Dependence of the Reactivities of Titanium Enolates on How They Are Generated: Diastereoselective Coupling of Phenylacetic Acid Esters Using Titanium Tetrachloride

Oxidative coupling of phenylacetic acid esters was easily achieved by treating the esters with TiCl(4) and then adding Et(3)N to the resulting solution. The products consisted of dl- and meso-2,3-diphenylsuccinic acid esters with the Claisen condensation product, and the ratio of these products depended on the reaction conditions. Reaction conditions suitable for high dl selectivity were determined, and a dimer of titanium enolate was postulated as an intermediate responsible for the high dl selectivity. The selectivities were compared with those in known oxidative couplings in which titanium enolate intermediates are prepared through lithium enolates and silyl enol ethers. The results suggest that the reactivities of titanium enolates intermediates depend on how they are generated.     

Recent progress of high-power negative ion beam development for fusion plasma heating

A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D⁻ ion beam. In the preliminary experiment using one ion source, a D⁻ ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D⁻ beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/I_D⁻ < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H⁻ ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.     

Effects of poly(ethylene glycol) (PEG) concentration on the permeability of PEG-grafted liposomes

Poly(ethylene glycol)-grafted liposomes (PEG-liposomes) were prepared from dipalmitoylphosphatidylcholine (DPPC) with various amounts of distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (DSPE-PEG) with PEG molecular weights of 1000, 2000, 3000 and 5000. The effects of DSPE-PEG concentration on the permeability of PEG-liposomes were investigated using carboxyfluorescein (CF). In the gel state, the CF leakage from PEG-liposomes was decreased with increasing mole fractions of DSPE-PEG for all PEG molecular weights. In the liquid-crystalline state, the CF leakage from PEG-liposomes containing DSPE-PEG1000 gradually increased with increasing mole fractions of DSPE-PEG, while that of PEG-liposomes whose molecular weight in PEG units was above 2000 rapidly decreased by the addition of DSPE-PEG. Furthermore, no effect of PEG molecular weight on CF leakage was observed. The relationship between the fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) (or 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene (TMA-DPH)) and the mole fraction of DSPE-PEG for PEG-liposomes was also investigated. No significant changes in fluorescence polarization of DPH for liposomal bilayer membranes was observed in the gel and liquid-crystalline states due to the addition of DSPE-PEG, while that of TMA-DPH was decreased compared with that of liposomes without DSPE-PEG in both states.     

Development of novel chiral urea catalysts for the hetero-Michael reaction

Chiral urea compounds 10a-g were synthesized as catalysts for conjugate addition of pyrrolidine (2) to gamma-crotonolactone (3). In the presence of a catalytic amount of the chiral ureas, this hetero-Michael reaction was greatly accelerated. Asymmetric induction was observed with the catalysts 10e, 10f, and 10g.     

Polymerization of vinyl chloride and copolymerization with propylene by a ternary catalyst system

Polymerization of vinyl chloride by the ternary catalyst system of VOCl₃–AIR_nCl_3–n complexing agent was investigated. It was suggested that the formation of a polar complex (or charge-transfer complex) between AlR_nCl_3–n and the complexing agent participated in the polymerization of vinyl chloride. In the copolymerization of vinyl chloride with propylene with the present catalyst system, it was more difficult to incorporate the propylene unit in the copolymer than with a typical radical catalyst.     

Second-derivative spectrophotometric study on the interactions of chlorpromazine and triflupromazine with bovine serum albumin

The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures.