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101.
K. Imai S. Higashidate A. Nishitani Y. Tsukamoto M. Ishibashi J. Shoda T. Osuga 《Analytica chimica acta》1989
Oxo-steroids and oxo-bile acid ethyl esters were derivatized with 5-N,N-dimethylamino-naphthalene-1-sulphonohydrazide (DNS-hydrazine) to DNS-hydrazone in the presence of hydrochloric acid in ethanol or trifluoroacetic acid in benzene, purified by high-performance gel-permeation chromatography, separated on an ODS column with an eluent containing tetrahydrofuran and detected via a peroxyoxalate chemiluminescence reaction using bis[4-nitro-2-(3,6,9-trioxadecyloxycarbonyl)phenyl] oxalate (TDPO). Sensitive detection (femtomole level) of each oxo-steroid which appeared as a single peak was achieved. The procedure for the isolation of oxo-bile acids developed for GC-MS allowed the detection by this system of an unusual oxo-bile acid, 7α-hydroxy-3-oxo-5β-cholanic acid, at the nanomole l?1 level in urine from a patient with cholestatic liver disease. 相似文献
102.
Koki Tsukamoto Toshio Watanabe Umpei Nagashima Yutaka Akiyama 《Journal of Molecular Structure》2005,732(1-3):87-98
A reaction mechanism of a nitric oxide reductase, cytochrome P450nor (P450nor) from Fusarium oxysporum, was clarified by using Density functional theory and Hartree–Fock calculations. In this reaction mechanism, molecular orbital (MO) analysis revealed that the NO ligand dissociates from the heme iron immediately after one-electron reduction by NADH, and MO energy analysis revealed that NADH acts as a one-electron reducer, not as a two-electron reducer, and that NADH has a pivotal role different from other one-electron reducers. The role of NADH is to act as a double one-electron donor (i.e. one-electron transfer occurring twice) and to combine with the NO− molecule by charge recombination reaction. Our quantum chemical calculations indicated that all reactions occurring in the heme pocket are too fast to become rate-limiting. Therefore, the rate-limiting steps in the proposed reaction mechanism are the process of capturing NO and NADH into the heme pocket and the process of expelling a product generated in the heme pocket. Kinetics of these processes was discussed based on large-amplitude vibration, which helps capturing and expelling processes in a widely opened heme pocket of P450nor. The reaction mechanism proposed here well explains published experimental data. 相似文献
103.
Masataka Sugimoto Hirokazu Hida Takashi Taniguchi Kiyohito Koyama Yuji Aoki 《Rheologica Acta》2007,46(7):957-964
Poly(vinyl chloride) (PVC)/di-isononyl phthalate systems with PVC content of 45.5 (PVC8) and 70.4 wt% (PVC6) were prepared
by a hot roller at 150 °C and press molded at 180 °C. The dynamic viscoelasticity and elongational viscosity of PVC8 and PVC6
were measured in the temperature range from 150 to 220 °C. We have found that the storage and loss shear moduli, G′ and G″, of PVC8 and PVC6 exhibited the power-law dependence on the angular frequency ω at 190 and 210 °C, respectively. Correspondingly, the tan δ values did not depend on ω. These temperatures indicate the critical gel temperature T
gel of each system. The critical relaxation exponent n obtained from these data was 0.75 irrespective of PVC content, which was in agreement with the n values reported previously for the low PVC concentration samples. These results suggest that the PVC gels of different plasticizer
content have a similar fractal structure. Below T
gel, the gradual melting of the PVC crystallites takes place with elevating temperature, and above T
gel, a densely connected network throughout the whole system disappears. Correspondingly, the elongational viscosity behavior
of PVC8 and PVC6 exhibited strong strain hardening below T
gel, although it did not show any strain hardening above T
gel. These changes in rheological behavior are attributed to the gradual melting of the PVC crystallites worked as the cross-linking
domains in this physical gel, thereby inapplicability of the of time–temperature superposition for PVC/plasticizer systems. 相似文献
104.
105.
106.
Ruthenium‐Immobilized Periodic Mesoporous Organosilica: Synthesis,Characterization, and Catalytic Application for Selective Oxidation of Alkanes
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Nobuhiro Ishito Dr. Hirokazu Kobayashi Dr. Kiyotaka Nakajima Yoshifumi Maegawa Dr. Shinji Inagaki Dr. Kenji Hara Prof. Dr. Atsushi Fukuoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15564-15569
Periodic mesoporous organosilica (PMO) is a unique material that has a crystal‐like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2(CO)3]2, is successfully immobilized onto 2,2’‐bipyridine (BPy) units of PMO to form a single‐site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru‐immobilized PMO oxidizes the tertiary C?H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C?H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis‐decalin to cis‐9‐decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions. 相似文献
107.
