Sequential Extraction-Spectrofluorimetric Determination of Mercury Using Cryptand Ethers

Abstract

A spectrofluorimetric study of the extraction of mercury with 1,2-dichloroethane as an ion-pair formed between the cryptand 2.2.1-mercury complex and the eosinate counter-ion is described.

The detection limit for mercury is 0.7 ng/ml, and the linear working range up to 125 ng/ml of mercury.

The relative standard deviation is found to be 2.0% at the 100 ng/ml level. The proposed method has been tested for the determination of mercury in coal.     

Extractive fluorimetric determination of ultratraces of lead with 18-crown-6 and eosin

A highly sensitive and selective spectrofluorimetric procedure for the determination of lead in the range 0.003-0.5 ppm, based on solvent extraction of the ion-pair formed between the eosinate anion and the cationic complex of Pb(2+) with 18-crown-6, has been developed. The relative standard deviation is 3.7% at the 0.1 ppm level. The metal :ligand: counter-ion molecular ratio in the ion-pair extracted is 1:1:1, but aggregation of the complex may occur in the organic phase. The system proposed is exceptionally selective for extraction of lead in the presence of other cations frequently associated with it. The proposed method has been tested in the determination of lead in tap water. The results show good agreement with those found by the more common extractive atomic-absorption method using ammonium tetramethylenedithiocarbamate.     

Sequential extraction-spectrofluorimetric determination of ultratraces of zinc using cryptand 2.2.1 and eosin

A highly sensitive and selective spectrofluorimetric method has been developed for the determination of ultratraces of zinc, based on solvent extraction with 1,2-dichloroethane of the ion-pair formed between eosinate anion and the positively charged cryptate of zinc with cryptand ethers. The detection limit for zinc is 1.5 ng/ml, and the linear working range up to 200 ng/ml. The relative standard deviation is 1.8% at the 100 ng/ml level. The proposed method has been tested for determination of zinc in coal and fly ash.     

Extractive fluorimetric determination of ultratraces of lead with cryptand 2.2.2 and eosin

A new speetrofluorimetric method for determination of ultratraces of lead is based on solvent extraction into chloroform of the ion-pair formed between the positively-charged cryptate of lead with cryptand 2.2.2 and the eosinate anion. The detection limit for lead is 1 ng ml , and the linear working range is from the detection limit to 250 ng ml . The relative standard deviation is 3.7% at the 100 ng ml level. The method is highly selective for the extraction and determination of lead in the presence of other cations, and has been tested for direct determination of lead contamination in soft drinks. Aggregation of the extracted ion-pair in the organic phase has been demonstrated in fundamental extraction studies.     

Ion-pair extraction and fluorimetric determination of cadmium with cryptand 2.2.1 and eosin

A method is described for the direct spectrofluorimetric determination of ultratraces of cadmium by extraction into 1,2-dichloroethane of the ion-pair formed between the eosinate anion and the cationic complex of Cd²⁺ with cryptand 2.2.1. The detection limit for cadmium is 0.5 ng/ml, and the linear working range is from the detection limit to 150 ng/ml. The relative standard deviation is 1.5% at the 100 ng/ml level. The equilibrium constant has been estimated and refined by the Letagrop-DISTR program. The proposed method has been tested in the determination of cadmium in high-purity zinc. The results show good agreement with those found by the more common ICP emission photometry and anodic stripping voltammetry methods.     

Sequential extraction--spectrofluorometric determination of lead and cadmium using cryptands.

A spectrofluorimetric method for the determination of ultratrace amounts of lead and cadmium is described based on the sequential extraction of the ternary ion-association complexes formed between the cation, a cryptand as the ligand and eosin as a counter ion. A linear working range from the detection limit (0.5 ng ml(-1) to 250 ng ml(-1) of lead and to 1 50 ng ml(-1) of cadmium was obtained. The relative standard deviation was 2-4%. The proposed method has been applied successfully to the determination of lead and cadmium in zinc metals and soft drinks.     

Sequential Extraction-Spectrofluorimetric Determination of Lead and Mercury Using Cryptand Ethers

Abstract

A spectrofluorimetric method for the determination of ultratrace amounts of lead and mercury is described based on the sequential extraction of the ternary ion-association complexes formed between the cation, a cryptand as the ligand and eosin as counter ion. A linear working range from the detection limit (9 ng/ml) to 250 ng/ml of lead and 12 ng/ml of mercury was obtained.

The relative standarddeviation was 3.5 % – 2.1 %. We propose that this method could be used routinely to control lead and mercury simultaneous.     

Ion-pair extraction and fluorimetric determination of ultratraces of strontium with cryptand 2.2.2 and eosin

A highly sensitive and selective fluorimetric determination of strontium is proposed, based on solvent extraction of the ion-pair formed between the cationic complex of Sr²⁺ with cryptand 2.2.2 and eosinate as counter ion. A linear working range from 0.7 ng/ml (limit of detection) to 500 ng/ml of strontium and a relative standard deviation of 3.5% at the 100 ng/ml level are obtained. The metal: ligand: counter ion molecular ratio in the extracted mononuclear ion-pair is 1 1 1. The equilibrium constants involved in the extraction process were calculated.     

