Enhanced selectivity and sensitivity for inorganic anions using an ion-pairing reagent and sample stacking in capillary zone electrophoresis with direct UV detection

In this paper, the use of an ion-pairing reagent to improve the separation selectivity of inorganic anions in CZE was demonstrated by the addition of tetramethylammonium hydroxide (TMAOH) to the electrolyte. The separation of inorganic anions (Cl(-), I(-), Br(-), NO(2)(-), NO(3)(-) and SCN(-)) was performed using co-electroosmotic flow (EOF) with direct UV detection at 185 nm. The parameters affecting the mobility of the tested anions and the EOF such as the electrolyte pH and concentration of TMAOH in the electrolyte were examined to optimise the separation conditions. In addition, sample-stacking techniques were investigated to improve detection sensitivity. Detection sensitivities were improved 5-13-fold using electrokinetic sample stacking. The detection limits ranged from 1-3 micro mol L(-1). Finally, the proposed method was used for the separation of anions in groundwaters.     

Spectrophotometric determination of flucythrinate (synthetic pyrethroid) using phenylhydrazines

Three spectrophotometric methods are described for determining flucythrinate, based on formation of coloured compounds when one of the hydrolysed products of flucythrinate is condensed with 2,4-dinitrophenylhydrazine (2,4-DNPH), 4-nitrophenylhydrazine (4-NPH) or 2,4,6-trinitrophenylhydrazine (2,4,6-TNPH) in the presence of methanolic potassium hydroxide. These coloured compounds absorb strongly at 465 nm (2,4-DNPH), 540 nm (4-NPH) and 485 nm (2,4,6-TNPH). The methods are applicable over the range 0.1-8.0 mug/ml for 2,4-DNPH, 0.5-6.5 mug/ml for 4-NPH and 0.1-6 mug/ml for 2,4,6-TNPH. The methods are rapid, sensitive and selective and can be used for microdetermination of flucythrinate in a commercial formulation, water, grains and crop samples.     

Spectrophotometric determination of traces of selenium(IV) in various environmental samples using the flow-injection technique (FIT)

A simple, sensitive, and rapid flow-injection spectrophotometric method was developed for the determination of trace amounts of selenium(IV). The method is based on the oxidation reaction of 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) by selenium(IV) followed by the coupling reaction with chromotropic acid (4.5-dihydroxy naphthalene-2.7-disulphonic acid) in a basic medium (phosphate buffer, pH 10.5) to give a pink derivative with λ_max 530 nm that is stable for more than 7 days at 35°C. The reaction and flow conditions of the full experimental design were optimized. A detection limit (2s) of 0.25 μg/L Se(IV) was obtained at a sampling rate of 10 samples per hour. Beer’s law is obeyed for a Se(IV) concentration range of 0.05–0.5 μg/mL at the wavelength of maximum absorption. The detailed study of various interference ions indicates that the method is highly selective. The method was successfully applied to the determination of traces of selenium(IV) in various water samples. The results obtained were in good agreement with those obtained by the reported methods at the 95% confidence level. The text was submitted by the authors in English.     

Solution structure and thermolysis of Cobeta-5'-deoxyadenosylimidazolylcobamide, a coenzyme B12 analogue with an imidazole axial nucleoside

The solution structure of Cobeta-5'-deoxyadenosylimidazolylcobamide, Ado(Im)Cbl, the coenzyme B(12) analogue in which the axial 5,6-dimethylbenzimidazole (Bzm) ligand is replaced by imidazole, has been determined by NMR-restrained molecular modeling. A two-state model, in which a conformation with the adenosyl moiety over the southern quadrant of the corrin and a conformation with the adenosyl ligand over the eastern quadrant of the corrin are both populated at room temperature, was required by the nOe data. A rotation profile and molecular dynamics simulations suggest that the eastern conformation is the more stable, in contrast to AdoCbl itself in which the southern conformation is preferred. Consensus structures of the two conformers show that the axial Co-N bond is slightly shorter and the corrin ring is less folded in Ado(Im)Cbl than in AdoCbl. A study of the thermolysis of Ado(Im)Cbl in aqueous solution (50-125 degrees C) revealed competing homolytic and heterolytic pathways as for AdoCbl but with heterolysis being 9-fold faster and homolysis being 3-fold slower at 100 degrees C than for AdoCbl. Determination of the pK(a)'s for the Ado(Im)Cbl base-on/base-off reaction and for the detached imidazole ribonucleoside as a function of temperature permitted correction of the homolysis and heterolysis rate constants for the temperature-dependent presence of the base-off species of Ado(Im)Cbl. Activation analysis of the resulting rate constants for the base-on species show that the entropy of activation for Ado(Im)Cbl homolysis (13.7 +/- 0.9 cal mol(-1) K(-1)) is identical with that of AdoCbl (13.5 +/- 0.7 cal mol(-1) K(-1)) but that the enthalpy of activation (34.8 kcal mol(-1)) is 1.0 +/- 0.4 kcal mol(-1) larger. The opposite effect is seen for heterolysis, where the enthalpies of activation are identical but the entropy of activation is 5 +/- 1 cal mol(-1) K(-1) less negative for Ado(Im)Cbl. Extrapolation to 37 degrees C provides a rate constant for Ado(Im)Cbl homolysis of 2.1 x 10(-9) s(-1), 4.3-fold smaller than for AdoCbl. Combined with earlier results for the enzyme-induced homolysis of Ado(Im)Cbl by the ribonucleoside triphosphate reductase from Lactobacillus leichmannii, the catalytic efficiency of the enzyme for homolysis of Ado(Im)Cbl at 37 degrees C can be calculated to be 4.0 x 10(8), 3.8-fold, or 0.8 kcal mol(-1), smaller than for AdoCbl. Thus, the bulky Bzm ligand makes at best a <1 kcal mol(-1) contribution to the enzymatic activation of coenzyme B(12).     

