1,2-bis(4-methoxyphenyl)ethylenediamine as a fluorogenic reagent for reducing carbohydrates

Eight 1,2-diarylethylenediamines in the meso- or DL-form produce fluorescence when heated with reducing carbohydrates in an alkaline medium. Of the diamines, meso-1,2-bis(4-methoxyphenyl)ethylenediamine is the most favourable reagent for reducing carbohydrates, including 2- deoxy sugars, amino sugars and sialic acids. The reagent permits the fluorimetric determination of reducing carbohydrates at concentrations as low as 0.2–0.9 nmol ml^?1.     

Resolution of lymphocyte subpopulations derived from rat spleen by polyamine-graft-PHEMA copolymer

The retention behavior of lymphocyte subpopulations, B cell, T cell and null cell, derived from rat spleen to polyamine-graft-poly(2-hydroxyethyl methacrylate) copolymer (HA) surface was investigated, focusing on the conformational transition of the polyamine side chain as well as the protonation of amino groups in the polyamine grafts. Furthermore, the availability of HA was discussed as a column adsorbent for separation of lymphocyte subpopulations derived from spleen. The conformational transition of polyamine grafts significantly influenced the mode of retention of lymphocyte subpopulations. When polyamine grafts existed in an aggregated conformation (protonatin degree α < 0.5), the retention of lymphocyte subpopulations was decreased in the order B cell> null cell> T cell. On the other hand, when polyamine existed in an extended conformation into the aqueous interior from the matrix interface (α > 0.5), T cell retention became greater than null cell retention, resulting in a decreased B cell> T cell> null cell order. These results indicate that the differential retention of spleen lymphocyte subpopulations is attributed to their differential responses to the change in matrix interface accompanied by the protonation of amino groups. Furthermore, spleen lymphocytes were compared with lymph node lymphocytes in terms of resolution efficacy by an HA copolymer column.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Synthesis and analgesic activity of novel heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives

In order to develop analgesic compounds possessing a sulfur atom in the alicyclic ring, novel cis-fused heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives (II) were synthesized via a unique cyclization reaction starting from 4-(4-methoxyphenylthio)-2-butanone (1) or 6-methoxy-3,4-dihydro-2H-1-benzothiopyran-4-one (7). The analgesic effects of benzothiopyranopyrroles (16, 18) were measured by means of the writhing test. The phenolic derivative 18 completely inhibited the appearance of writhing at the dose of 50 mg/kg, but the methoxy derivative 16 had no analgesic effect.     

Syntheses and biological activities of renin inhibitors containing statine analogues

Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h.     

Systematic enantiomeric separation of [60]fullerene bisadducts possessing an inherent chiral addition pattern

The optical resolution of trans-2 and trans-3 [60]fullerene bisadducts with an inherent chiral addition pattern, modified by Bingel reaction, cycloaddition by benzyne, Prato reaction, and cycloaddition by o-quinodimethane, was systematically investigated by using chiral HPLC columns (Chiralcel OD and Chiralpak AD). The chiroptical properties of enantiomers separated were also examined.     

Cobaltporphyrin‐adsorbed carbon black: highly efficient electrocatalysts for oxygen reduction

meso‐Substituted cobalt porphyrins adsorbed on carbon black were prepared as catalysts for the electroreduction of O₂. The catalyst, which was prepared by using a homogenizer in mixing cobalt tetraethylporphyrin and carbon black, gave rise to electroreduction of O₂ at a remarkably positive potential (E_p = 0.45 V versus saturated calomel electrode (SCE)) and showed a high selectively for the four‐electron reduction (n = 3.8). Electrochemical study and extended X‐ray absorption fine structure (EXAFS) analysis revealed that the adsorbed face‐to‐face dimeric aggregates of cobalt porphyrin molecules were highly efficient catalysts for electroreduction of O₂. Copyright © 2005 John Wiley & Sons, Ltd.     

Studies on polyyne polymers containing transition metals in the main chain. VII. Synthesis and characterization of palladium-polyyne polymers

Metal-polyyne polymers consisting of palladium and conjugated acetylenic systems, where P_D and R represent the —Pd(PBu₃)₂—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω-diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu₃ (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R¹ = R² = H) having M?_w = 29,000 was obtained.     

Construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols

The construction of a liquid-membrane type periodate ion-selective electrode and its application to the potentiometric titration of alpha-diols and alpha-amino-alcohols are described. The ion-pair of periodate anion with Capriquat (tri-n-octylmethylammonium chloride), is easily extracted into nitrobenzene, and this extract is employed as a liquid ion-exchange membrane. The calibration curve shows Nernstian response towards periodate ion over the concentration range from 10(-1)M to 10(-7)M with a slope of 60 mV/pIO(-)(4). Selectivity coefficients with respect to various ions were evaluated. The electrode potential was independent of pH in the range 2.5-7.5. Some alpha-diols and monoethanolamine were successfully titrated potentiometrically with the aid of the present electrode.     

Supramolecular Templating of Mesopores in Phase-Separating Silica Sol-Gels Incorporated with Cationic Surfactant

Silica gels with hierarchical macropores and mesopores have been prepared by inducing phase separation in the alkoxide-based sol-gel system with an addition of alkyltrimethylammonium salt. Narrowly distributed mesopores were observed in the heat-treated gel samples possibly as a result of supramolecular templating of silica oligomers in the reacting solution. The ionic attractive interaction and hydrophobicity of the attached alkyl group cooperatively determined the phase separation tendency. No indication of long-range order of the mesopores was obtained.