Determination of vinca alkaloids in mouse tissues by high-performance liquid chromatography.

A high-performance liquid chromatographic method is described for the determination of vinblastine in various normal mouse tissues, such as lung, heart, liver, kidney and muscles, and in implanted MO4 tumours. Vincristine was used as the internal standard. Freshly obtained mouse tissue or tumour tissue was frozen at -20 degrees C and then lyophilized. After lyophilisation, the dry tissues were pulverized and homogeneously mixed, and an aliquot was suspended in 0.1 M hydrochloric acid. The drugs of interest were then isolated from this suspension using ion-pair extraction at pH 3 with octylsulphate as counter-ion. The obtained extracts were analysed on a reversed-phase system with a cyanopropyl stationary phase. The detection limit was 1 ng/l in plasma and 10 ng/g in tissue. The extraction recoveries of vincristine and vinblastine were between 45 and 67%, and there were no interferences from blank components. Preliminary pharmacokinetic data for different mouse tissues and tumour implanted in muscle tissue are presented.     

Spectrofluorimetric Determination of Germanium Traces Using 1,2,4-Trihydroxyantraquinone

ABSTRACT

A new spectrofluorimetric method for determination of germanium traces based on its reaction with 1,2,4-Trihydroxyantraquinone, at an apparent pH 8.8 provided by an ammonia/ammonium chloride buffer, in a 80:20(v/v) ethyleneglycol water medium is proposed. The calibration graph is linear over the range 70–725 ng/ml and features a detection limit of 2.5 ng/ml. The effect of potential major interferences has been investigated and the proposed method was successfully applied to the determination of germanium in synthetic samples and industrial concentrates, after extraction with CCl₄, in an 9 M HCl medium.     

Sensitive determination of josamycin and rokitamycin in plasma by high-performance liquid chromatography with fluorescence detection.

Rokitamycin and josamycin were successfully derivatized with dansylhydrazine in 20 min at 60 degrees C. Rokitamycin and josamycin levels were determined in plasma after ion-pair extraction into hexane-isoamyl alcohol with lauryl sulphate and precolumn derivatization. Resolution was obtained by liquid chromatography with fluorescence detection (352/537 nm) in 12 min. The limit of detection was 20 ng/ml macrolide starting from 1 ml of plasma, and linearity was demonstrated between 50 and 400 ng/ml. Inter-run coefficients of variation were 10.2% at 100 ng/ml and 9.1% at 300 ng/ml. The system was reliably used for pharmacokinetic studies in plasma.     

Fluorimetric determination of anionic surfactants by extraction as safranine-T ion-pairs

A simple and rapid method is proposed for the spectrofluorimetric determination of anionic surfactants. It is based on formation of an ion-pair at pH 2 with safranine-T and its subsequent extraction into chloroform. Fluorescence intensity is increased by a factor of about 5 with respect to that of the reagent. The calibration graph is linear in the concentration range 0.015–0.40 mg l^?1 dodecyl sulfate; the relative standard deviation is 5.6% at 0.22 ml l^?1 surfactant. The method is applied to determine anionic surfactants in city waste-waters, giving recoveries close to 100%.     

Extraction-fluorimetric determination of microgram amounts of thallium with 2-phenylbenzo[8,9]quinolizino[4,5,6,7-fed]phenanthridinylium perchlorate

In 0.5 M hydrochloric acid medium, thallium(III) forms with 2-phenylbenzo [8,9]quinolizino[4,5,6,7-fed]phenanthridinylium perchlorate (PQPP) an ion-association compound which is extractable in isoamyl acetate. The extracted ion-pair has a mole ratio Tl/PQPP in 1:1 and has been used for the spectrofluorimetric determination of thallium in the concentration range 0.06–1.6 μg per 5 ml of organic layer. The interference of a large number of foreign ions has been investigated. The method is sensitive, accurate, precise, and specially useful for the determination of thallium in different materials with low contents of this element.     

Revised HPLC Determination of Atenolol in Plasma and Urine

Abstract

An HPLC method for analysis of atenolol in human plasma and urine is presented. Based on alkaline extraction, acid backextraction and reverse phase ion-pair chromatography this method is quite specific for atenolol. For a 0.5 ml plasma sample the sensitivity ranges from 20 ng/ml in fasted healthy volunteers to 50 ng/ml in various groups of patients. A sensitivity in urine of 1.0 mcg/ml was sufficient for all samples studied. As presented this method has been used in several clinical pharmacokinetic studies involving hundreds of samples.     

On-line ion-pair solid-phase extraction-liquid chromatography-mass spectrometry for the analysis of quaternary ammonium herbicides

An ion-pair on-line solid-phase extraction procedure using C8 extraction disks, suitable for liquid chromatography-mass spectrometry analysis is developed to determine quaternary ammonium herbicides (quats) in water samples. The separation of these compounds was performed using ion-pair chromatography with heptafluorobutyric acid (15 mM, pH 3.3) and acetonitrile gradient elution. Detection was carried out using a quadrupole mass spectrometer. Water sample volumes up to 50 ml can be preconcentrated with recoveries higher than 70%. Good precision and accuracy (day-to-day and run-to-run) were obtained and the detection limits ranged from 6 to 85 ng l(-1). The proposed on-line ion-pair solid-phase method enables compliance with European Community directives for drinking waters (100 ng l(-1)).     

