Effects of added metal ions on the interaction between polyvinylpyrrolidone and azo dyes carrying hydroxyl groups

The extent of binding of chrome violet, which is a monoazo dye and involves two hydroxyl groups in o and o′ positions to azo group, by polyvinylpyrrolidone is markedly enhanced in the presence of Co²⁺ ion. The amount of binding in the presence of 1 × 10^?4 mol/L of Co²⁺ ion increases by a factor of about 10 compared to that in the absence of the metal ion. Ni²⁺ and Zn²⁺ ions do not perceptively influence the binding affinity of the dye. Cu²⁺ ion, in contrast, suppresses the binding. To investigate further the action of added metal ions, a cobalt–complex dye was prepared and its binding property for the polymer was compared to that of chrome violet in the presence of metal ions. Some possible mechanisms for the enhancement of chrome violet binding by the addition of Co²⁺ ion are described.     

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.     

Aggregated structure analysis of polymer-protected platinum/ruthenium colloidal dispersions using EXAFS, HRTEM, and electron diffraction measurements

Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed.     

Control of calcium carbonate polymorphism and morphology through biomimetic mineralization by means of nanotechnology

In vitro biomimetic mineralization by means of nanotechnology allows the formation of calcium carbonate polymorphs at low temperatures (<25 degrees C) under a CO(2) atmosphere of 500-1500 ppm. A two-dimensional zinc-ion ordered array (zinc array), which acts as an active-site mimic of carbonic anhydrase, has been prepared by immersing the self-organized monolayer of 3-(2-imidazolin-1-y)propyltriethosilane on mica (ImSi substrate) into aqueous zinc solution. The zinc array mounted on the ImSi substrate catalyzed the conversion from CO(2) to HCO(3) (-), and accelerated the formation of calcium carbonate. In situ X-ray diffraction data of the formed calcium carbonate on the poly(L-aspartate)-coated chitin substrate (pAsp substrate), with calcium ion-recognition sites, demonstrated that the interaction between the zinc array and pAsp substrates formed both vaterite and calcite at low temperature (15 degrees C) and mainly vaterite at 25 degrees C; this interaction also controlled the morphology of calcium carbonate formed on pAsp substrate.     

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.     

Chiral recognition of amino acids and dipeptides by a water-soluble zinc porphyrin

A chiral water-soluble zinc porphyrin was optically resolved on a chiral HPLC column, and the binding of chiral amino acids and peptides to each of the enantiomers was examined spectrophotometrically in basic aqueous solution. The binding data apparently indicated that the zinc porphyrin has chiral selectivity for amino acids and dipeptides. This was reasonably explained in terms of the triple cooperation of coordination, Coulomb, and steric interactions of the chiral amino carboxylates with the porphyrin. A compensatory relationship among the thermodynamic parameters for chiral recognition was also shown.     

Metal-dependent regioselective oxidative coupling of 5,10,15-triarylporphyrins with DDQ-Sc(OTf)3 and formation of an oxo-quinoidal porphyrin

[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions.     

Synthetic alpha-mannosyl ceramide as a potent stimulant for an NKT cell repertoire bearing the invariant Valpha19-Jalpha26 TCR alpha chain

A NKT cell repertoire is characterized by the expression of the Valpha19-Jalpha26 invariant TCR alpha chain (Valpha19 NKT cell). This repertoire, as well as a well-established Valpha14-Jalpha281 invariant TCR alpha(+) NKT cell subset (Valpha14 NKT cell), has been suggested to have important roles in the regulation of the immune system and, thus, is a major therapeutic target. Here, we attempted to find specific antigens for Valpha19 NKT cells. Valpha19 as well as Valpha14 NKT cells exhibited reactivity to alpha-galactosyl ceramide (alpha-GalCer). Thus, a series of monoglycosyl ceramides with an axially oriented glycosidic linkage between the sugar and ceramide moiety were synthesized and their antigenicity to Valpha19 NKT cells was determined by measuring their immune responses in culture with glycolipids. Comprehensive examinations revealed substantial antigenic activity for Valpha19 NKT cells by alpha-mannosyl ceramide.     

Investigation of the detection limit for the determination,by pyrolysis-capillary GC,of the thickness of ultra thin PMMA layers coated on to PET film

The determination of nanometer thick layers of poly(methyl methacrylate) coated on to the surface of poly(ethylene terephthalate) film has been investigated by high resolution pyrolysis gas chromatography without sample pretreatment or modification of the instrumentation used. A good linear relationship was observed between the quantity of the characteristic pyrolysate and the thickness of the poly(methyl methacrylate) layer; the detection limit was sufficient to enable the quantitation of poly(methyl methacrylate)-to-poly(ethylene terephthalate) film thickness ratios of 1:20000 in composite materials.     

Chimeric (alpha/beta + alpha)-peptide ligands for the BH3-recognition cleft of Bcl-XL: critical role of the molecular scaffold in protein surface recognition

Molecules that bind to specific surface sites on proteins are of great interest from both fundamental and practical perspectives. We are exploring a ligand development strategy that is based on oligomers with discrete folding propensities ("foldamers"); we target a specific cleft on the cancer-associated protein Bcl-xL because this system is well characterized structurally. In vivo, this cleft binds to alpha-helical segments (BH3 domains) of other proteins. We evaluated several types of helical foldamer, built entirely from beta-amino acid residues or from mixtures of alpha- and beta-amino acid residues, and ultimately identified foldamers in the latter class that bind very tightly to Bcl-xL. Our results suggest that combining different types of foldamer backbones will be an effective and general strategy for creating high-affinity and specific ligands for protein surface sites.