Hydrolysis and Condensation Processes of Titanium iso-Propoxide Modified with Catechol: An NMR Study

The hydrolysis and condensation processes of titanium iso-propoxide modified with catechol (C₆H₄(OH)₂; H₂cat) have been investigated by ¹H, ¹³C and ¹⁷O nuclear magnetic resonance spectroscopy. The hydrolysis reactions of the modified titanium iso-propoxide in the system with Ti:tetrahydrofuran (THF):H₂O = 1:20:x (x = 1, 2 and 5 in a molar ratio) are essentially completed in the initial stage (<1 h), and the condensation reactions also proceed significantly during this stage. Upon hydrolysis with H₂O/Ti = 1, the iso-propoxy groups are selectively hydrolyzed and the catecholate groups remain bound to titanium. With H₂O/Ti = 2 and 5, both the iso-propoxy and catecholate groups are hydrolyzed, and the hydrolysis of the iso-propoxy groups is relatively preferential. Approximately half the catecholate groups are stably bound to titanium, even after hydrolysis with H₂O/Ti = 5.     

Reliable and fast allele-specific extension of 3'-LNA modified oligonucleotides covalently immobilized on a plastic base, combined with biotin-dUTP mediated optical detection.

In the present work, a convenient microarray SNP typing system has been developed using a plastic base that covalently immobilizes amino-modified oligonucleotides. Reliable SNP allele discrimination was achieved by using allelic specificity-enhanced enzymatic extension of immobilized oligonucleotide primer, with a locked nucleic acid (LNA) modification at the SNP-discriminating 3'-end nucleotide. Incorporation of multiple biotin-dUTP molecules during primer extension, followed by binding of alkaline phosphatase-conjugated streptavidin, allowed optical detection of the genotyping results through precipitation of colored alkaline phosphatase substrates onto the surface of the plastic base. Notably, rapid primer extension was demonstrated without a preliminary annealing step of double-stranded template DNA, allowing overall processes to be performed within a couple of hours. Simultaneous evaluation of three SNPs in the genes TGFB1, SOD2 and APEX1, previously investigated for association with radiation sensitivity, in 25 individuals has shown perfect assignment with data obtained by another established technique (MassARRAY system).     

Controlled expansion of a molecular cavity in a steroid host compound.

Expansion of a molecular cavity is described by using elongation of the side chain of a bile acid host compound. Bishomocholic acid (2), which has a side chain that is longer by two methylene unit than cholic acid (1), includes many organic substances at 1:1 host:guest ratios. X-ray crystallographic studies revealed that 2 has two types of open host frameworks: a bilayer type and a crossing type. Both of them are isostructural to those of 1, indicating that they are robust against the elongation of the side chain. In the former type, the increment of the width of the host channel corresponds to that of the length of the molecular structures. Larger aromatic guest components such as 1-methylnaphthalene and 1-tetralone, are included in 2, but not in 1.     

Experimental verification of laser photocathode RF gun as aninjector for a laser plasma accelerator

The feasibility of the laser photocathode RF gun, BNL/GUN-IV, as an injector for a laser plasma accelerator was investigated at the subpicosecond S-band twin linac system of the Nuclear Engineering Research Laboratory, University of Tokyo. Electron beam energy of 16 MeV, emittance of 6π mm mrad, bunch length of 240 fs (FWHM), and charge per bunch of 350 pC were confirmed at 10 Hz. As for diagnosis of the femtosecond electron bunch, the quantitative comparison of performance of the femtosecond streak camera, the coherent transition radiation (CTR) Michelson interferometer, and the far-infrared polychromator was carried out. We concluded that the streak camera is the most reliable up to 200 fs and that the polychromator is the best for the shorter electron bunch. The 3.5-ps (rms) resolved synchronization between the YLF laser driver for the gun and the electron bunch was achieved. Based on the above experiences, we have designed and installed a much better laser-electron synchronization system using the Kerr-lens mode-locked Ti:Sapphire laser with the min harmonics synchrolocker and the stable 15-MW klystron. The timing jitter is expected to be suppressed down to 320 fs (rms)     

