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111.
Ohki Y Matsuura N Marumoto T Kawaguchi H Tatsumi K 《Journal of the American Chemical Society》2003,125(26):7978-7988
A series of sulfido-bridged tungsten-ruthenium dinuclear complexes Cp*W(mu-S)(3)RuX(PPh(3))(2) (4a; X = Cl, 4b; X = H), Cp*W(O)(mu-S)(2)RuX(PPh(3))(2) (5a; X = Cl, 5b; X = H), and Cp*W(NPh)(mu-S)(2)RuX(PPh(3))(2) (6a; X = Cl, 6b; X = H) have been synthesized by the reactions of (PPh(4))[Cp*W(S)(3)] (1), (PPh(4))[Cp*W(O)(S)(2)] (2), and (PPh(4))[Cp*W(NPh)(S)(2)] (3), with RuClX(PPh(3))(3) (X = Cl, H). The heterolytic cleavage of H(2) was found to proceed at room temperature upon treating 5a and 6a with NaBAr(F)(4) (Ar(F) = 3, 5-C(6)H(3)(CF(3))(2)) under atmospheric pressure of H(2), which gave rise to [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (7a) and [Cp*W(NHPh)(mu-S)(2)RuH(PPh(3))(2)](BAr(F)(4)) (8), respectively. When Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b) was treated with a Br?nstead acid, [H(OEt(2))(2)](BAr(F)(4)) or HOTf, protonation occurred exclusively at the terminal oxide to give [Cp*W(OH)(mu-S)(2)RuH(PPh(3))(2)](X) (7a; X = BAr(F)(4), 7b; X = OTf), while the hydride remained intact. The analogous reaction of Cp+W(mu-S)(3)Ru(PPh(3))(2)H (4b) led to immediate evolution of H(2). Selective deprotonation of the hydroxyl group of 7a or 7b was induced by NEt(3) and 4b, generating Cp*W(O)(mu-S)(2)Ru(PPh(3))(2)H (5b). Evolution of H(2) was also observed for the reactions of 7a or 7b with CH(3)CN to give [Cp*W(O)(mu-S)(2)Ru(CH(3)CN)(PPh(3))(2)](X) (11a; X = BAr(F)(4), 11b; X = OTf). We examined the H/D exchange reactions of 4b, 5b, and 7a with D(2) and CH(3)OD, and found that facile H/D scrambling over the W-OH and Ru-H sites occurred for 7a. Based on these experimental results, the mechanism of the heterolytic H(2) activation and the reverse H(2) evolution reactions are discussed. 相似文献
112.
The potential energy surface of benzene (C(6)H(6)) with a He*(2(3)S) atom was obtained by comparison of experimental data in collision-energy-resolved two-dimensional Penning ionization electron spectroscopy with classical trajectory calculations. The ab initio model interaction potentials for C(6)H(6)+He*(2(3)S) were successfully optimized by the overlap expansion method; the model potentials were effectively modified by correction terms proportional to the overlap integrals between orbitals of the interacting system, C(6)H(6) and He*(2(3)S). Classical trajectory calculations with optimized potentials gave excellent agreement with the observed collision-energy dependence of partial ionization cross sections. Important contributions to corrections were found to be due to interactions between unoccupied molecular orbitals and the He*2s orbital. A C(6)H(6) molecule attracts a He*(2(3)S) atom widely at the region where pi electrons distribute, and the interaction of -80 meV (ca. -1.8 kcal/mol) just cover the carbon hexagon. The binding energy of a C(6)H(6) molecule and a He* atom was 107 meV at a distance of 2.40 A on the sixfold axis from the center of a C(6)H(6) molecule, which is similar to that of C(6)H(6)+Li and is much larger than those of the C(6)H(6)+[He,Ne,Ar] systems. 相似文献
113.
Tadashi Matsushita 《Synchrotron Radiation News》2013,26(1):29-30
The scope of this two-day meeting (held June 25–26, 2007), organized by the French MELUSYN (Medicine and Synchrotron Light) work group at the new synchrotron radiation facility SOLEIL (Saint-Aubin, France), was to create a timely forum for multi-disciplinary discussions on modern radiation biology. The meeting brought together physicists of diluted and condensed matter, chemists, biochemists, biologists, as well as physicians having a common interest in using synchrotron radiation in the UV, VUV, soft and hard X-ray ranges and the related techniques in order to explore at molecular, cellular or tissular levels various aspects of radiation effects on living systems and the medical consequences for radiotherapy. 相似文献
114.
