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101.
A theoretical investigation of the X(2)A" and A(2)A' electronic states of the HO(2) radical is reported. Both electronic states have nonlinear equilibrium geometries and they correlate with a (2)Pi state at linear geometries so that they exhibit the Renner effect. In highly excited bending states, there is tunneling between two equivalent minima (with geometries where the H nucleus is bound to one, or the other, of the two O nuclei), and the two linear geometries H-O-O and O-O-H become accessible to the molecule. Thus, HO(2) affords an example of the so-called double Renner effect. Three-dimensional potential energy surfaces for the X(2)A" and A(2)A' electronic states of HO(2) have been calculated ab initio and the global potential energy surfaces for the states have been constructed. These surfaces have been used, in conjunction with the computer program DR [Odaka et al., J. Mol. Structure 795, 14 (2006); Odaka et al., J. Chem. Phys. 126, 094301 (2007)], for calculating HO(2) rovibronic energies in the "double-Renner"-degenerate electronic states X(2)A" and A(2)A'. The results of the ab initio calculations, the rovibronic energies obtained, and analyses of the wavefunctions for selected states are presented. 相似文献
102.
103.
[reaction: see text] Nickel catalyst systems for 1,4-addition of trialkylboranes to alpha,beta-unsaturated esters have been developed. Addition of methanol was found to be essential for the alkylation reaction with 9-alkyl-9-BBNs. 相似文献
104.
Gel-based proteomics reveals potential novel protein markers of ozone stress in leaves of cultivated bean and maize species of Panama 总被引:1,自引:0,他引:1
Torres NL Cho K Shibato J Hirano M Kubo A Masuo Y Iwahashi H Jwa NS Agrawal GK Rakwal R 《Electrophoresis》2007,28(23):4369-4381
We examined responses of cultivated bean (Phaseolus vulgaris L. cv. IDIAP R-3) and maize (Zea mays L. cv. Guarare 8128) plants exposed to ozone (O(3)) using a leaf injury assessment and proteomics approach. Plants grown for 16 days in greenhouse were transferred to an O(3) chamber and exposed continuously to 0.2 ppm O(3) or filtered pollutant-free air for up to 72 h. CBB-stained gels revealed changes in ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO) protein. By Western analysis changes in marker proteins for O(3) damage in leaves by 1-DE were checked. In bean leaves, two superoxide dismutase (SOD) protein (19 and 20 kDa) were dramatically decreased, while ascorbate peroxidase (APX, 25 kDa), small heat shock protein (HSP, 33 kDa), and a naringenin-7-O-methyltransferase (NOMT, 42 kDa) were increased by O(3). In maize leaves, expression levels of catalase (increased), SOD (decreased), and APX (increased) were drastically changed by O(3) depending on the leaf stage, whereas crossreacting HSPs (24 and 30 kDa) and NOMT (41 kDa) proteins were strongly increased in O(3)-stressed younger leaves. These results indicated a clear modulation of oxidative stress-, heat shock-, and secondary metabolism-related proteins by O(3). Finally, 2-DE at 72 h after O(3) exposure revealed changes (induction/suppression) in expression levels of 25 and 12 protein spots in bean and maize leaves, respectively. Out of these, ten and nine nonredundant proteins in bean and maize, respectively, were identified by MS. A novel pathogenesis-related protein 2 may serve as a potential marker for O(3) stress in bean. 相似文献
105.
Sushko PV Shluger AL Hirano M Hosono H 《Journal of the American Chemical Society》2007,129(4):942-951
Recently, a novel inorganic electride stable at room temperatures has been obtained by reducing a complex nanoporous oxide 12CaO.7Al2O3 (C12A7) in a Ca atmosphere (Matsuishi, S.; Toda, Y.; Miyakawa, M.; Hayashi, K.; Kamiya, T.; Hirano, M.; Tanaka, I.; Hosono, H. Science 2003, 301, 626). In this system, up to 2.3 x 1021/cm3 electrons can be accommodated in a three-dimensional network of cages formed by a positively charged oxide framework. We demonstrate theoretically that at all concentrations, ne, the electrons are neither associated with specific atoms nor fully delocalized. At low ne, the electrons are isolated from each other and resemble the color centers in insulating materials. They are well localized in some of the lattice cages and yield strong inhomogeneous lattice distortions that provide polaron-type cage-to-cage electron hopping. As ne increases, the electrons form a denser electron gas and become more evenly spread over all available lattice cages. At sufficiently high ne, the system becomes metallic but still retains partially localized character of the conducting electrons. We describe the nature of the electronic states at the Fermi level and predict the changes in the optical and magnetic properties of this system as a function of ne. 相似文献
106.