Spectrophotometric methods for the determination of omeprazole in bulk form and pharmaceutical formulations

Four simple and sensitive methods for the assay of omeprazole (OMZ) were developed. These methods are based on the formation of colored species by treating OMZ with 3-methyl-2-benzothiazolinone hydrazone (MBTH) following oxidation with ferric chloride (method A) or m-aminophenol following oxidation with chloramine-T (CAT) (method B) or Folin-Ciocalteau reagent (FC) (method D), or by oxidizing OMZ with excess N-bromosuccinimide (NBS) and determining the consumed NBS with a decrease in color intensity of Celestine blue (CB) (method C). All variables have been optimized. Regression analysis of Beer's plots showed good correlation in the concentration range of 1.0-10, 2.0-32, 0.4-2.4 and 0.8-10 mug ml(-1) for methods A, B, C and D, respectively. No interference was observed for formulation additives and the validity of each method was tested by analysing capsules containing OMZ. Recoveries were 98.7-100.1%.     

Isotope exchange between bis/diethyl dithiocarbamate/ copper/II/ complex and Cu2+ ion

Isotope exchange behaviour of bis/diethyl dithiocarbamate/ copper/II/ complex has been studied at 30 °C and 40 °C varying the concentration of the complex and metal ion. Results indicate that the complex is labile in chloroform dimethyl sulphoxide medium. Increase in concentration has significant effect on the rate of the reaction. Similarly the increase in temperature increased the rate of the reaction.     

On-column complexation capillary electrophoretic separation of Fe2+ and Fe3+ using 2,6-pyridinedicarboxylic acid coupled with large-volume sample stacking

On-column complexation of Fe2+ and Fe3+ with 2,6-pyridinedicarboxylic acid (2,6-PDCA) formed anionic complexes, which were then separated by capillary zone electrophoresis with direct UV detection at 214 nm. To achieve reasonable separation selectivity and on-column complexation, the conditions such as pH, the concentration of 2,6-PCDA and the EOF modifiers in the electrolyte were examined. The electrolyte contained 5.0 mM 2,6-PDCA, 0.25 mM tetradecyltrimethlammonium bromide (TTAB) and 5% (v/v) acetonitrile at pH 4.0 was optimised for on-column complexation and the separation of Fe[PCDA]2(2-) and Fe[PCDA]2(-). To enhance the detection sensitivity, large-volume sample stacking (LVSS) was used for the on-line preconcentration of Fe[PCDA]2(2-) and Fe[PCDA]2(-). Under the optimised conditions, satisfactory working ranges (0.5-50 microM), lower detection limits (less than 0.1 microM) and good repeatability of the peak areas (R.S.D.: 5.2-7.8%, n = 5) was achieved using LVSS (300 s). With LVSS, the detection sensitivity was enhanced more than 50-fold compared to conventional hydrodynamic injection. The proposed method was used successfully for the determination of Fe2+ and Fe3+ in water samples.     

Depression in the cloud point of Tween in the presence of glycol additives and triblock polymers

Cloud point (C_P) measurements of Tween 20 and Tween 80 were carried out in the presence of various glycol oligomers and triblock polymers (TBP). The cloud points of both Tween 20 and 80 decrease in the presence of both types of additives. Among the glycol oligomeric additives, ethylene glycol monobutyl ether was found to reduce the C_P maximum. An increase in the repeating units of polymeric glycol additives leads to a decrease in C_P. Reduction in the C_P in the presence of TBP depends upon the increase in hydrophobic/hydrophilic ratio among the polypropylene to polyethylene units.     

A first principle study of hydrogen storage in titanium-doped small carbon clusters (C2nTin,n = 2–6)

Structural Chemistry - Hydrogen storage in Ti-doped small carbon clusters, C2nTin (n = 2–6), has been studied using density functional theory. Using the principle of maximum hardness (η)...