Asymmetric activation of chiral alkoxyzinc catalysts by chiral nitrogen activators for dialkylzinc addition to aldehydes: super high-throughput screening of combinatorial libraries of chiral ligands and activators by HPLC-CD/UV and HPLC-OR/RIU systems

Asymmetric catalysts, prepared by chiral ligand exchange or chiral modification, can evolve further into highly activated catalysts through engineering with chiral activators. Two new methodologies for "super high-throughput screening" (SHTS) of chiral ligands and activators have been developed as a combination of HPLC-CD/UV (CD/ UV = circular dichroism/ultraviolet spectroscopy) or -OR/RIU (OR/RIU = optical rotation/refractive index unit) with a combinatorial chemistry (CC) factory. With these techniques, the % ee of the product is determined within minutes without separation of the enantiomeric products by using a nonchiral stationary phase. Therefore, those SHTS techniques combined with our 'asymmetric activation' concept can provide a powerful strategy for finding the best activated chiral catalyst.     

Orosomucoid 1 and orosomucoid 2 types in the Taiwanese and Japanese: evidence for five new orosomucoid variants

The genetic polymorphisms of orosomucoid, ORM1 and ORM2, were analyzed by isoelectric focusing on polyacrylamide gels and subsequent immunoprinting. Sera from 600 unrelated individuals in Taiwan and Japan were examined. Five new alleles, designated ORM1*7, ORM1*8, ORM1*4.2, ORM2*8 and ORM2*10, were observed together with common and rare alleles that have been found in the Japanese and the Filipinos. As compared with the Japanese, the Taiwanese have a higher frequency of ORM1*1, and a significantly lower frequency of ORM1*2.1.     

Substoichiometry in trace analysis

Substoichiometric methods of analysis are simple in principle and involve the addition of a smaller amount of reagent than is required for complete reaction with the element to be determined. They can be used with great effect in trace analysis.     

Technetium(VII) sulfide colloid growing observed by laser-induced photoacoustic spectroscopy

Particle growing processes were investigated for technetium(VII) sulfide (Tc₂S₇) colloids produced in a mixture of Na₂S and TcO₄ ^- solutions by laser-induced photoacoustic spectroscopy (LPAS). Analysis of the LPAS signal intensities indicated that the particle size increased in the solution with an increase of standing time, while the number of particles remained constant. It was revealed that the size of colloid particles increased by deposition of Tc₂S₇ on the particle surfaces, not by coagulation of colloid particles. The formation mechanism and growing process of the colloids are discussed based on the LaMer model, which deals with nucleation processes.     

Adsorption of bile acid by chitosan-orotic acid salt and its application as an oral preparation

The orotic acid (OT) salt of chitosan (CS), CS-OT, and that of a CS derivative, CP, were prepared, and the adsorption of primary or secondary bile acid was investigated. Calcium-induced alginate gel beads (Alg-Ca) containing CS-OT were also prepared and autoclaved, and the possibility of these beads to act as a vehicle for oral administration to prevent hyperlipidemia was investigated. When taurocholate (TCA) and glycocholate (GCA) were present together in the medium, CS-OT adsorbed identical amounts of both bile acids. This trend was seen in all CPs, although the capacity to adsorb bile acid was affected by the number and/or structure of the amino groups in the CP. On the other hand, taurodeoxycholate, a secondary bile acid was preferentially adsorbed over TCA and GCA. Alg-Ca containing CS-OT took up bile acids in a similar manner as CS-OT irrespective of the water content of the gel matrix. As all elements can be taken as a food, Alg-Ca containing CS-OT could serve as a useful dietary agent for the prevention of hyperlipidemia, which is a lifestyle-related disease.     

Hydration effect on the ion-pair extraction of lithium picrate by hydrophobic benzo-15-crown-5 ether into various less-polar diluents.

The ion-pair formation constant (K(MLA)(0) in mol(-1) dm(3)) for Li(B15C5)(+) with a picrate ion (Pic(-)) in water was determined by potentiometry with a K(+)-selective electrode at 25 degrees C and an ionic strength of 0, where B15C5 denotes benzo-15-crown-5 ether. Using the concentration equilibrium constants, K(MLA), estimated from this value, the extraction constants (mol(-2) dm(6) unit) of about ten diluents were re-calculated from previously reported extraction data. Also, the distribution constants of an ion-pair complex, Li(B15C5)Pic, between water and the diluents were re-estimated. A disagreement in the determined K(MLA) value between a solvent-extraction method and potentiometry was explained in terms of the Scatchard-Hildebrand equation; it came from the fact that the hydration of Li(I) in Li(B15C5)Pic was larger than that of free B15C5 in water. Then, the previously determined value by the former method was re-estimated using the potentiometric K(MLA) value.     

Xenon-plasma light ultrahigh-resolution ARPES study of low-energy single-particle excitation gap in (Bi,Pb)2Sr2CuO6

We have performed ultrahigh-resolution angle-resolved photoemission spectroscopy of (Bi,Pb)₂Sr₂CuO₆ by using a newly developed xenon-plasma light source to clarify the origin of the pseudogap (PG). We determined the comprehensive momentum and temperature dependences of the superconducting (SC) gap and the PG, and revealed a smooth evolution of the PG from the SC gap. We also found a linear scaling behavior of the characteristic PG temperature with the SC gap size regardless of the momentum location. These experimental results strongly suggest that the observed PG is caused by the precursor pairing.