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71.
H. Muramatsu T. Miura H. Nakahara M. Fujioka E. Tanaka A. Hashizume 《Hyperfine Interactions》1984,20(4):305-325
Radioactive119Sb was implanted into six host matrices (CaSnO3, Pt, Y, Au,-Sn, Pb) and internal conversion electrons of the 23.87 keV transition in119Sn were measured with an iron-free magnetic spectrometer as well as Mössbauer spectra. In the analysis of the conversion spectra of outermost electrons, the overlapping K-LM Auger lines were subtracted using the Auger spectrum of tin measured with another source of117mSn, and the shake-off effect accompanying the conversion process was considered. From the correlation between the Mössbauer isomer shifts and the intensity ratios of O-shell to N1-shell conversion electrons, the change of the nuclear charge radius of the 23.87 keV transition of119Sn was deduced to be R/R=(0.87 ± 0.25) × 10–4 for a uniform charge distribution ofR= 1.2 ×A
1/3 fm or, equivalently, r2>—=(3.6 ± 1.0) ×10–3 fm2. 相似文献
72.
Makoto OzawaTakaaki Taguchi Takayuki ItohYutaka Ebizuka Kevin I Booker-MilburnG.Richard Stephenson Koji Ichinose 《Tetrahedron》2003,59(44):8793-8798
A novel shunt product was isolated from a disruptant of the actVI-ORFA gene involved in the biosynthesis of actinorhodin (ACT) in Streptomyces coelicolor A3(2). Its structure was elucidated as 1,4-naphthoquinone-8-hydroxy-3-[3(S)-acetoxy-butyric acid], (S)-NHAB, based on NMR, MS, and CD spectroscopic data as well as a single crystal X-ray crystallographic analysis. The formation of (S)-NHAB involves a retro-Claisen type C-C bond cleavage of an ACT biosynthetic intermediate. Feeding experiments with [1-13C] and [2-13C] acetates indicated its biosynthetic origin as a single octaketide chain. The relevant gene product, Act-ORFA, which is a functionally unknown protein, is proposed to play a regulatory role related to the multi-enzymatic steps to ACT production, based on the metabolic profile of its disruptant and the wide distribution of actVI-ORFA homologues in the gene clusters for Streptomyces aromatic polyketides. 相似文献
73.
Baba T Abe Y Nomoto K Inazu K Echizen T Ishikawa A Murai K 《The journal of physical chemistry. B》2005,109(9):4263-4268
Methane is shown to react with ethene over In-loaded ZSM-5 to higher hydrocarbons such as propene and toluene at around 673 K. Such methane conversion is not catalyzed by proton-exchanged ZSM-5 (H-ZSM-5) under the same conditions, only C2H4 being converted to higher hydrocarbons. By using 13C-labeled methane (13CH4) as a reactant, the reaction paths for the formation of propene, benzene and toluene were examined. 13C-labeled propene (13CC2H6) is formed by the reaction of 13CH4 with C2H4. The lack of 13C-labeled benzene revealed that propene is not transformed to benzene, which instead originates entirely from C2H4. The 13C atom is inserted both into the methyl group and benzene ring in the toluene formed. This indicates that toluene is formed by two reaction paths; the reaction of 13CC2H6 with butenes formed by the dimerization of C2H4 and the reaction of benzene with 13CH4. The existence of the latter path was proved by the direct reaction of 13CH4 with benzene. The reaction of methane with benzene was also carried out in a continuous flow system over In-loaded ZSM-5. The reaction afforded 7.6% and 0.9% yields of toluene and xylenes, respectively, at 623 K. 相似文献
74.
We report the synthesis of open-ended MoS2 nanotubes and their application as the catalyst for methanation of carbon monoxide with hydrogen. Because the catalysis of the methanation reaction occurs at relatively low temperatures, such nanotubes may provide new solutions toward harnessing the environmental load caused by CO emission. 相似文献
75.
Yoichiro Iwase Koichi Kondo Kenji Kamada Koji Ohta 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3534-3541
1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 104 (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002 相似文献
76.