A Basic Germanodecatungstate with a −7 Charge: Efficient Chemoselective Acylation of Primary Alcohols

The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ‐Keggin germanodecatungstate, [γ‐HGeW₁₀O₃₆]^7? ( A ), having a ?7 charge was, for the first time, successfully synthesized by the reaction of [γ‐H₂GeW₁₀O₃₆]^6? with one equivalent of [(n‐C₄H₉)₄N]OH under non‐aqueous conditions. The activities of germanodecatungstates for base‐catalyzed reactions dramatically increased with increase in the number negative charges from ?6 to ?7. In the presence of A , various combinations of acylating agents and primary alcohols including those with acid‐sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.     

Remarkable Charge Separation and Photocatalytic Efficiency Enhancement through Interconnection of TiO2 Nanoparticles by Hydrothermal Treatment

Although tremendous effort has been directed to synthesizing advanced TiO₂, it remains difficult to obtain TiO₂ exhibiting a photocatalytic efficiency higher than that of P25, a benchmark photocatalyst. P25 is composed of anatase, rutile, and amorphous TiO₂ particles, and photoexcited electron transfer and subsequent charge separation at the anatase–rutile particle interfaces explain its high photocatalytic efficiency. Herein, we report on a facile and rational hydrothermal treatment of P25 to selectively convert the amorphous component into crystalline TiO₂, which is deposited between the original anatase and rutile particles to increase the particle interfaces and thus enhance charge separation. This process produces a new TiO₂ exhibiting a considerably enhanced photocatalytic efficiency. This method of synthesizing this TiO₂, inspired by a recently burgeoning zeolite design, promises to make TiO₂ applications more feasible and effective.     

Luminescence of tris(2,2'-bipyridine)ruthenium(II) cations ([Ru(bpy)(3)]2+) adsorbed in mesoporous silicas modified with sulfonated phenethyl group

The adsorption of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3)]2+) complex cation into modified mesoporous silicas was investigated. In order to immobilize [Ru(bpy)(3)]2+, the mesopore surface was modified with sulfonic acid groups by the reactions between MCM-41 and phenethyl(dichloro)methylsilane and the subsequent sulfonation of the attached phenethyl groups with chlorosulfonic acid. The modified mesoporous silicas effectively adsorbed [Ru(bpy)(3)]2+ from ethanol solution. It was thought that the effective adsorption was the cause of the cooperative effects of the electrostatic interactions between [Ru(bpy)(3)]2+ cation and sulfonic acid group and the interactions between the phenyl rings on the mesopore surface and the bipyridine rings of the complex. The variation of the position and the intensity of the luminescence of [Ru(bpy)(3)]2+ suggested that the average distance between the adjacent [Ru(bpy)(3)]2+ changed with the loading amounts.     

Transparent electrodes fabricated via the self-assembly of silver nanowires using a bubble template

To shore up the demand of transparent electrodes for wide applications such as organic light emitting diodes and solar cells, transparent electrodes are required as an alternative for indium tin oxide electrodes. Herein the self-assembly method with a bubble template paves the way for cost-effective fabrication of transparent electrodes with high conductivity and transparency using self-assembly of silver nanowires (AgNWs) in a bubble template. AgNWs were first dispersed in water that was bubbled with a surfactant and a thickening agent. Furthermore, these AgNWs were assembled by lining along the bubble ridges. When the bubbles containing the AgNWs were sandwiched between two glass substrates, the bubble ridges including the AgNWs formed continuous polygonal structures. Mesh structures were formed on both glass substrates after air-drying. The mesh structures evolved into mesh transparent electrodes following heat-treatment. The AgNW mesh structure exhibited a low sheet resistance of 6.2 Ω/square with a transparency of 84% after heat treatment at 200 °C for 20 min. The performance is higher than that of transparent electrodes with random networks of AgNWs. Furthermore, the conductivity and transparency of the mesh transparent electrodes can be adjusted by changing the amount of the AgNW suspension and the space between the two glass substrates.