Free volumes in polystyrene probed by positron annihilation

Free volume characteristics in three samples of monodisperse polystyrene were investigated by positron annihilation technique over a temperature range from 300 to 380 K. The number-average molecular weight of the samples ranged from 5730 to 1,524,000. The observed lifetime spectra were resolved into three components, where the longest lifetime, τ₃ was associated with the pick-off annihilation of ortho-positronium (o-Ps) trapped by free volumes. The change of the temperature coefficient of τ₃ was observed at around 350 K, at which the value of τ₃ was a constant value of 2,3 ns for all specimens with different molecular weights. There was no discrete change of τ₃ in intensity, which is corresponding to the number of free volumes. The size of free volume at glass transition was evaluated to be 0.l nm³. © 1996 John Wiley & Sons, Inc.     

A high‐performance liquid chromatography assay with a triazole‐bonded column for evaluation of d‐amino acid oxidase activity

Elution profiles of kynurenic acid (KYNA) and 7‐chlorokynurenic acid (Cl‐KYNA) were examined by high‐performance liquid chromatography (HPLC) using a triazole‐bonded stationary phase column (Cosmosil® HILIC) under isocratic elution of a mobile phase consisting of CH₃CN–aqueous 10 mm ammonium formate between pH 3.0 and 6.0. The capacity factors of KYNA and Cl‐KYNA varied with both the CH₃CN content and the pH of the mobile phase. The elution order of KYNA and Cl‐KYNA was reversed between the CH₃CN‐ and H₂O‐rich mobile phases, suggesting that hydrophilic interactions and anion‐exchange interactions caused retention of KYNA and Cl‐KYNA in the CH₃CN‐ and H₂O‐rich mobile phases, respectively. The present HPLC method using a triazole‐bonded column and fluorescence detection (excitation 250 nm, emission 398 nm) was applied to monitor in vitro production of KYNA from d ‐kynurenine (d ‐KYN) by d ‐amino acid oxidase (DAO) using Cl‐KYNA as an internal standard. A single KYNA peak was clearly observed after enzymatic reaction of d ‐KYN with DAO. Production of KYNA from d ‐KYN was suppressed by the addition of commercial DAO inhibitors. The present HPLC method can be used to evaluate DAO activity and DAO inhibitory effects in candidate drugs for the treatment of schizophrenia. Copyright © 2015 John Wiley & Sons, Ltd.     

Annulation of Alkynyl Aryl Ethers with Allyl Pivalates To Give 2,3‐Bismethylenechromanes through Double C−H Bond Cleavage

The treatment of silylethynyloxyarenes with allylic pivalates in the presence of a palladium catalyst led to efficient C?H bond cleavage in both substrates and a novel annulation reaction to give 2,3‐bismethylenechromanes. When ortho‐allylated silylethynyloxybenzenes were used as the substrates, the same products were obtained. This result shows that site‐selective intramolecular hydrovinylation is involved in the annulation reaction. The synthetic utility of the products was demonstrated by the construction of condensed polycycles.     

Photoregulation of DMA Photolyases in Broom Sorghum Seedlings

Abstract— Using dark-grown 3 day-old Sorghum bicolor seedlings, photorepair of cyclobutane pyrimidine dimers (CPD) by CPD-photoIyase and pyrimidine-(6–4)pyrimidinone photoproducts ([6–4]PP) by [6–4]PP-photolyase was studied in vivo and in vitro. The two types of DNA photoproducts were measured with specific monoclonal antibodies. Sorghum seedlings have different photorepair enzymes for CPD and [6–4]PP. The CPD-photolyase was found to be increased in response to light with maximal efficiency in the UVA/blue spectral range, whereas [6–4]PP-photolyase was not influenced by light.     

8-Endo selective Friedel-Crafts cyclization of vinyloxiranes with Co2(CO)6-complexed acetylene

An 8-endo selective Friedel-Crafts cyclization of vinyloxirane 8 with Co₂(CO)₆-complexed benzeneacetylene was found to give poly-functional eight-membered cyclic compound 9 in high yields.     

Single-molecule force spectroscopy for studying kinetics of enzymatic dextran elongations

Catalytic elongation of dextran by a single molecule of dextransucrase (DSase) was directly monitored by observing the movements of the positions of a rupture peak, which represented the adhesive force between an isomaltoheptaose (dextran 7-mer)-immobilized probe and a DSase-immobilized mica surface. This was initiated with the addition of sucrose monomers. From the histograms of the rupture peaks after elongation reactions on each individual enzyme and the continuous peak shift of certain single enzymes, the catalytic elongation rate constant (k(cat)) was ascertained to be 1.2-2.7 s(-1).     

Ambient-pressure organic superconductors kappa-(DMEDO-TSeF)2[Au(CN)4](solv.): Tc tuning by modification of the solvent of crystallization

The unsymmetrical pi donor dimethyl(ethylenedioxy)tetraselenafulvalene (DMEDO-TSeF) has provided six new organic superconductors with a monovalent square-planar [Au(CN)(4)](-) ion and cyclic ethers as solvent of crystallization. The six new organic superconductors kappa-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) [solv.=1,3-dioxolane (DOL), 2,5-dihydrofuran (DHF), tetrahydropyran (THP), 1,3-dioxane (1,3-DOX), 3,4-dihydro-2H-pyran (DHP), or 1,4-dioxane (1,4-DOX)] are classified into two subphases kappa(L) and kappa' according to the differences in their space group symmetry. kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL, DHF, THP, 1,3-DOX or DHP) crystallizes in the orthorhombic space group Pnma, and T(c) of the kappa(L) phase varies by 1.7-5.3 K according to the size and shape of the solvent of crystallization. On the other hand, kappa'-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL or 1,4-DOX) crystallizes in the noncentrosymmetric monoclinic space group Cc. The kappa'-phase containing 1,4-DOX shows superconductivity at 4.2 K, but the kappa'-phase containing DOL does not show superconductivity down to 1.4 K. Systematic investigation of the six new organic superconductors, together with the two previously reported superconductors kappa(H)- and kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](THF), revealed that the T(c) of the present system is finely tunable by utilizing the effect of the solvent of crystallization.     

Crystallization Behavior of Sol-Gel Derived Films by Self-Seeding Process

We propose the novel preparation method, Self-seeding Process, based on the following concept for low temperature crystallization of oxide films. Introduction of desirable inhomogeneity should give lowering of a crystallization temperature through heterogeneous nucleation accompanied with reduced activation energy. We carried out inspection of the above concept through use of PZT films. PZT gel films with the desirable inhomogeneity of microstructure were prepared, and their crystallization behaviors was examined. The PZT film was successfully crystallized at 500°C by the self-seeding process. The single phase (001) oriented PZT film with 0.55 m in thickness was obtained at 550°C for 5 min. The self-seeding process by microstructure control is efficient for the low temperature process of the oxide thin film.