Phase transition between hidden and antiferromagnetic order in URu2Si2

We have carried out thermal expansion measurements on the heavy fermion compound URu2Si2. We have discovered a new anomaly that appears only under pressure for both the tetragonal a and c axes. Plotting these temperatures on a temperature-pressure plane, we have constructed a phase diagram, in which there is a first order phase transition boundary separating a hidden and antiferromagnetic order. When the system enters the antiferromagnetic phase from the hidden order, the lattice constant shrinks along the a axis and elongates along the c axis, leading to an increase in the lattice constant ratio of c/a. We conclude that the system lies close to a bicritical point from which the first order phase transition line emanates.     

Computer-aided modeling of pentachlorophenol 4-monooxygenase and site-directed mutagenesis of its active site

Homology modeling was used to construct a model of the three-dimensional structure of pentachlorophenol 4-monooxygenase (PcpB). A PSI-BLAST homology search was initially performed to identify the 3D structure of proteins homologous with PcpB. The feasibility of modeled structures of PcpB was evaluated by Verify3D, which calculated structural compatibility scores based on 3D-1D profiles. The predicted structure of PcpB had an acceptable 3D-1D self-compatibility score, beyond the incorrect fold score threshold. A PcpB-pentachlorophenol (PCP) complex was then constructed utilizing the modeled PcpB structure. After energy minimization of the complex, and successive minimizations of the system that consisted of the complex and the water layer surrounding the complex, the molecular dynamics of the system were simulated. The active-site residues of PcpB were identified on the basis of the modeled structure, and PcpB mutants were then designed to change the active site residues, expressed, and purified by affinity chromatography. The mutant activity was compared with that of the wild-type to investigate the validity of the modeled structure. The experimental results suggested that Phe85, Tyr216, and Arg235 were relevant to enzyme activity, and that Tyr397 and Phe87 were important for stabilization of the structure of PcpB.     

Ultrafast optical nonlinearity in the quasi-one-dimensional mott insulator Sr2CuO3

We report strong instantaneous photoinduced absorption in the quasi-one-dimensional Mott insulator Sr2CuO3 in the IR spectral region. The observed photoinduced absorption is to an even-parity two-photon state that occurs immediately above the absorption edge. Theoretical calculation based on a two-band extended Hubbard model explains the experimental features and indicates that the strong two-photon absorption is due to a very large dipole coupling between nearly degenerate one- and two-photon states. Room temperature picosecond recovery of the optical transparency suggests the strong potential of Sr2CuO3 for all-optical switching.     

Highly efficient synthesis of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-bi-2-naphthol and -naphthylamine derivatives by partial hydrogenation of 1,1'-binaphthyls with carbon nanofiber supported ruthenium nanoparticles

Use of Ru/CNF-P, nanoruthenium particles dispersed on a nanocarbon fiber support, realizes highly efficient catalytic partial hydrogenation of 1,1'-bi-2-naphthol and -naphthyl-amine derivatives. The reactions proceed in high turnover numbers without racemization of the axial chirality, offering a practical procedure for the production of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyls in good to high yields.     

Unusual behavior of CMC for binary mixtures of alkyltrimethylammonium bromides: dependence on chain length difference

The critical micelle concentrations (CMC) of binary mixtures of alkyltrimethylammonium bromides (CnTAB) were measured by a conductivity method. The CMCs of C12TAB-C14TAB and C14TAB-C16TAB systems exhibit the usual behavior, namely a monotonic decrease of the CMC with the mole fraction of the longer chain surfactant. However, the CMC behaviors of C10TAB-C16TAB, C11TAB-C16TAB, C12TAB-C16TAB, and C11TAB-C14TAB are unusual. The behaviors of the CMCs with mole fraction for these systems consist of three regions, of which the first is characterized by a very small decrease of the CMC in the range of low mole fraction, followed by a second where there is an abrupt decrease of the CMC, and a third where the CMCs exhibit their usual behavior. The molecular interaction parameter omega is almost equal to zero for mixtures that have the usual CMC behavior, but is small and positive for those systems with unusual CMCs. We infer that for very low mole fractions of C16TAB, the C16TA ion in the C12TAB-C16TAB system penetrates imperfectly into the micelle and its two methylene groups exist outside the micelle.     

Deuterium and oxygen-18 determination of microliter quantities of a water sample using an automated equilibrator

We describe a modified version of the equilibration method and a correction algorithm for isotope ratio measurements of small quantities of water samples. The deltaD and the delta(18)O of the same water sample can both be analyzed using an automated equilibrator with sample sizes as small as 50 microL. Conventional equilibration techniques generally require water samples of several microL. That limitation is attributable mainly to changes in the isotope ratio ((18)O/(16)O or D/H) of water samples during isotopic exchange between the equilibration gas (CO(2) or H(2)) and water, and therefore the technique for microL quantities of water requires mass-balance correction using the water/gas (CO(2) or H(2)) mole ratio to correct this isotopic effect. We quantitatively evaluate factors controlling the variability of the isotopic effect due to sample size. Theoretical consideration shows that a simple linear equation corrects for the effects without determining parameters such as isotope fractionation factors and water/gas mole ratios. Precisions (1-sigma) of 50-microL meteoric water samples whose isotopic compositions of -1.4 to -396.2 per thousand for deltaD are +/-0.5 to +/-0.6 per thousand, and of -0.37 to -51.37 per thousand for delta(18)O are +/-0.01 to +/-0.11 per thousand.     

Monometallic and heterobimetallic azanickellacycles as ethylene polymerization catalysts

The azanickellacyclic complex (1) produced by trimerization of an isocyanide on the nickel atom is found to be a new ethylene polymerization catalyst; catalytic activity is increased by incorporation of the second metal to a diimino moiety of 1 leading to formation of heterobimetallic complexes.     

Mössbauer spectroscopic studies on the products of [2]ferrocenophane with CF3COOH,CCl3COOH,CF3SO3H,CH3COOH and SbCl5

Reaction products of [2]ferrocenophane with CF₃COOH, CCl₃COOH, CF₃SO₃H and SbCl₅ were prepared. Mössbauer spectroscopic data and magnetic susceptibility measurements suggest the bond formation of Fe–H⁺ and Fe–Cl⁺, in which iron atoms are in a high-spin Fe/II/state.