Noncatalytic reaction pathways and rates of dimethyl ether (DME) in supercritical water are determined in a tube reactor made of quartz according to liquid- and gas-phase 1H and 13C NMR observations. The reaction is studied at two concentrations (0.1 and 0.5 M) in supercritical water at 400 degrees C and over a water-density range of 0.1-0.6 g/cm3. The supercritical water reaction is compared with the neat one (in the absence of solvent) at 0.1 M and 400 degrees C. DME is found to decompose through (i) the proton-transferred fragmentation to methane and formaldehyde and (ii) the hydrolysis to methanol. Formaldehyde from reaction (i) is consecutively subjected to four types of redox reactions. Two of them proceed even without solvent: (iii) the unimolecular proton-transferred decarbonylation forming hydrogen and carbon monoxide and (iv) the bimolecular self-disproportionation generating methanol and carbon monoxide. When the solvent water is present, two additional paths are open: (v) the bimolecular self-disproportionation of formaldehyde with reactant water, producing methanol and formic acid, and (vi) the bimolecular cross-disproportionation between formaldehyde and formic acid, yielding methanol and carbonic acid. Methanol is produced through the three types of disproportionations (iv)-(vi) as well as the hydrolysis (ii). The presence of solvent water decelerates the proton-transferred fragmentation of DME; the rate constant is reduced by 40% at 0.5 g/cm3. This is caused by the suppression of low-frequency concerted motion corresponding to the reaction coordinate for the simultaneous C-O bond scission and proton transfer from one methyl carbon to the other. In contrast to the proton-transferred fragmentation, the hydrolysis of DME is markedly accelerated by increasing the water density. The latter becomes more important than the former in supercritical water at densities greater than 0.5 g/cm3. 相似文献
77.
Thermal motion of CH4+ is investigated by performing an ab initio molecular dynamics method with the second-order M?ller-Plesset (MP2)/6-311G** force field. In the trajectories obtained at 400 K, we have observed rapid interconversion behavior of the geometrical parameters of CH4+ with the frequency of 0.6/ps, where the C-H pair forming the small angle around 55 degrees is switched to another pair on subpicosecond time scale. The switching patterns are found to be classified into the following two types. Type 1: one C-H of the small angled C-H pair is switched to one C-H of the other C-H pair. Type 2: the small angled C-H pair is switched to the other C-H pair, which has been newly observed in the present ab initio MD calculation. The four C-H bonds of CH4+ are characterized by the long and short C-H bonds in a time region of the trajectories, and also for the time-evolution of C-H bonds such interconversion behavior is observed. The switching patterns of the geometrical parameters are compared with those in the interconversion scheme between six equivalent C2v symmetry structures of CH4+ [Paddon-Row, M. N. et al., J Am Chem Soc 1985, 107, 7696]. We have also investigated the electronic energy fluctuation due to thermal motion of CH4+. The standard deviation of total electronic energy at 400 K is evaluated to be 1.2 kcal/mol. 相似文献
78.
CO is found to be oxidized by non-dissociatively adsorbed NO in O2-containing atmosphere over -Al2O3 supported Rh, Ru and their Sn-alloys at 473 K. Reaction between adsorbed N and O to NO seems to lead to low conversion of NO to N2 in an O2-containing atmosphere.
NO - Rh, Ru Sn 473 . NO N2.相似文献
79.
Y. Watanabe M. Nakada K. Endo H. Nakahara H. Sano 《Journal of Radioanalytical and Nuclear Chemistry》1989,136(4):257-266
KX-ray-gated emission Mössbauer spectra of57Co-labelled CoF2 and CoF2.2H2O were measured at room temperature, using the coincidence technique. A difference was found in the relative intensity of57Fe(II)/57Fe(III) between the X-ray-gated and non-gated emission spectra. The results are explained in terms of local radiolytic effects of water of crystallization and the chemical effects associated with the de-excitation processes caused by EC-decay. 相似文献
80.
Sugimoto H Harihara M Shiro M Sugimoto K Tanaka K Miyake H Tsukube H 《Inorganic chemistry》2005,44(18):6386-6392
The cis-dioxo-molybdenum(VI) complexes, [MoO2(L(H))2]2- (1b), [MoO2(L(S))(2)]2- (2b), and [MoO2(L(O))2]2- (3b) (L(H) = cyclohexene-1,2-dithiolate, L(S) = 2,3-dihydro-2H-thiopyran-4,5-dithiolate, and L(O) = 2,3-dihydro-2H-pyran-4,5-dithiolate), with new aliphatic dithiolene ligands were prepared and investigated by infrared (IR) and UV-vis spectroscopic and electrochemical methods. The mono-oxo-molybdenum(IV) complexes, [MoO(L(H))2]2- (1a), [MoO(L(S))2]2- (2a), and [MoO(L(O))2]2- (3a), were further characterized by X-ray crystal structural determinations. The IR and resonance Raman spectroscopic studies suggested that these cis-dioxo molybdenum(VI) complexes (1b-3b) had weaker Mo=O bonds than the common Mo(VI)O2 complexes. Complexes 1b-3b also exhibited strong absorption bands in the visible regions assigned as charge-transfer bands from the dithiolene ligands to the cis-MoO2 cores. Because the oxygen atoms of the cis-Mo(VI)O2 cores are relatively nucleophilic, these complexes were unstable in protic solvents and protonation might occur to produce Mo(VI)O(OH), as observed with the oxidized state of arsenite oxidase. 相似文献