Isolation of Biphenyl and Polychlorinated Biphenyl-Degrading Bacteria and Their Degradation Pathway 总被引:1,自引:0,他引:1
Young-Cheol Chang Kazunori Takada DuBok Choi Tadashi Toyama Ken Sawada Shintaro Kikuchi 《Applied biochemistry and biotechnology》2013,170(2):381-398
Four strains of biphenyl-degrading bacteria were isolated from a sewage and identified from the Rhodococcus genus (SK-1, SK-3, and SK-4) and Aquamicrobium genus (SK-2) by 16S rRNA sequence. Among these strains, strain SK-2 was most suitable for biphenyl degradation. When 0.65, 1.3, 2.6, or 3.9 mM of biphenyl was used, the biphenyl was completely degraded within 24 and 96 h of culture, respectively. However, in the case of 6.5 and 9.75 mM of biphenyl, the biphenyl degradation yields were about 80 % and 46.7 % after 120 h of culture, respectively. The isolated strains could degrade a broad spectrum of aromatic compounds including high-chlorinated polychlorinated biphenyl (PCB) congeners in the presence of biphenyl. In addition, strain SK-2 could utilize PCB congeners containing one to six chlorine substituents such as 2,2′,4,4′,5,5′-hexachlorobiphenyl. The PCB utilization rate by the strain SK-2 was increased compared to that of other PCB congener-utilizing bacteria. The four isolates metabolized 4-chlorobiphenyl to 4-chlorobenzoic acid and 2-hydroxy-6-oxo-6-(4′-chlorophenyl)-hexa-2,4-dienoic acid. These results suggest the isolated strains might be good candidates for the bioremediation of PCB-contaminated soil, especially high-saline soils. 相似文献
115.
Franziska Pecho Dr. You-Quan Zou Johannes Gramüller Prof. Dr. Tadashi Mori Prof. Dr. Stefan M. Huber Dr. Andreas Bauer Prof. Dr. Ruth M. Gschwind Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5190-5194
A chiral phosphoric acid with a 2,2’-binaphthol core was prepared that displays two thioxanthone moieties at the 3,3’-position as light-harvesting antennas. Despite its relatively low triplet energy, the phosphoric acid was found to be an efficient catalyst for the enantioselective intermolecular [2+2] photocycloaddition of β-carboxyl-substituted cyclic enones (e.r. up to 93:7). Binding of the carboxylic acid to the sensitizer is suggested by NMR studies and by DFT calculations to occur by means of two hydrogen bonds. The binding event not only enables an enantioface differentiation but also modulates the triplet energy of the substrates. 相似文献
116.
Type I (α-) and II cleavages are two of the best known photochemical processes of alkanone.2 Extensive and intensive investigations have been done on both types of reactions in order to clarify the influence of structural changes on the reactivity, specificity, and efficiency of photoreactions of alkanones.3 The type I cleavage of medium-ring alkanones is believed to produce a radical pair, the fate of which will be determined by the ready formation of transition states for transfer of Ha, Hb, and recyclization. We now wish to report 相似文献
117.
The title compound was obtained from 1,3-dichloro-adamantane and some silylating reagents with Na-HMPA. 相似文献
118.
Nallusamy Venkatachalam Eva Hemmer Tomoyoshi Yamano Hiroshi Hyodo Hidehiro Kishimoto Kohei Soga 《Progress in Crystal Growth and Characterization of Materials》2012,58(2-3):121-134
Yttrium hydroxyl carbonate (Y(OH)CO3) precursors were synthesized by the homogeneous co-precipitation method in the presence of polyacrylic acid (PAAc). Resultant precursor particle size is about 15–20 nm with narrow size distribution whereas the particle size is smaller than those acquired by the conventional homogeneous precipitation method. Effective decrease of Y(OH)CO3 particle size was found to be higher for the presence of weak polyanionic ionomer such as PAAc than the presence of strong polyanionic ionomer such as sodium polystyrene sulfonate (PSS). It was observed that the morphology and size of the precursors are almost unchanged after the calcination process. Er3+ doped Y2O3 nanoparticles were synthesized by PAAc assisted homogeneous co-precipitation method showed bright green (550 nm) and red (660 nm) upconversion (UC) as well as near-infrared (NIR) fluorescence (1550 nm) under 980-nm excitation. UC and NIR fluorescence bioimaging and in-vitro cytotoxicity assay of Er3+ doped Y2O3 nanoparticles were successfully attempted with commercially available macrophages and B-cell hybridomas. Cellular uptake of nanoparticles is evidenced from bright field, UC and NIR fluorescence images of macrophages. 相似文献
119.
120.
Masahito Segi Hiroaki Yamamoto Takeyoshi Hori Tadashi Nakajima 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):599-602
Selenoaldehydes and selenoketones, generated by thermal retro-Diels-Alder reaction of their cycloadducts with cyclopentadiene, reacted with oxygen-functionalized conjugated dienes such as 1-acetoxy-1,3-butadiene, Danishefsky's diene, and 1,4-diacetoxy-1,3-butadiene to give the corresponding cycloadducts in good yields regioselectively. 相似文献