Determination of ppb levels of tryptophan derivatives by capillary electrophoresis with homogeneous liquid-liquid extraction and sweeping method

Tryptophan (Trp) derivatives were selectively separated from 24 kinds of amino acid mixture solutions. Capillary electrophoresis (CE) with UV detection using the described pretreatment system was able to separate and determine 4 kinds of Trp derivatives: 5-hydroxy L-tryptophan, 5-methyl L-tryptophan, 1-methyl L-tryptophan and L-tryptophan. The pretreatment system used a combination of a homogeneous liquid-liquid extraction and a sweeping method, the two are different kinds of powerful preconcentration/separation methods. Trp derivatives were thus separated by two different separation systems. First, these derivatives were selectively extracted at 57-100% by a homogeneous liquid-liquid extraction; secondly, they were respectively separated by micellar electrokinetic chromatography (MEKC) with a sweeping effect. The detection limits following complete separation of the Trp derivatives were 10(-8) mol l(-1) levels, respectively. The proposed method provided a more than 10-fold the improvement in sensitivity compared with fluorescence labeling/fluorophotometric analysis; the proposed method was also applied to the component analysis of nutritious medicine.     

Novel flow injection-fluorometric method for the determination of trace silicate and its application to ultrapurified water analysis

A highly sensitive fluorescence quenching method for the determination of silicate based on the formation of an ion associate between molybdosilicate and Rhodamine B (RB) in nitric acid medium was developed. A flow injection system coupled with a fluorescence detector was used for the measurement of fluorescence intensity at 560 and 580 nm as excitation and emission wavelengths, respectively. The calibration graph for Si showed a linear range of 0.1–5 ng cm⁻³ with correlation coefficient of 0.9999, and the detection limit of 0.06 ng cm⁻³. The proposed method was successfully applied to the determination of silicate in ultrapurified water with satisfactory results.     

Semidifferential electroanalysis with a solid working electrode

Semidifferential electroanalysis is described for hexacyanoferrate(III), dichromate, copper(II), p-aminophenol, p-benzoquinone, m-dinitrobenzene, guanine, guanosine, adenine, and adenosine at a stationary solid working electrode. Nearly symmetrical, peaked curves are obtained for the electrode processes of all the samples investigated. The predicted dependence of peak height and peak potential on concentration, electrode area, and potential scan rate are confirmed-experimentally for the glassy carbon disk electrode. It is demonstrated that the technique with the solid working electrode provides higher sensitivity and better resolution than ordinary linear sweep voltammetry. The sensitivity is somewhat worse than in differential pulse voltammetry, but the technique has the advantage of Speed.     

Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling

The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjected to Suzuki-Miyaura cross-coupling with aryliodides to afford highly substituted biaryls in 53-76% yields.     

Simultaneous assay of four stereoisomers of diltiazem hydrochloride. Application to in vitro chiral inversion studies

Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride (2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5h nor under visible light for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life of 5h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem hydrochloride (2S, 3S) was not observed.     

Catalytic,asymmetric Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen

[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated.     

Significance of anti-HBc IgM in acute hepatitis and hepatitis B associated chronic liver disease

To determine the diagnostic value of anti-HBc IgM in acute viral hepatitis or chronic liver disease B, Anti-HBc IgM was measured by a RIA and an ELISA in 32 patients with acute hepatitis (4 with type A, 15 with type B and 13 with type non A non B), 18 patients with chronic hepatitis and 19 patients with liver cirrhosis. In acute hepatitis B, anti-HBc IgM (both RIA and ELISA) was positive in 14(93%) of 15 patients and its cut-off index value was very high. However, anti-HBc IgM was always negative in one patient with typical course of type B. In 1 of 4 patients with acute hepatitis A and 2 of 13 with non A non B, anti-HBc IgM (RIA and/or ELISA) was positive. These 3 patients were positive for anti-HBs at the onset of disease, so we could not made the diagnosis of acute hepatitis B. Anti-HBc IgM was positive in 21(51%) of 37 patients with HBsAg-positive chronic liver disease by RIA and in 11 (30%) by ELISA, and its cut-off index value was relatively low. These results suggest that when adequate cut-off index value is established, anti-HBc analysis is useful for differentiating recent and current infections from remote infections.