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Shawn Shih 《中国化学会会志》2003,50(4):815-822
A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules. 相似文献
3.
B. Sun Yu. A. Litvinov P. M. Walker K. Beckert P. Beller F. Bosch D. Boutin C. Brandau L. Chen C. Dimopoulou H. Geissel R. Knöbel C. Kozhuharov J. Kurcewicz S. A. Litvinov M. Mazzocco J. Meng C. Nociforo F. Nolden W. R. Plass C. Scheidenberger M. Steck H. Weick M. Winkler 《The European Physical Journal A - Hadrons and Nuclei》2007,31(3):393-394
A new long-lived isomeric state in the near proton dripline nucleus 125Ce has been identified with Schottky mass spectrometry at GSI. The excitation energy E
* = 103(12)keV and the decay time of 193(1)s have been obtained from a single stored fully ionized 125m
Ce58+ ion. The data implies an E3 transition and a 1/2+ assignment for the spin of the isomer. 相似文献
4.
Alick KT Law Deepak Gupta Shawn Levy Douglas C Wallace Robert J McKeon Charles R Buck 《BMC neuroscience》2004,5(1):1
Background
The adenine nucleotide translocator 1 (Ant1) is an inner mitochondrial membrane protein involved with energy mobilization during oxidative phosphorylation. We recently showed that rodent Ant1 is upregulated by transforming growth factor-beta (TGF-β) in reactive astrocytes following CNS injury. In the present study, we describe the molecular mechanisms by which TGF-β1 regulates Ant1 gene expression in cultured primary rodent astrocytes. 相似文献5.
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C. Andreoiu D. Rudolph I. Ragnarsson C. Fahlander R.A.E. Austin M.P. Carpenter R.M. Clark J. Ekman R.V.F. Janssens T.L. Khoo F.G. Kondev T. Lauritsen T. Rodinger D.G. Sarantites D. Seweryniak T. Steinhardt C.E. Svensson O. Thelen J.C. Waddington 《The European Physical Journal A - Hadrons and Nuclei》2002,14(3):317-348
High-spin states in 59Cu were populated using the fusion-evaporation reaction 28Si + 40Ca at a beam energy of 122 MeV. The Gammasphere Ge-detector array in conjunction with the 4π charged-particle detector array
Microball allowed for the detection of γ-rays in coincidence with evaporated light particles. The resulting extensive high-spin
decay scheme of 59Cu is presented, which comprises more than 320 γ-ray transitions connecting about 150 excited states. Their spins and parities
have been assigned via directional correlations of γ-rays emitted from oriented states. Average quadrupole moments of rotational
bands have been determined from the analysis of residual Doppler shifts. Shell model calculations in the fp shell are invoked to study some of the low-spin states, while the experimental characteristics of the rotational bands are
analyzed in the configuration-dependent cranked Nilsson-Strutinsky (CNS) approach.
Received: 15 February 2002 / Accepted: 23 April 2002 相似文献
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Alexopoulos T Allen C Anderson EW Areti H Banerjee S Beery PD Biswas NN Bujak A Carmony DD Carter T Cole P Choi Y De Bonte RJ Erwin AR Findeisen C Goshaw AT Gutay LJ Hirsch AS Hojvat C Kenney VP Lindsey CS LoSecco JM McMahon T McManus AP Morgan N Nelson KS Oh SH Piekarz J Porile NT Reeves D Scharenberg RP Stampke SR Stringfellow BC Thompson MA Turkot F Walker WD Wang CH Wesson DK 《Physical review letters》1990,64(9):991-994
9.
Stuart D Breedon RE Kim GN Ko W Lander RL Maeshima K Malchow RL Smith JR Imlay R Kirk P Lim J McNeil RR Metcalf W Myung SS Cheng CP Gu P Li J Li YK Ye MH Zhu YC Abashian A Gotow K Hu KP Low EH Mattson ME Piilonen L Sterner KL Lusin S Rosenfeld C Wang AT Wilson S Frautschi M Kagan H Kass R Trahern CG Abe K Fujii Y Higashi Y Kim SK Kurihara Y Maki A Nozaki T Omori T Sagawa H Sakai Y Sugimoto Y Takaiwa Y Terada S Walker R Kajino F Perticone D Poling R Thomas T Ishi Y Miyano K Miyata H Sasaki T 《Physical review letters》1990,64(9):983-986
10.