Use of micellar mobile phases for the chromatographic determination of clorazepate, diazepam, and diltiazem in pharmaceuticals

An ODS-2 column, a micellar mobile phase of high elution strength containing 0.1M sodium dodecyl sulfate and 3% (v/v) butanol, and ultraviolet detection at 230 nm are used for the determination of either of two benzodiazepines (clorazepate and diazepam) and a benzothiazepine (diltiazem) in pharmaceuticals. The procedure is shown to be competitive against conventional chromatography with methanol-water mobile phases, especially for diltiazem. The composition of the micellar mobile phase is selected using a predictive strategy based on an accurate retention model and assisted by computer simulation. Calibration graphs are linear at least in the 2.5 to 20 microg/mL, 4 to 20 microg/mL, and 5 to 40 microg/mL ranges for clorazepate, diazepam, and diltiazem, respectively. The intra- and interday repeatabilities (%) are clorazepate (1.7, 5.2), diazepam (0.43, 3.7), and diltiazem (0.36, 3.1). Limits of detection are well below the concentrations of the drugs found in the commercial pharmaceutical preparations analyzed. The drug contents evaluated with the proposed procedure are compared with the declared contents given by the manufacturers. The achieved percentages of label claim are usually between 95 and 104%.     

Analytical applications of membrane extraction in chromatography and electrophoresis

An overview of the analytical applications of membrane-based systems for sample enrichment in chromatography and capillary electrophoresis is presented. A brief introduction to the different types of membranes and the main forces related to the transport through them is also given.     

Determination of six metals in galician red wines (in northwestern Spain) by capillary electrophoresis

A simple technique is described for the routine simultaneous capillary electrophoretic determination of 6 cations in wine. Separation was achieved on a fused silica capillary column with a UV-Cat-1, alpha-hydroxysobutyric acid and 18-crown-6-ether buffer at pH 4.5 and indirect UV detection at 214 nm. The content of magnesium, sodium, potassium, calcium, manganese, and lithium was determined. The method is quantitative, with recoveries in the 92-102% range, and linear over more than one order of magnitude. The precision is better than 2.5-3.4%. The method is sensible, with detection limits between 0.01 and 0.06 mg/L. Twenty-five red wines with a Certified Brand of Origin from Galicia (north-western Spain) were analyzed by the proposed method. Various wines showed very similar electrophoretic profiles, but significant quantitative differences were observed.     

Genomic clustering of the Trypanosoma cruzi nonlong terminal L1Tc retrotransposon with defined interspersed repeated DNA elements

We have analyzed the genomic distribution and organization of the long interspersed nucleotide element (LINE) L1Tc, a nonlong terminal repeat (LTR) retrotransposon of Trypanosoma cruzi. The results indicate that the L1Tc element is dispersed along the parasite genome and that in some regions it is organized in tandem repeats. The data allowed us to define the existence of short direct-repeated sequences flanking the genomic L1Tc elements. Relevant is the finding that the LINE L1Tc is located in genomic regions rich in short interspersed nucleotide elements (SINE)-like sequences. In particular, the L1Tc element is found associated to E13-related sequences, redefined in this work and renamed RS13Tc, and to a newly described RS1Tc sequence. The RS1Tc sequence is present, per haploid genome, in about 3,200 copies. Northern blot analysis showed that the RS1Tc is being transcribed into RNAs of different sizes. The analysis of the chromosomal distribution of these elements in various strains of T. cruzi suggested that this type of clustering might be a common feature of the genome of these parasites.     

Determination of grepafloxacin in plasma samples by HPLC: Application to clinical pharmacokinetic studies

Summary A sensitive HPLC assay for the determination of grepafloxacin (GRE) in biological samples is described. Sample preparations were carried out by adding phosphate buffer (pH 7.4, 0.1M), followed by extraction with trichloromethane. GRE and the internal standard, enrofloxacin (ENR), were separated on a reversed-phase column using an aqueous phosphate solution-acetonitrile (78∶22) mobile phase. The concentrations of ENR and GRE eluting of the column with retention times of 2.55, and 4.90 min, respectively were monitored by fluorescence atλ _ex 338 andλ _em 425 nm. The method was shown to be linear from 5 to 4000 ng mL⁻¹. The detection and quantitation limits were 5 and 10 ng mL⁻¹, respectively. Mean recovery was determined as 90%. Inter- and intra-assay precisions were 3.0% and 3.5% respectively. The method was applied to the determination of GRE in plasma samples collected during clinical pharmacokinetic studies.     

Fluorimetric determination of diacetyl and 2,3-pentanedione with isoniazide and a zirconium salt

Diacetyl and 2,3-pentanedione react with isoniazide in acidified solutions to give the corresponding hydrazones which, by reacting with a zirconium (IV) salt, form fluorescent complexes. Both reactions have been studied separately. Variables such as pH, heating time, and excess of reactives are discussed. The method may be used for the determination of these compounds in foods.     

Direct electrochemical synthesis and characterization of copper(II), iron(II) and iron(III) complexes with 1- and 2-substituted pyridines

Summary The electrochemical oxidation of anodic metals (iron and copper) in MeCN solutions of 2-pyridinone (HOPy), 1-hydroxy-2-pyridinethione (HPT), 2-pyridinemethanethiol-1-oxide (HPMTO) or its dimer 2,2-dithiodimethyldipyridine-1,1-dioxide (PMTO)₂, gave the simple complexes Fe(OPy)₂ · H₂O, Cu(OPy)₂ · 3H₂O, Fe(PT)₂ · 3H₂O, Fe(PT)₃, Cu(PT)₂, Fe(PMTO)₂·3H₂O and Cu(PMTO)₂·H₂O, respectively. When 1,10-phenanthroline (phen) was added to the electrolytic phase, only two mixed complexes were obtained: Cu(OPy)₂phen·3H₂O and Fe(PT)₂phen·2H₂O. The possible molecular structures of the complexes were studied on the basis of their i.r. spectra and magnetic properties.     

A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems

Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems, have been used to test the validity of the equations obtained. Also, it has been verified, from an experimental point of view, that in cosolvent ternary polymer systems there is coincidence in both compositions while in cononsolvent ternary polymer systems, such coincidence does not appear.     

Potassium-selective optrode based on an immobilized fluorogenic crown ether

A new optical sensor phase for potassium ions has been developed based on the immobilization of the pH-dependent fluorogenic crown ether 4-acryloylamidobenzo-18-crown-6 on the non-ionic polymeric resin Amberlite XAD-2.Two different optical designs, a flow-through sensor and a fibre optic probetype sensor (optrode), have been constructed and their analytical performance characteristics have been evaluated. The resulting fluorimetric sensors for K⁺ ions exhibited detection limits of 0.4 or 0.8 M of K⁺ (16 g/l or 31 g/l), depending on the design, while the linear response occurred from 1 to 25 M of the metal concentrations. The precision, evaluated as the relative standard deviation of measurements of K⁺ levels at around ten times the detection limit (e.g. 5 M), turned out to be around ±2%.Advantageous features of this fluorimetric sensing phase and optrode include ease of construction, simplicity of use, reversibility, short response times (ca. 1 min full scale deflection) selectivity and operational stability, suitable for sensing potassium at low levels in complex matrices such as biological fluids.The fluorimetric optical sensor has been successfully applied to the direct determination of potassium in clinically important samples (serum and urine) and in natural waters. Very good accuracy has been obtained just using adequate synthetic aqueous potassium standards for calibration.