固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.     

Reactivity of the 1,2-Diphenytethyl Radical in a Solvent Cage

The 1,2-diphcnylethyl radical and derivatives were generated from photolysis of tran-f-stilbene and its derivatives 1–13 with secondary amines as quenchers. The 1,2-diphenylelhyl radicals that escaped from the solvent cage were trapped by 2-methyl-2-nitrosopropane (MNP) and were detected by the HPLCEPR method. The yield of the spin adduct is greater for tertiary amines. The smaller yields of the spin adduct formed from secondary amines are ascribed to greater reactivities of the 1,2-diphenylethyl and dialkylamino radicals within the solvent cage.     

包结法拆分1,1'-联-2-萘酚:包结物的晶体结构及CD光谱

以D/L-缬氨醇为原料,通过二步反应得到价廉易得的拆分剂碘化(R)/(S)-N,N,N-三甲基-1-羟基-3-甲基-2-丁铵,采用包结拆分法,成功实现了对1,1′-联-2-萘酚(BINOL)的拆分.对具有(R)-构型的季铵盐与(R)-BINOL在甲醇中所形成包结物的晶体结构分析结果表明:I-离子桥联主体(拆分剂)的醇羟基和客体(BINOL)的酚羟基形成O-H…I-氢键,以及相邻层的主客体分子之间的C-H…O氢键相互作用是在包结物中实现手性识别的关键.同时对两个包结物的溶液和固体圆二色(CD)光谱进行了研究.     

On characterization and perturbation of local -semigroups

Let be a -group with generator , and let be a local -semigroup commuting with . Then the operators , , form a local -semigroup. It is proved that if is injective and is the generator of , then is closable and is the generator of . Also proved are a characterization theorem for local -semigroups with not necessarily injective and a theorem about solvability of the abstract inhomogeneous Cauchy problem:

     

Sodium atom in strong magnetic fields：a pseudospectral approach

Energies and wavefunctions of low-lying states and Rydberg states for the sodium atom in uniform magnetic fields varying from 0 to 10^5T are calculated using a pseudospectral approach with a model potential in spherical coordinates. The energies are comparable with experimental results as well as those obtained by other calculations. The spectra of oscillator strength are worked out. The evolution of them with the magnetic field is shown.     

固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究, 对固体CD光谱在手性配合物研究中的应用, 特别是手性样品固体CD光谱的测试方法进行了概述, 通过对四对手性席夫碱M(II) (M = Ni、Cu)配合物的固体和溶液CD光谱进行比较研究, 发现配合物的手性构型在固液相中保持一致, 但其固液CD光谱之间存在不同程度的差异, 可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.     

Hermitian and Positive Integrated C-cosine Functions on Banach Spaces

Peculiar properties of hermitian and positive n-times integrated C-cosine functions on Banach spaces are investigated. Among them are: (1) Any nondegenerate positiven -times integrated C-cosine function is infinitely differentiable in operator norm; (2) An exponentially bounded, nondegenerateC -cosine function on L ^p () (1L ¹(), C₀ , in case C has dense range) is positive if and only if its generator is bounded, positive, and commutes with C.     

The normed finiteness property of compact contraction operators

We study the joint spectral radius given by a finite set of compact operators on a Hilbert space. It is shown that the normed finiteness property holds in this case, that is, if all the compact operators are contractions and the joint spectral radius is equal to 1 then there exists a finite product that has a spectral radius equal to 1. We prove an additional statement in that the requirement that the joint spectral radius be equal to 1 can be relaxed to the asking that the maximum norm of finite products of a length norm is equal to 1. The length of this product is related to the dimension of the subspace on which the set of operators is norm preserving.     

Chemical Phosphorylation of Nucleosomes and Histone H4

Using N,N′-Dicyclohexylcarbodiimide (DCC) as a condensing agent, ³²P-cyanoethylphosphate and NH₃ were combined to yield ³²P-cyanoethylphosphoramidate. Treatment with NaOH resulted in a β-elimination step to yield ³²P-phosphoramidate and acrylonitrile. The phosphoramidate was purified via DEAE-cellulose chromatography. At pH 7.4 the histidine residues of histone H4 were chemically phosphorylated using ³²P-phosphoramidate as the phosphoryl donor. The nucleophilic nitrogen of the imidazole ring is attracted to the phosphorus of phosphoramidate resulting in the displacement of NH₃ and formation of the protein phosphoryl-nitrogen linkages. Chromatin monomers (nucleosomes) were prepared by a mild digestion of chromatin with micrococcal nuclease. This report also presents the chemical phosphorylation of these nucleosomes by ³²P-phosphoramidate.