Prof. Hiroshi Watanabe Ming-Long Yao Atsuko Yamagishi Kunihiro Osaki Toshiyuki Shitata Hirokazu Niwa Yotaro Morishima 《Rheologica Acta》1996,35(5):433-445
Linear and nonlinear viscoelastic properties were examined for a 50 wt% suspension of spherical silica particles (with radius of 40 nm) in a viscous medium, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The effective volume fraction of the particles evaluated from zero-shear viscosities of the suspension and medium was 0.53. At a quiescent state the particles had a liquid-like, isotropic spatial distribution in the medium. Dynamic moduli G* obtained for small oscillatory strain (in the linear viscoelastic regime) exhibited a relaxation process that reflected the equilibrium Brownian motion of those particles. In the stress relaxation experiments, the linear relaxation modulus G(t) was obtained for small step strain (0.2) while the nonlinear relaxation modulus G(t, ) characterizing strong stress damping behavior was obtained for large (>0.2). G(t, ) obeyed the time-strain separability at long time scales, and the damping function h() (–G(t, )/G(t)) was determined. Steady flow measurements revealed shear-thinning of the steady state viscosity () for small shear rates (< –1; = linear viscoelastic relaxation time) and shear-thickening for larger (>–1). Corresponding changes were observed also for the viscosity growth and decay functions on start up and cessation of flow, + (t, ) and – (t, ). In the shear-thinning regime, the and dependence of +(t,) and –(t,) as well as the dependence of () were well described by a BKZ-type constitutive equation using the G(t) and h() data. On the other hand, this equation completely failed in describing the behavior in the shear-thickening regime. These applicabilities of the BKZ equation were utilized to discuss the shearthinning and shear-thickening mechanisms in relation to shear effects on the structure (spatial distribution) and motion of the suspended particles.Dedicated to the memory of Prof. Dale S. Parson 相似文献
108.
Toshiyuki Fujii Genki Okude Akihiro Uehara Shun Sekimoto Hirokazu Hayashi Mitsuo Akabori Kazuo Minato Hajimu Yamana 《Journal of Radioanalytical and Nuclear Chemistry》2011,288(1):181-187
Distribution behavior of Ce(III), Am(III), and Cm(III) between tri-n-butyl phosphate solution and molten calcium nitrate hydrate Ca(NO3)2·RH2O or molten calcium chloride hydrate CaCl2·RH2O was studied radiochemically. In Ca(NO3)2·RH2O systems, maximum separation factors of Ce and Cm to Am were observed to be 12 (Ce/Am) and 1.7 (Cm/Am). The distribution
ratios of these elements increased with the decrease of water activity in the hydrates, and the extractabilities at the water
deficient region was less sensitive compared to those at the water abundant region. This trend was similar to the coordination
circumstance change observed in electronic absorption spectra of Nd(III) in the hydrates. 相似文献
109.
Tsukamoto D Ikeda M Shiraishi Y Hara T Ichikuni N Tanaka S Hirai T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(35):9816-9824
Semiconductor TiO2 particles loaded with WO3 (WO3/TiO2), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO3/TiO2 catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO2. In particular, a catalyst loading 7.6 wt % WO3 led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO2 surface of the catalyst, which is active for oxidation, is partially coated by the WO3 layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO2 surface. This suppresses subsequent decomposition of the aldehyde on the TiO2 surface and results in high aldehyde selectivity. The WO3/TiO2 catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity. 相似文献
110.
Lupoli TJ Tsukamoto H Doud EH Wang TS Walker S Kahne D 《Journal of the American Chemical Society》2011,133(28):10748-10751
The β-lactams are the most important class of antibiotics in clinical use. Their lethal targets are the transpeptidase domains of penicillin binding proteins (PBPs), which catalyze the cross-linking of bacterial peptidoglycan (PG) during cell wall synthesis. The transpeptidation reaction occurs in two steps, the first being formation of a covalent enzyme intermediate and the second involving attack of an amine on this intermediate. Here we use defined PG substrates to dissect the individual steps catalyzed by a purified E. coli transpeptidase. We demonstrate that this transpeptidase accepts a set of structurally diverse D-amino acid substrates and incorporates them into PG fragments. These results provide new information on donor and acceptor requirements as well as a mechanistic basis for previous observations that noncanonical D-amino acids can be introduced into the bacterial cell wall. 相似文献