NMR AND DFT STUDY OF Co-C BOND ACTIVATION MECHANISM IN VITAMIN B_(12) COMPOUNDS

This report focuses on a theoretical study of the cobalt-cabon bond activation mechanism in Vitamin B12, its co enzyme complexes, and model compounds such as cobalamins (Cbl), cobaloximes and cobalt porphyrins. In particular, emphasis is placed on the nucleotide loop and its role in the base on and base off mechanism.     

A New Convenient Method for the Resolution of 1, 1''''-Binaphthalene-2, 2''''-diol Via a Phosphite Using (-)-Menthol as Resolving Agent

Optically active 1,1-binaphthalene-2, 2-diol has become a quite important chiral source in different fields of chirotechnology, especially in asymmetric synthesis1. Its synthesis and resolution has been extensively studied and various resolution methods have been reported2. Among the reported resolution methods, the following three, namely, via the formation of phosphoric acid derivatives3, boric acid derivatives4 and inclusion complexes5, are the most important. OHOH+_( )-1(-)-(S)-1(+)-(R)…     

Effect of Strong Electron-Phonon Interactions on an Interface Polaron

The present work deals with an electron interacting strongly with both bulk longitudinal optical (LO) phonons and interface (IF) optical phonons in which we adopt and generalize the Tokuda's variational method for studying the interface polaron properties in polar crystals at zero temperature, In our approach, we can reduce the Hamiltollian equation of the system to a pair of integro-differential equations in two variational parameters of the electron wavefunction from which we can calculate various physical properties of an interface polaron including the ground state energy, average numbers of interacting phonons, the average distance from the interface and the anisotropic effective masses of the interface polaron. Numerical results are obtained explicitly for LiF crystal interfaced with NaF crystal as well as other similar systems with varying physical constants, which show the typical trends of variations for the effects of strong electron-phonon interactions on different physical properties of an interface polaron.     

Calculations of Local Distortions Around the Orthorhombic Gd3+ : M+: CaF2 Complexes

A reliable lattice relaxation model is developed in detail for calculating the ionic positions of Gd³⁺ at orthorhombic sites in CaF₂ with a nearby charge-compensating M⁺ ion (M=Li,Na, KJ Rb and Cs). In this model, all the ionic displacements induced by the Gd³⁺ and M⁺ impurity ions are treated using the discrete atomistic basis. In comparison with some experimental data on the ionic shifts in the Gd³⁺: M⁺: CaF₂ complex, our calculated results are found to be much better than the previous calculations based on the semi-discrete approach with a dielectric continuurn approximation.     

Calculation of Vacancy Induced Properties in FCC Metals Using an Alternative Lattice Dynamical Model

Combining the conventional Kanzaki's lattice statics method with an alternative lattice dynamical model called decoupling transformation, a new approach is proposed to calculate the vacancy induced properties in FCC metals. This approach has the advantage over the traditional least-square fit approach in the way that all the model parameters are linearly independent and so it can avoid the problem of non-uniqueness in dynamical model parameters when interactions with more distant atoms are taken into account by fitting to the experimental phonon frequencies only. Numerical results on the lattice dynamical properties such as phonon dispersion curves and interatomic interaction force constants and the vacancy induced properties such as the atomic displacements, lattice relaxation energy, divacancy interaction energy and relaxation volume are obtained specifically for two similar FCC metals, to wit, Cu and Ni and are compared with previous calculations. It is concluded that the interatomic interactions up to the fourth nearest neighbours are already good enough for describing both the lattice vibrational and vacancy induced properties for both metals.     

Influence of Electron-Phonon Interactions on the Physical Properties of an Interface Polaron

Taking into account the interactions of both bulk longitudinal optical (LO) pltonons and surface optical (SO) pltonons and using Haga's perturbatioit method, we derive an effective Hamiltonian for the interface magnetopolaron in polar crystals at zero temperature. We illustrate in details how to solve this effective Hamiltonian analytically and we obtain explicit formulae not on1y for the electron cyclotron mass associated with the Landau levels but also for the self-trapping energy of the magnetopolaron with respect to its first three quantum states in the direction normal to the interface of the system. Numerical results are calculated for some Ⅱ-Ⅵ and Ⅲ-Ⅴ semiconductor compounds,indicting that the bulk LO phonons and SO phonons do have different trends of effects on the electron in different quantum states.     

一种简单组装纳米沸石粒子层的方法及其二次法成膜研究

使用一种简单、新颖的纳米沸石晶体自组装方法, 以γ-氨丙基三甲氧基硅烷(AP-TMS)为偶联剂, 成功地实现了纳米A型沸石粒子在多孔不锈钢、陶瓷以及单晶硅表面的沉积组装, 获得了覆盖度高的续、均匀的沸石粒子层. 组装过程在合成釜内分为载体功能化和晶种化两步. 以该沸石粒子层为晶种二次法成膜, 形成了交织生长的连续、均匀的沸石膜, 并用含少量水的苯甲醛混合液评价了微型膜的渗透蒸发性能, 水-苯甲醛分离系数超过10 000以上. 考察了使用γ-氨丙基三甲氧基硅烷(AP-TMS)、γ-氯丙基三甲氧基硅烷(CP-TMS)和γ-巯丙基三甲氧基硅烷(SP-TMS)三种不同偶联剂时, 纳米A型沸石晶体在多孔不锈钢、陶瓷以及单晶硅表面的自组装效果. 研究发现, 使用CP-TMS作为偶联剂时, 只在不锈钢载体上形成较为连续的粒子层, 而使用SP-TMS作为偶联剂时, 在三种载体上纳米A型沸石粒子均不能沉积形成粒子层. 对偶联剂的作用和粒子组装机制进行了讨论和预测.     

Determination of Metallothionein in Different Organs of Ovariectomized Rat by the Cd-Saturation Method

Metallothionein (MT) is a low molecular weight (approximately 6,700 Da), cysteine-rich, heat-stable protein that can be induced by a variety of metals including cadmium, copper and zinc. One of the main functions of metallothionein is to protect against toxicity mediated by metals. Besides metal detoxification, the abundant sulfur molecules of the protein contribute to its function as free radical scavengers.     

用亚微米级晶种涂层法合成NaA沸石膜及其结构表征

 在大孔α-Al2O3陶瓷管载体上,采用亚微米级晶种涂层法在澄清溶液体系中二次生长成膜,制备了NaA沸石膜. 采用TEM,SEM和XRD等手段对晶种、陶瓷载体及沸石膜的结构、晶体形貌和成膜情况进行了表征. 结果表明,合成晶种的晶粒呈立方体,颗粒小(约150 nm)而均匀,无杂晶,可作为晶种在载体上进行预涂. 载体的孔径大而不均匀,表面粗糙不平整,直接成膜则表面仅有较少的沸石晶粒沉积,不能连续成膜. 经亚微米级晶种涂层后,载体表面形成了一层均匀、光滑的晶种层(厚度为2～3 μm); 水热晶化成膜后,膜表面晶粒相互交织生长完好,无晶间隙,所得膜致密,连续,规整,清晰,无裂缺. 该法是一种制备沸石膜的好方法.