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141.
NeK X-rays have been measured when various thick targets were irradiated by Ne+, ++ ions. For Mg, Al and Ti targets, the X-ray yield dependence on Ne energy agrees qualitatively with the electron promotion model prediction. 相似文献
142.
Reaction profiles and energetics for the reactions of substituted benzaldehydes with a series of different simple metal hydrides (BH(3), BMeH(2), BMe(2)H, AlH(3), and AlMe(2)H) are examined computationally. B3LYP/6-31G optimizations and MP2/6-311G single point energy calculations revealed that the Al reagents are more reactive than B reagents. Replacement of H with Me on BH(3) or AlH(3) makes the reduction transition state (TS) less stable. Accordingly the overall reactivity is in the order AlH(3) > AlMe(2)H > BH(3) > BMe(2)H. The Hammett rho value for substituted benzaldehydes (BAs) is negative for the initial complex formation and positive for the hydride-transfer step. The size and the sign of the apparent rho value depend on the relative stabilities of the separated reactants and the complex. The TS structures vary according to the Hammond postulate for substituted BAs and the variation is reflected in carbonyl-carbon and aldehyde-deuterium isotope effects. Comparison of the reaction profiles of the monomer and dimer reagents reveals that the real reacting species is the monomer in the gas phase for BH(3) but the dimer for BMe(2)H. 相似文献
143.
Shima S Lyon EJ Thauer RK Mienert B Bill E 《Journal of the American Chemical Society》2005,127(29):10430-10435
The iron-sulfur cluster-free hydrogenase (Hmd) from methanogenic archaea harbors an iron-containing, light-sensitive cofactor of still unknown structure as prosthetic group. The enzyme is reversibly inhibited by CO and cyanide and is EPR silent. We report here on M?ssbauer spectra of the (57)Fe-labeled enzyme and of the isolated cofactor. The spectrum of the holoenzyme measured at 80 K revealed a doublet peak with an isomer shift delta = 0.06 mm.s(-)(1) and a quadrupole splitting of DeltaE(Q) = 0.65 mm.s(-)(1) (at pH 8.0). The signal intensity corresponded to the enzyme concentration assuming 1 Fe per mol active site. Upon addition of CO or cyanide to the enzyme, the isomer shift decreased to -0.03 mm.s(-)(1) and -0.00(1) mm.s(-)(1), and the quadrupole splitting increased to 1.38 mm.s(-)(1) and 1.75 mm.s(-)(1), respectively. The three spectra could be perfectly simulated assuming the presence of only one type of iron in Hmd. The low isomer shift is characteristic for Fe in a low oxidation state (0, +1, +2). When the spectra of the holoenzyme and of the CO- or cyanide-inhibited enzyme were measured at 4 K in a magnetic field of 4 and 7 T, the spectra obtained could be simulated assuming the presence of only the external magnetic field, which excludes that the iron in the active site of Hmd is Fe(I), high-spin Fe(0), or high-spin Fe(II). M?ssbauer spectra of the isolated Hmd cofactor are also reported. 相似文献
144.
Akine S Taniguchi T Saiki T Nabeshima T 《Journal of the American Chemical Society》2005,127(2):540-541
Ca2+-selective recognition was achieved by using the site-selective transmetalation of homotrinuclear metallohost [L1Zn3]2+ containing a linear tetraoxime ligand. The selectivity (log(KCa/KMg) > 5.1) is comparable to those of the excellent Ca2+ receptors or sensors such as BAPTA, Quin2, and K23E1. X-ray crystallography revealed that the Ca2+ complex [L1Zn2Ca]2+ has a helical structure. On the other hand, the larger analogue H6L2 gave a mixture of [L2Zn4]2+ isomers, which selectively recognizes Ba2+ to give a single tetranuclear complex, [L2Zn3Ba]2+. 相似文献
145.
Ir-catalyzed enantioselective [2 + 2 + 2] cycloaddition of tetraynes or an octayne with monoalkynes proceeded to give helically-chiral quinquearyl and noviaryl compounds, which respectively have four and eight consecutive axial chiralities, in an almost enantiomerically pure form. 相似文献
146.
147.
Edward A. Nodiff Shuichiro Ina Noriichi Oda Takanori Hayazaki Sansei Nishibe Tetsuya Kohno Martin Hausman Albert A. Manian 《Journal of heterocyclic chemistry》1967,4(2):239-245
The title compounds and various derivatives have been prepared as analytical standards for the identification of chlorpromazine metabolites in biological materials. Additional evidence is presented for the existence of a halogen-induced Smiles rearrangement in the phenothiazine series. 相似文献
148.
When the design work was commenced on the YS-11 transport airplane in 1959, the fatigue behavior of the structure was one of the most cardinal problems in the structural design, then the various design principles were introduced in order to overcome the fatigue problems, and the fatigue test of the full-scale airplane structure was planned to guarantee a fatigue life of 30,000 flight hours. In order to perform the fatigue test of the full-scale air-plane structure, the equipment for the wing fatigue test and for the fuselage fatigue test was developed separately. The former consisted of sixteen hydraulic actuators, controlled automatically, and a program device, being able to program the four different repeated loads; the latter was a familiar water tank in which the fuselage was pressurized by water and loaded, the external loads corresponding to gust loads, standing on the ground loads and the others by actuators. Concerning these tests, the following problems will be explained in our report:
- 1.The structure and operation of the equipment of the full-scale fatigue test. 相似文献
149.
Kazunari Shima 《Zeitschrift fur Physik C Particles and Fields》1983,18(1):25-30
From the group theoretical arguments, we find that among allSO(N) supergravitiesN=10 is the minimal supersymmetry group which unifies all fundamental forces of weak, electromagnetic, strong and gravitational interactions. The (super)symmetry is broken throughSO(10)→SU(3)?SU(2)?U(1)→SU(3)?U(1). All observed particles of the low energy physics (three generations of quarks and leptons, γ,Z, W ± and gluons) and graviton can be minimally accomodated with the correctSU(3)?SU(2)?U(1) quantum numbers. Some characteristic predictions, which can be checked in the coming high energy experiments, are briefly discussed. 相似文献
150.