107.
Odaka TE Melnikov VV Jensen P Hirano T Lang B Langer P 《The Journal of chemical physics》2007,126(9):094301
The authors report here the implementation of a newly developed, highly efficient matrix diagonalization routine in the DR program [T. E. Odaka et al., J. Mol. Struct. 795, 14 (2006)]. The DR program solves the rovibronic Schrodinger equation for a triatomic molecule with a double Renner effect, i.e., with two accessible linear arrangements of the nuclei at which the electronic energy is doubly degenerate. With the new routines, the authors can extend the DR calculations of rovibronic energies for A 2Pi MgNC/MgCN by considering a much larger set of rovibronic states, in particular, states at higher J values, than the authors were able to access previously. 相似文献
108.
Makiko Seno Tomoya Fukui Tomohiro Hirano Tsuneyuki Sato 《Journal of polymer science. Part A, Polymer chemistry》2000,38(23):4264-4271
Polymerization of N‐(2‐phenylethoxycarbonyl)methacrylamide (PECMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was investigated in tetrahydrofuran (THF) kinetically and by means of electron spin resonance (ESR). The overall activation energy of the polymerization was calculated to be 58 kJ/mol. The initial polymerization rate (Rp) is expressed by Rp = k[MAIB]0.3[PECMA]2.3 at 60 °C. Such unusual kinetics may be ascribable to primary radical termination and to acceleration of propagation due to monomer association. Propagating poly(PECMA) radical was observed as a 13‐line spectrum by ESR under practical polymerization conditions. ESR‐determined rate constants of propagation (kp, 4.7–10.5 L/mol s) and termination (kt, 4.6 × 104 L/ml s) at 60 °C are much lower than those of methacrylamide and methacrylate esters. The Arrhenius plots of kp and kt gave activation energies of propagation (24 kJ/mol) and termination (25 kJ/mol). The copolymerizations of PECMA with styrene (St) and acrylonitrile were examined at 60 °C in THF. Copolymerization parameters obtained for the PECMA (M1) − St(M2) system are as follows: r1 = 0.58, r2 = 0.60, Q1 = 0.73, and e1 = +0.22. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4264–4271, 2000 相似文献
109.
Nazrul Islam Peter M. Campbell Thomas J. V. Higgins Hisashi Hirano Raymond J. Akhurst 《Electrophoresis》2009,30(11):1863-1868
Differential in‐gel electrophoresis showed contrasting effects of the transgenic expression of an α‐amylase inhibitor from beans on the proteomes of two pea cultivars. One cultivar showed minor changes relative to its non‐transgenic parent with only one protein changing by more than about twofold. Changes in the abundance of certain endogenous proteins in the other cultivar were of greater number and magnitude with some endogenous proteins undetected while some new protein spots appeared in the transgenic proteome. The sets of proteins with altered expression were generally different between the two cultivars. Some of the proteins that were differentially expressed were identified by MS. Most were seed storage globulins, which are sited together with the transgenic product. Some of the changes may be due to alterations in expression levels but there were also changes due to post‐translational processing. 相似文献
110.
Hayashi S Hirano K Yorimitsu H Oshima K 《Journal of the American Chemical Society》2006,128(7):2210-2211
Treatment of tertiary homoallyl alcohol with aryl halide under palladium catalysis resulted in the transfer of the allyl moiety of the homoallyl alcohol to aryl halide and yielded the corresponding cross-coupling product stereo- and regiospecifically. The transfer process includes retro-allylation, which proceeds via a conformationally regulated six-membered transition state. The retro-allylation can be regarded as a method for the stereo- and regiospecific preparation of sigma-allylpalladium. 相似文献