聚丙烯微孔膜基渐变聚合物的制备,结构与性能的研究

以聚丙烯微孔膜为基材，通过扩散控制原位共聚合的方法在人填充了组成沿膜的厚度方向逐渐改变的无规共聚物，Ｘ－光电子能谱（ＸＰＳ）、全反射红外光谱（ＡＴＲ）以及动态粘弹谱的分析结果。说明所制备得到的合膜具有明显的渐变聚合物性质。     

An efficient ab initio gradient program

An ab initio Hartree-Fock gradient program is described. It is characterized by (1) efficiency of the gradient evaluation, and (2) capability of handling higher angular momentum (d andf) basis functions. The latter are constructed from shifted Cartesian Gaussian p-type primitives. A satisfactory solution is presented for the problems connected with the neglect of small integrals in a gradient program. Methods for increasing the efficiency of the SCF procedure are discussed.     

A practical approach to transferring linear gradient elution methods

Attempts to theoretically address the problems involved in transferring linear gradient elution methods have been somewhat ad hoc due to the simplifying assumptions usually made in conventional gradient elution theory. Until now, all equations based on the k* parameter of linear gradient elution theory used as the basis for predicting the separation selectivity have not explicitly included the effect of the dwell volume (VD). Using an exact equation for predicting k*, that is, one which fully accounts in an a priori fashion for VD, we find a set of simple yet exact equations which unequivocally must be satisfied to transfer an optimized linear gradient elution method from one system (column or instrument or both) to another. These relationships absolutely mandate that a change in the instrument dwell volume requires a proportional change in the column volume; in turn, a change in the column volume requires a proportional change in the flow rate and/or gradient time to maintain a constant gradient steepness. Although we are not the first to suggest these guidelines, this work provides a complete theoretical foundation for these exact guidelines for the maintenance of gradient selectivity for the case of transferring a linear gradient elution method between different columns packed with the same particles and/or between different instruments.     

Spherical coordinate representations of solvent composition for liquid chromatography method development using experimental design

One of the major techniques used for the method development of ternary and quaternary high performance liquid chromatography (HPLC) systems has been to use mixture designs, often referred to as "Glajch's Triangle". This technique does not allow for the systematic and simultaneous optimization of other factors such as gradient time, pH and temperature that affect the quality of separations. An alternative approach is to use experimental designs. The condition, however, that the composition of all components of the mobile phase must total 100% presents a problem when trying to mathematically represent ranges of each mobile phase constituent of a ternary or quaternary system. A method is described here, based on spherical coordinate representations, that adheres to the constraints of the mobile phase composition and allows experimental designs, such as central composite and factorial designs, to be applied to the simultaneous optimization of the mobile phase composition. Other factors, in particular temperature and gradient time, can then be included in the design. As a result of applying these designs to the HPLC separation of phenols and corticosteroids, it was found necessary to include three-way interactions between experimental factors in the model. The significance of these interactions shows that they need to be considered in HPLC method development.     

任意多阶梯度场强毛细管凝胶电泳中谱带的迁移和展宽

在自行制备的毛细管凝胶电泳柱上，通过实验考察毛细管凝胶电泳（ＣＧＥ）中场强（Ｅ）和组分迁移率（μ）的关系，发现在一般ＣＧＥ使用的场强范围内，μ随Ｅ增大而成近似线性的增加。并讨论了产生这种现象的原因。以此为基础提供了任意多阶梯度场强毛细管凝胶电泳中组分的迁移时间和距离的计算公式，用于编制计算机程序。     

Molecular vibrations in a gradient extremal path

Summary The calculation of vibrational states using a gradient extremal path is discussed. Gradient extremal paths are defined by local criteria, which lead to stable solutions. This has certain advantages in comparison with a steepest-descent path, which is often difficult to determine accurately. For cases where a reaction path formalism is applicable, a path based on the gradient extremal concept gives results in close agreement with those obtained using traditional steepest-descent methods. We present algorithms for carrying out such calculations and also give some numerical results.     

