophotometrically involving complexation reaction with some thiazolylazo compounds

Three new heterocyclic azo compounds, 5(2-benzothiazolylazo)2,2 biphenyldiol (I), 5-(2-benzothiazolylazo)-8-hydroxyquinolene (II) and 4-(2-benzothiazo-lylazo)3-hydroxy-2-naphthoic acid (III) were synthesized. The formation constant of the reagents in 30% (v/v) ethanol and reactions with various metal ions were studied. These reagents (I-III) reacts with nickel ion to form (2:1) colored complex with an absorption band at 604, 635 and 643 nm. The apparent stability constants and the optimum conditions for complete color development were investigated. Beer's law is obeyed over the concentration ranges of 0.05-3.50, 0.05-4.00 and 0.05-3.10 micrograms ml-1. For more accurate analyses, Ringbom optimum concentration ranges were found to be 0.20-3.25, 0.20-3.80 and 0.20-2.90 micrograms ml-1 using reagents I, II and III, respectively. The apparent molar absorptivity and Sandell sensitivity were also calculated. The interference of various foreign ions on the determination of nickel was investigated. The proposed method has been successfully applied to the determination of nickel substrates in various biological samples.     

Study of the reaction of proteins with Beryllon II-AlIII by the Rayleigh light scattering technique and its application

The determination of proteins with tetrasodium 2-(3,6-disulfo-8-hydroxynaphthylazo)-1,8-dihydroxynaphthalene-3,6-disulfonate (Beryllon II) by Rayleigh light scattering (RLS) was studied. The weak RLS of the Beryllon II-bovine serum albumin (BSA) complex can be greatly enhanced by the addition of Al3+ in the pH range 5.6-7.2; there was a maximum RLS platform at 400-420 nm. Based on the reaction between Beryllon II, Al3+ and proteins, a new method for the determination of proteins was developed. This method is very sensitive [0.20-41.42 micrograms ml-1 for BSA and 0.18-48.15 micrograms ml-1 for human serum albumen (HSA)], rapid (< 2 min), simple (one step) and tolerant towards most interfering substances. The effects of different surfactants were also examined. Four samples of protein in human serum were determined; the maximum relative error was no more than 5% and the recovery was 96-105%.     

Determination of beta-lactams and their biosynthetic intermediates in fermentation media by pre-column derivatisation followed by fluorescence detection

This paper describes a novel and sensitive pre-column derivatisation method for the detection and quantitation of beta-lactams and their biosynthetic precursors at trace levels in fermentation media. Filtered broths from fermentations of strains of Penicillium chrysogenum and Cephalosporium acremonium, after deproteination and centrifugation, were incubated with 9-fluorenylmethylchloroformate for 5 min at 20 degrees C in 0.2 M borate buffer at pH 7.7. Following two-fold pentane extraction of the reagent hydrolysis product, the aqueous layer was injected directly onto a C18 reversed-phase column, and products were detected spectrofluorimetrically with excitation and emission wavelengths of 260 and 313 nm, respectively. Detection limits of 0.01 and 0.05 micrograms ml-1 were achieved for both 6-aminopenicillanic acid (6-APA) and isopenicillin N in borate buffer and filtered fermentation broths, respectively, using a 10-microliter injection volume. A linear calibration for 6-APA in fermentation broth was obtained for a very wide concentration range (0.05-100 micrograms ml-1). Detection limits for solutions of cephalosporin C, deacetylcephalosporin C and deacetoxycephalosporin C in broth were all 0.25 micrograms ml-1. The detection limit for the beta-lactam precursor delta-(L-aminoadipyl)-L-alpha-cysteinyl-D-valine (ACV) dimer in borate buffer was 0.5 microgram ml-1. The cephalosporins and ACV dimer gave linear plots in the ranges 3-25 and 1-100 micrograms ml-1, respectively. Repeated analysis of 6-APA at a concentration of 10 micrograms ml-1 in filtered broth gave a mean peak area of 2.5.10(6) with a standard deviation of 2.6.10(5) using a 10-microliter injection volume. Ampicillin spiked into deproteinated blood serum gave a linear calibration in the concentration range 2-100 micrograms ml-1.