酸糖蛋白手性柱分离6种手性化合物

通过考察缓冲液种类、浓度及其pH值对对映体在手性柱上的保留和分离行为的影响,以及流动相中加入不同种类、不同浓度的不带电荷的有机溶剂乙腈、甲醇、正丙醇、异丙醇、流动相流速和柱温对对映体分离能力的影响,优化了含碳手性中心的碱性药物苯丙哌林、酸性化合物MT-A5及MT-酸和含硫手性中心的质子泵抑制剂奥美拉唑、泮托拉唑、雷贝拉唑对映体分离条件,最佳手性分离条件为:苯丙哌林,0.05 mol/L磷酸二氢铵缓冲液(pH 3.0)-乙腈(95∶5,V/V)为流动相,流速为0.7 mL/m in,柱温为20℃;MT-A5及MT-酸,流动相为0.01 mol/L醋酸铵缓冲液(pH 5.0)-乙腈(74∶26,V/V),流速为0.9 mL/m in,柱温为20℃;泮托拉唑,流动相为10 mmol/L醋酸铵缓冲液(pH 5.5)-乙腈(93∶7,V/V),流速为0.9 mL/m in;柱温为20℃;奥美拉唑和雷贝拉唑,流动相为0.01 mol/L醋酸铵缓冲液(pH 3.0)-乙腈(95∶5,V/V),流速为0.7 mL/m in,柱温为20℃。实现了应用高效液相色谱法在α1-酸糖蛋白手性柱上对上述化合物的对映体分离,并成功用于手性药物合成中的对映体过量百分率的测定。     

Relation between the Hydrodynamic and Elastic Parameters in Surface Wave Diffraction on a Floating Plate

The problem of surface wave diffraction on a floating elastic plate is considered. The relation between the parameters of the elastic vibrations of the plate and the transmitted and reflected wave amplitudes is investigated. It is shown that the maximum amplitudes of the plate stresses and deflections depend nonmonotonically on the incident wave frequency and are reached simultaneously with the maxima of both the transmission coefficient and the length of the wave penetrating into the plate. This makes it possible to use the transmission coefficient as a parameter for investigating the maximum and minimum amplitudes of the hydroelastic vibrations of the plate. As an example, this criterion is used to minimize the vibrations of a plate whose leading edge is elastically connected to the bottom.     

锂锰尖晶石红外光谱的研究

本文对锂锰尖晶石的红外光谱进行了研究。由于锂锰尖晶石的晶体结构属于Fd3m空间群,锂离子占据四面体空隙(8a位置),锰离子占据八面体空隙(16d位置)。根据群论的知识,对锂锰尖晶石晶体中离子的振动方式与红外活性之间的内在关系进行了讨论。并列出了锂锰尖晶石的红外光谱实验数据。通过理论分析,我们推断:位于618.6和501.5cm~(-1)的红外吸收带分别来源于Mn(Ⅳ)-O和Mn(Ⅲ)-O键在晶体中的不对称伸缩振动(单元为Mn(Ⅳ)O_6和Mn(Ⅲ)O_6八面体),位于1124cm~(-1)的弱红外吸收带来源于Li-O键的不对称伸缩(单元为LiO_4四面体)。还有一些低于400cm~(-1)的可能吸收带在400～4000cm~(-1)范围内未能检测到。这一结论的可靠性通过锂锰尖晶石和掺杂的锂锰尖晶石的红外光谱实验数据得到证实。     

On the structure of stationary sets

We isolate several classes of stationary sets of [k]ωand investigate implications among them. Under a large cardinal assumption, we prove a structure theorem for stationary sets.     

弱混强平稳序列随机容量、随即秩次序统计量的极限分布律

设W(1n)W2(n)…W(nn)是严平稳随即序列{Xn,n 1}的前几个变量的顺序统计量,Nn Mn是两正整值r.v,n 1.在较弱一些的混合条件下,本文给出了W(NMn)n标准化后的极限分布,从而使一些提法更趋一般化,主要结果推进了Rao(1984)和张国胜(1993)的工作.由于混合条件的减弱,使得对m-相关和正态平稳过程的具体应用讨论更加充分.     

On the convergence rate and optimization of a numerical method with splitting of boundary conditions for the stokes system in a spherical layer in the axisymmetric case: Modification for thick layers

The convergence rate of a fast-converging second-order accurate iterative method with splitting of boundary conditions constructed by the authors for solving an axisymmetric Dirichlet boundary value problem for the Stokes system in a spherical gap is studied numerically. For R/r exceeding about 30, where r and R are the radii of the inner and outer boundary spheres, it is established that the convergence rate of the method is lower (and considerably lower for large R/r) than the convergence rate of its differential version. For this reason, a really simpler, more slowly converging modification of the original method is constructed on the differential level and a finite-element implementation of this modification is built. Numerical experiments have revealed that this modification has the same convergence rate as its differential counterpart for R/r of up to 5 × 10³. When the multigrid method is used to solve the split and auxiliary boundary value problems arising at iterations, the modification is more efficient than the original method starting from R/r ～ 30 and is considerably more efficient for large values of R/r. It is also established that the convergence rates of both methods depend little on the stretching coefficient η of circularly rectangular mesh cells in a range of η that is well sufficient for effective use of the multigrid method for arbitrary values of R/r smaller than ～ 5 × 10³.     

Electronic spectra of cationic forms of meso-tetrapropylporphin in a nanoporous silicate gel matrix

We have studied the fluorescence and fluorescence excitation spectra at 300 K, 77 K, and 4.2 K for silicate gel matrices colored with meso-tetrapropylporphin by impregnation of the matrix with a solution of the pigment. Comparison of the data obtained with the absorption spectra in acidified solutions and analysis of the low-temperature fine-structure vibronic spectra, and also taking into account data obtained earlier for octaethylporphin in a xerogel showed formation of two cationic forms of meso-tetrapropylporphin in the gel matrix: the short-wavelength form has a dicationic structure, while the long-wavelength form has a monocationic structure. We have traced out the correlations of the vibrational structure in the spectra of the dicationic form with data for the porphin dication, and we have drawn a number of conclusions concerning the normal vibrational modes that are active in the vibronic fluorescence and absorption spectra of the studied cationic forms. Using the AM1 semiempirical quantum chemical method, we optimized the geometry of the mesotetrapropylporphin dication: the most stable of the possible conformers is the dication structure with saddleshaped macrocycle nonplanarity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 453–461, July–August, 2006.     

Enantioseparation of Dencichine and D-Isomer on L-Cysteine Derivative Phase by Ligand-exchange Chromatography

Dencichine (β-N-oxalyl-L-α, β-diaminopropionic acid, L-ODAP), a nonprotein amino acid, is a haemostatic agent present in important Chinese medicinal herbs such as Panax notoginseng, as well as other Panax species1. It was first isolated from the seeds …