Møller-Plesset (MP2) perturbation theory for large molecules

Summary A novel formulation of MP2 theory is presented which starts from the Laplace transform MP2 ansatz, and subsequently moves from a molecular orbital (MO) representation to an atomic orbital (AO) representation. Consequently, the new formulation is denoted AO-MP2. As in traditional MP2 approaches electron repulsion integrals still need to be transformed. Strict bounds on the individual MP2 energy contribution of each intermediate four-index quantity allow to screen off numerically insignificant integrals with a single threshold parameter. Implicit in our formulation is a bound to two-particle density matrix elements. For small molecules the computational cost for AO-MP2 calculations is about a factor of 100 higher than for traditional MO-based approaches, but due to screening the computational effort in larger systems will only grow with the fourth power of the size of the system (or less) as is demonstrated both in theory and in application. MP2 calculations on (non-metallic) crystalline systems seem to be a feasible extension of the Laplace transform approach. In large molecules the AO-MP2 ansatz allows massively parallel MP2 calculations without input/output of four-index quantities provided that each processor has in-core memory for a limited number of two-index quantities. Energy gradient formulas for the AO-MP2 approach are derived.Dedicated to Prof. W. Kutzelnigg whose books on theoretical chemistry aroused my interest in this field     

梯度淋洗离子色谱法同时分析有机酸与无机酸阴离子的应用研究

利用梯度离子色谱法和抑制电导检测器对有机酸与无机酸阴离子的色谱分析条件进行了研究,建立了最佳梯度程序。通过浓缩柱的富集,可使方法的检出限达1×10-3μg·L-1,各离子的相对标准偏差大部分在5%以下。此方法可用于火电厂水汽系统中痕量低分子有机酸和无机酸阴离子的快速、准确分析,结果满意。     

Quantitative aspects of gradient HPLC of copolymers from styrene and ethyl methacrylate

Summary Prerequisite of quantitative evaluation in chromatography is equivalence of sample composition and detector signal. This includes complete retention and proper elution of all sample constituents. In polymer HPLC, complete retention requires a poor starting eluent, a sufficiently active column, and a low ratio of injection volume to column volume. On small pore columns, insufficient retention caused the polymer to elute either in the interstitial volume (sample exclusion), together with the sample solvent, or immediately after the solvent plug.Stat-copoly(styrene/ethyl methacrylate) samples are more difficultly retained thanstat-copoly(styrene/acrylonitrile) specimes. With the former copolymer it could be shown that incomplete retention did not cause sample demixing. In order to gain complete retention, non-exclusion HPLC of polymers should be performed with columns whose solvent volume is at least 50 times as large as the injection volume. This consequence is of practical importance in chromatographic cross-fractionation where rather large volumes of SEC eluate are injected into the apparatus for gradient HPLC.     

Normal-phase high-performance liquid chromatographic separations using ethoxynonafluorobutane as hexane alternative. II. Liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry applications with methanol gradients

We have reported recently that high-speed normal-phase (NP) HPLC separations of a broad range of organic compounds can be performed on cyano columns using gradients of methanol in hexane-like solvent-ethoxynonafluorobutane (ENFB), available commercially. In this communication, we demonstrate that atmospheric pressure chemical ionization (APCI) in combination with mass spectrometry (MS) can be effectively used for detection in such separations. The efficiency of APCI under conditions studied has also been compared to the efficiency of traditional electrospray ionization (ESI) in combination with MS for reversed-phase (RP) HPLC of the same compounds. The compounds included in this study were steroids, benzodiazepines, and other central nervous system-active substances, nonsteroidal anti-inflammatory drugs, tricyclic antidepressants, and beta-adrenergic blocking agents. Non-polar compounds were found to respond stronger when APCI-MS technique was used, whereas APCI and ESI ionization efficiencies were comparable when polar substances were studied. The combination of normal-phase HPLC separation conditions with mass spectral detection may expand the range of LC-MS applications traditionally associated with reversed-phase HPLC and ESI-MS detection.