Solvent extraction-spectrophotometric determination of phosphate with molybdate and malachite green in river water and sea-water

Molybdophosphate, formed between orthophosphate and molybdate in sulphuric acid solution, is extracted into a mixture of toluene and 4-methylpentan-2-one (1:3 v v ) with Malachite Green as counter-ion. A single extraction with equal phase volumes gives an apparent molar absorptivity for phosphate of 2.3 x 10(5) l.mole(-1).cm(-1) at 630 nm; the absorbance of the reagent blank is 0.03. With an organic to aqueous phase-volume ratio of 1:10, the molar absorptivity is 2.5 x 10(5) l.mole(-1).cm(-1) and the absorbance of the reagent blank 0.08. By the proposed method, ng ml levels of phosphorus can be determined, and the detection limit is about 0.1 ng ml . The standard deviation and relative standard deviation for the determination of phosphorus in tap water (4.3 ng ml ) are 0.05 ng ml and 1.1%, respectively. The method can also be applied to the determination of phosphorus in river water and sea-water.     

Determination of the oximes 2-hydroxyiminomethyl-3-methyl-1-[2-(3-methyl- 3-nitrobutyloxymethyl)]imidazolium chloride and 1-[1-(3-butynyloxymethyl)]-2-hydroxyiminomethyl-3-methylimida zolium chloride in plasma by high-performance liquid chromatography

An assay is presented for the extraction and quantitation of two oximes, 2-hydroxyimino-methyl-3-methyl-1-[2-(3-methyl-3-nitrobutyloxyme thyl)] imidazolium chloride (oxime A) and 1-[1-(3-butynyloxymethyl)]-2-hydroxyiminomethyl-3-methylimidazo lium chloride (oxime B), in human plasma and is demonstrated to be linear over two overlapping concentration ranges: 10-500 and 100-1000 ng/ml. The assay utilizes a liquid-liquid, ion-pair extraction and a normal-phase chromatographic separation on a silica column with ultraviolet detection at 270 nm. The method is sensitive, rapid and accurate. The limit of detection is 10 ng/ml (signal-to-noise ratio S/N greater than 10). The mean extraction recoveries of the oximes were greater than 86% at all concentration levels. The intra-assay variability was less than 3.3%, the inter-assay variability less than 7.2%. The compound is stable in plasma for 23 weeks when stored at -15 degrees C or -80 degrees C.     

Simultaneous Analysis of Cimetidine and Ranitidine in Human Plasma by HPLC

Abstract

A rapid method for the simultaneous quantitation of the H₂-receptor antagonist drugs cimetidine and ranitidine in human plasma by isocratic ion-pair reverse-phase HPLC is described. The method involves a simple organic extraction step of the alkalinized plasma containing added internal standard followed by back extraction of the extract with dilute acetic acid and subsequent analysis of the aqueous acidic phase on a reverse-phase (C18) column. The eluting solvent was acetonitrile-water (20:80 v/v) containing 0.005 mole/litre octanesulphonic acid and was monitored at 229 nm. The run time for the assay was 12.5 minutes, with a detection limit for cimetidine of 50 ng/m1/(0.2 μmole/1) and that for ranitidine was 20 ng/ml (0.06 umole/1).     

Fast determination of ochratoxin A in serum by liquid chromatography: comparison with enzymic spectrofluorimetric method.

A rapid high-performance liquid chromatographic method for the determination of low concentrations of ochratoxin A in serum is described. The extraction procedure was simple and short, and liquid chromatographic analysis was carried out isocratically on a reversed-phase C18 column, with methanol-water-acetic acid (30:70:1) as mobile phase and fluorescence detection (excitation at 336 nm, emission at 465 nm). The examined concentration range, 5-50 ng/ml ochratoxin, the recovery method was 87-94%, compared with 62-67% for the enzymic spectrofluorimetric method. The high-performance liquid chromatographic method was faster because the extraction procedure was shorter, and more sensitive so that small sample volumes could be used.     

Bioanalysis of the investigational anti-tumour drug 5,10-dideaza-5,6,7,8-tetrahydrofolic acid by high-performance liquid chromatography with ultraviolet detection.

A high-performance liquid chromatographic (HPLC) method with ultraviolet detection at 278 nm is presented for the determination of 5,10-dideaza-5,6,7,8-tetrahydrofolic acid in plasma. Sample pretreatment was achieved by using cation-exchange solid-phase extraction columns with methotrexate as internal standard. Chromatographic separation was based on ion-pair HPLC with 1-octanesulphonic acid as the ion-pairing compound. The detection limit was 10 ng/ml using an 500-microliters sample volume. The assay was linear from the detection limit up to 5000 ng/ml with good reproducibility. The applicability of the assay was demonstrated in a study in the rat.