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101.
Yasuhiro Kajihara Hironobu Hashimoto Hisashi Kodama Tomio Wakabayashi Ken-ichi Sato 《Journal of carbohydrate chemistry》2013,32(7):991-995
Abstract Specific inhibitors of glycosyltransferases have become of interest1 not only for investigation of carbohydrate-participating cell-surface phenomena but also for practical use such as chemotherapeutic reagents. Glycosyltransferases catalyze the transfer of glycosyl moieties from nucleotide donors to oligosaccharide acceptors. Therefore, two kinds of substrate-analog inhibitors are possible. The donor analogs have been rather well studied, but are not specific. On the other hand, glycosyltransferases have in general smct acceptor specifkity. Recently, acceptor analogs which inhibit the corresponding glycosyltransferases were reported2-5 and as expected were acceptor-specific inhibitors. 相似文献
102.
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
103.
104.
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
105.
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
106.
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
107.
Atsunori Ono Yohei Takahashi Sumio Kato Masataka Ogasawara Takashi Wakabayashi Yuunosuke Nakahara Shinichi Nakata 《Research on Chemical Intermediates》2011,37(9):1225-1230
A10(PO4)6(OH)2 (A = Ca and Sr)-supported Pt catalysts were prepared and their catalytic activity in NO reduction were investigated. The Sr10(PO4)6(OH)2-supported catalyst had high catalytic activity in the C3H6?CNO?CO2 reaction; the activity was higher than that of the ??-Al2O3-supported catalyst at 300 °C. The basicity of the apatite supports would affect the chemical state of Pt on catalyst, resulting in promotion of NO reduction. 相似文献
108.
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
109.
Usuki H Yamamoto Y Kumagai Y Nitoda T Kanzaki H Hatanaka T 《Organic & biomolecular chemistry》2011,9(8):2943-2951
The reducing tetrasaccharide TMG-chitotriomycin (1) is an inhibitor of β-N-acetylglucosaminidase (GlcNAcase), produced by the actinomycete Streptomyces anulatus NBRC13369. The inhibitor shows a unique inhibitory spectrum, that is, selectivity toward enzymes from chitin-containing organisms such as insects and fungi. Nevertheless, its structure-selectivity relationship remains to be clarified. In this study, we conducted a structure-guided search of analogues of 1 in order to obtain diverse N,N,N-trimethylglucosaminium (TMG)-containing chitooligosaccharides. In this approach, the specific fragmentation profile of 1 on ESI-MS/MS analysis was used for the selective detection of desired compounds. As a result, two new analogues, named TMG-chitomonomycin (3) and TMG-chitobiomycin (2), were obtained from a culture filtrate of 1-producing Streptomyces. Their enzyme-inhibiting activity revealed that the potency and selectivity depended on the degree of polymerization of the reducing end GlcNAc units. Furthermore, a computational modeling study inspired the inhibitory mechanism of TMG-related compounds as a mimic of the substrate in the Michaelis complex of the GH20 enzyme. This study is an example of the successful application of a MS/MS experiment for structure-guided isolation of natural products. 相似文献
110.
Usuki H Yamamoto Y Arima J Iwabuchi M Miyoshi S Nitoda T Hatanaka T 《Organic & biomolecular chemistry》2011,9(7):2327-2335
A new S9 family aminopeptidase derived from the actinobacterial thermophile Acidothermus cellulolyticus was cloned and engineered into a transaminopeptidase by site-directed mutagenesis of catalytic Ser(491) into Cys. The engineered biocatalyst, designated aminolysin-A, can catalyze the formation of peptide bonds to give linear homo-oligopeptides, hetero-dipeptides, and cyclic dipeptides using cost-effective substrates in a one-pot reaction. Aminolysin-A can recognize several C-terminal-modified amino acids, including the l- and d-forms, as acyl donors as well as free amines, including amino acids and puromycin aminonucleoside, as acyl acceptors. The absence of amino acid esters prevents the formation of peptides; therefore, the reaction mechanism involves aminolysis and not a reverse reaction of hydrolysis. The aminolysin system will be a beneficial tool for the preparation of structurally diverse peptide mimetics by a simple approach. 相似文献