Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

Time-resolved fluorescence study of the single tryptophan in thiocyanate and azide derivatives of horseradish peroxidase: Implication for a p H-induced conformational change in the heme cavity

Detailed pH-dependent steady state and picosecond time-resolved tryptophan fluorescence studies on thiocyanate and azide complexes of horseradish peroxidase have been carried out. The fluorescence decay of the single tryptophan in these species was fitted to a discrete three exponential model. Maximum entropy method analysis also gave three distinct regions of lifetime distributions. The fast subnanosecond lifetime component was found to have > 97% amplitude contribution while other two longer lifetime components have small contributions. Small contributions from the nanosecond lifetime components possibly arise from apoprotein impurity or some small amount of disordered heme conformer of the protein. pH dependence of the fast picosecond lifetime components was found to show a systematic behavior which has been interpreted in the light of obligatory conformation change associated with activation of the enzyme at low pH.     

Effect of the three-body force on triton asymptotic normalization constants by the hyperspherical harmonics expansion method

We investigate the change in the calculated value of asymptotic normalization constant (ANC) by the hyperspherical harmonics expansion method with the inclusion of three nucleon force (3BF) in addition to two nucleon force. We see that ANC does not change very much with the inclusion of 3BF indicating that the 3BF does not alter the asymptotic behaviours of HHE wavefunction significantly.     

Room temperature, high-yield synthesis of multiple shapes of gold nanoparticles in aqueous solution

A seed-mediated growth method was used to control the morphology and dimensions of Au nanocrystals by the manipulation of the experimental parameters in aqueous solution at room temperature. This chemical route produces various structural architectures with rod-, rectangle-, hexagon-, cube-, triangle-, and starlike profiles and branched (such as bi-, tri-, tetra-, and multipod) Au nanocrystals of various dimensions in high yield in the presence of a single surfactant, cetyltrimethylammonium bromide.     

Molecular and absolute crystal structure of pindolol-1-(1H-indol-4-yloxy)-3-[(1-methylethyl)amino]-2-propanol: A specific beta-adrenoreceptor antagonist with partial agonist activity

The crystal and molecular structure of pindolol, 1-(1H indol-4-yloxy)-3-[(1-methylethyl)amino]-2-propanol, has been determined by direct methods. Crystals are tetragonal, ,a=b=15.809(4),c=11.246(2) Å,Z=8,D _c=1.174 mg m^–3. The finalR-factor for 2271 reflections withI>2(I) is 0.038. Refinement by full-matrix least-squares on F² also enabled the absolute configuration of the structure to be established. The molecule is essentially planar, including much of the side-chain which is stabilized by the existence of two intramolecular H-bonds, between the ethyl oxygen and OH group, and between the OH and side-chain amide groups, respectively. The crystal structure is formed by three intermolecular hydrogen bonds including two side-chain-side-chain interactions, between ethyl oxygen to amide and OH to amide, and an interaction between the side-chain OH to indole NH.     

Aerial oxidation of primary alcohols and amines catalyzed by Cu(II) complexes of 2,2'-selenobis(4,6-di-tert-butylphenol) providing [O,Se,O]-donor atoms

Seven copper(II)-complexes 1-7 with the ligand 2,2'-selenobis(4,6-di-tert-butylphenol) providing [O,Se,O]-donor atoms have been isolated and characterized. Three of them 1, 2 and 3 are mononuclear, two 4 and 7 dinuclear and 5, 6 are trinuclear. The crystal structures of the complexes were determined by X-ray diffraction and the electronic structures were established by various physical methods including EPR and variable temperature (2-290 K) susceptibility measurements. The magnetic behaviour of the compounds 4-6 exhibits antiferromagnetic exchange coupling resulting in well-isolated S(t)= 1/2 ground state for 5 and 6 and a diamagnetic spin state for 4. Complexes 5 and 6 belong to the class of asymmetric trinuclear copper(II) complexes modelling the trinuclear copper site in multicopper oxidases. Complex 1 is a catalyst in the presence of a strong base for the aerial oxidation of primary alcohols to the corresponding aldehydes. A dinuclear complex, seemed to be 4, prepared in situ has been found to be a catalyst for the aerial oxidation of primary amines containing alpha-C-H atoms. Primary kinetic isotope effects show that H-abstraction from the alpha-carbon atom of a coordinated substrate (alcoholato or amine) is the rate-determining step in both cases. Two functional models for the metalloenzymes galactose oxidase and amine oxidases are thus described.     

Stereoselective syntheses of (−)-chloramphenicol and (+)-thiamphenicol

Chloramphenicol and thiamphenicol have been enantioselectively synthesized using an asymmetric halohydrin reaction as a key step. In particular, halomethoxylation reaction was used, where O-methyl functions as a hydroxyl protecting group and eliminates an additional protection step.     

Nomenclature of polymers (based on structure)

In the complete absence of a systematic polymer nomenclature, a scheme of nomenclature based on structure is proposed. The problem of naming a “mer” has been solved for an addition polymer by adding “ne” to the monomer name, the justification being on withdrawal of a π bond a monomer becomes a mer. To furnish completeness to the nomenclature, condensation polymers were included in the system. The present nomenclature system of polymers is very arbitrary. Some polymers are not chemically named, some named incorrectly, and there are some fantastic names. After pointing these out, the possible solutions were shown, encompassing a systematic discussion on nearly every type of polymer–linear, branched, or crosslinked–and copolymer (including block or graft), and plastic, fiber, or rubber, and stereospecific polymer. One or more names were proposed for different cases.     

Synthesis, X-ray structure and properties of a new nitrite-bound copper(II) complex with 2-(3,5- dimethylpyrazol-1-ylmethyl)pyridine in a CuN4(O) coordination

Synthesis and characterization of a nitrite-bound copper(II) compound [CuL⁴)₂(ONO)]ClO₄ have been achieved (L⁴ = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L⁴ provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the d_x²−y² orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible Cu^II---Cu^I response [cathodic peak potential, E_pc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible Cu^II---Cu^I redox response [ ].     

Mechanisms and kinetics of trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate adsorption onto chitosan

Chitosan, a naturally abundant biopolymer, has widely been studied for metal adsorption from various solutions, but the extension of chitosan as an adsorbent to remove organic substances from water and wastewater has seldom been explored. In this study, the adsorption of an azo dye, trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate (1), from aqueous solution onto the various degrees of deacetylated chitosan has been investigated. Equilibrium studies have been carried out to determine the capacity of chitosan for dye. The experimental data were analyzed using two isotherm correlations, namely, Langmuir and Freundlich equations. The linear correlation coefficients were determined for each isotherm and the Langmuir provided the best fit. The experimental adsorption isotherms were perfectly reproduced in the simulated data obtained from numerical analysis on the basis of the Langmuir model and the isotherm constants. Adsorption of (1) onto the chitosan flakes was found to be strongly depending on degrees of deacetylation in chitosan and temperatures. Significant amounts of (1) were adsorbed by chitosan 8B (higher degree of deacetylated chitosan), but the adsorption capacity was reduced remarkably with increasing solution temperatures. Thermodynamic parameters such as change in free energy (DeltaG), enthalpy (DeltaH), and entropy (DeltaS) were also determined. In addition, kinetic study indicated that the adsorption process mechanisms were both transport- and attachment-limited.