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71.
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
72.
We study the generalization of the Willmore functional for surfaces in the three-dimensional Heisenberg group. Its construction is based on the spectral theory of the Dirac operator entering into theWeierstrass representation of surfaces in this group. Using the surfaces of revolution we demonstrate that the generalization resembles the Willmore functional for the surfaces in the Euclidean space in many geometrical aspects. We also observe the relation of these functionals to the isoperimetric problem. 相似文献
73.
Alpeshkumar K. Malde Santosh A. Khedkar Evans C. Coutinho 《Journal of Physical Organic Chemistry》2007,20(2):151-160
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
74.
In this article, a kind of auxiliary design BSA* for constructing BSAs is introduced and studied. Two powerful recursive constructions on BSAs from 3‐IGDDs and BSA*s are exploited. Finally, the necessary and sufficient conditions for the existence of a BSA(v, 3, λ; α) with α = 2, 3 are established. © 2006 Wiley Periodicals, Inc. J Combin Designs 15: 61–76, 2007 相似文献
75.
We prove that three automorphisms of the rooted binary tree defined by a certain 3-state automaton generate a free non-Abelian
group of rank 3.
Both authors are supported by the NSF grants DMS-0308985 and DMS-0456185. Yaroslav Vorobets is supported by a Clay Research
Scholarship. 相似文献
76.
Diming Lu 《中国科学A辑(英文版)》1998,41(2):139-146
Let (H,R) be a triangular Hopf algebra. The monoidal functors on the category of representations ofH is studied, and a universal quantum commutative algebraSeR(M) and a dual H°-comoduleM° for any H-moduleM with an integrale are constructed. Both constructions given here have tensor isomorphism properties.
Project supported by the National Natural Science Foundation of China. 相似文献
77.
G. R. Everest A. J. van der Poorten 《Proceedings of the American Mathematical Society》1997,125(5):1293-1298
We study factorisation in the ring of exponential polynomials and provide a proof of Ritt's factorisation theorem in modern notation and so generalised as to deal with polynomial coefficients as well as with several variables. We do this in the more general context of a group ring of a divisible torsion-free ordered abelian group over a unique factorisation domain.
78.
A. E. Chmel’ 《Journal of Applied Spectroscopy》1997,64(4):566-568
Using Raman spectroscopy, a quantitative analysis of the distribution of OH− ions on the boundary between a bearing pipe and a glass layer deposited from chlorides in billets for quartz fiber light
guides is carried out. Water penetrated into the light-reflecting shell to a depth of several tenths of a millimeter, depending
on the composition of the doping layer (i.e., ultimately on the temperature of the depsoition process).
A. F. Ioffe Physical-Technical Institute, Academy of Sciences of Russia, 26, Politekhnicheskaya St., St. Petersburg, 194021,
Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 548–550, July–August, 1997. 相似文献
79.
80.
Chein-Shan Liu 《Journal of Mathematical Analysis and Applications》2007,331(1):547-566
In this paper we study a circular differential equation under a discontinuous periodic input, developing a quadratic differential equations system on S1 and a linear differential equations system in the Minkowski space M3. The symmetry groups of these two systems are, respectively, PSOo(2,1) and SOo(2,1). The Poincaré circle map is constructed exactly, and a critical value αc of the parameter is identified. Depending on α of the input amplitude the equation may exhibit periodic, subharmonic or quasiperiodic motions. When α varies from α>αc to α<αc, there undergoes an inverse tangent bifurcation; consequently, the resultant Poincaré circle map offers one route to the quasiperiodicity via a type I intermittency. In the parameter range of α<αc the orbit generated by the Poincaré circle map is either m-periodic or quasiperiodic when n/m is a rational or an irrational number. 相似文献