聚苯胺在一些有机溶剂中溶解性

本文通过改变反应条件用化学方法制得了不同分子量的聚苯胺，考察了它们在有机溶剂中的溶解性．实验结果表明：分子量的大小是影响它们在有机溶剂中溶解度的主要因素，能在有机溶剂中溶解的只是聚苯胺中分子量较小的级分．我们还用聚苯胺（［η］＝０．４９ｄｌ／ｇ）与－ＣＯＣＩ封端的果对苯二甲酰对苯二胺（ＰＰＴＡ）进行嵌段共聚，经过产物的元素分析与计算结果比较，确定出特性黏数为０．４９ｄｌ／ｇ的聚苯胺平均分子量．     

New chemosensor for larger guests based on modified cyclodextrin bearing seven hydrophobic chains each with a hydrophilic end group

A new chemosensor for larger guests was prepared. The new chemosensor bears hydrophobic units at the primary hydroxy side and a dansyl unit at the secondary hydroxy side of β-cyclodextrin. Due to the hydrophobic units, the new chemosensor is sensitive to large or slender guests such as SDS and insensitive to 1-adamantanol, which is a good guest for the natural β-CD.     

Predicting the performance of molecularly imprinted polymers: Selective extraction of caffeine by molecularly imprinted solid phase extraction

A rational design approach was taken to the planning and synthesis of a molecularly imprinted polymer capable of extracting caffeine (the template molecule) from a standard solution of caffeine and further from a food sample containing caffeine. Data from NMR titration experiments in conjunction with a molecular modelling approach was used in predicting the relative ratios of template to functional monomer and furthermore determined both the choice of solvent (porogen) and the amount used for the study. In addition the molecular modelling program yielded information regarding the thermodynamic stability of the pre-polymerisation complex. Post-polymerisation analysis of the polymer itself by analysis of the pore size distribution by BET yielded significant information regarding the nature of the size and distribution of the pores within the polymer matrix. Here is proposed a stepwise procedure for the development and testing of a molecularly imprinted polymer using a well-studied compound—caffeine as a model system. It is shown that both the physical characteristics of a molecularly imprinted polymer (MIP) and the analysis of the pre-polymerisation complex can yield vital information, which can predict how well a given MIP will perform.     

New designs for inhibitors of the NF-κB: DNA binding

We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-^12,14 -prostaglandin J₂ (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs.     

SAPO-34分子筛骨架稳定性的研究

利用差热分析，原位ＸＲＤ技术，高温条件下的焙烧和水蒸气处理并关联其催化性能变化，研究了ＳＡＰＯ－３４分子筛的热及水热稳定性，差热分析结果表明，ＳＡＰＯ－３４的骨架破坏温度高于１３００Ｋ，原位ＸＲＤ跟踪研究证实，ＳＡＰＯ－３４分子筛原粉在高温焙烧以除掉有机胺及随后的降温过程中无明显的骨架破坏；而焙烧型ＳＡＰＯ－３４在空气中放置一定时间后，水分子吸附微孔中明业降低样品的ＸＲＤ峰强度，且降低幅度随放置时     

Molecular integrals over Gaussian-type geminal basis functions

We present formulas for the evaluation of molecular integrals over basis functions with an explicit Gaussian dependence on interelectronic coordinates. These formulas use expansions in Hermite Gaussian functions and represent an extension to the work of McMurchie and Davidson to two-electron basis functions. Integrals that depend on the coordinates of up to four electrons are discussed explicitly. A key feature of this approach is that it allows full exploitation of the shell structure of the orbital part of the basis. Received: 24 February 1997 / Accepted: 4 March 1997     

One-Pot Formation of Carbonates from the Reactions of Carbonyl Compounds with Samarium Diiodide and Methyl Chloroformate

Treatment of carbonyl compounds with SmI₂ and methyl chloroformate in the presence of molecular sieves provides the cyclic carbonates or biscarbonates of pinacols. This one-pot reaction proceeds rapidly even with aliphatic ketones. The stereochemistry obtained by this procedure is different from that of conventional pinacolic couplings.     

Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: new energy gradients and molecular surface tessellation

New equations are derived and implemented for efficient and accurate computation of solvation energy derivatives for the conductor-like polarizable continuum model (C-PCM) and the isotropic integral equation formalism polarizable continuum model (IEF-PCM). Two new molecular surface tessellation procedures GEPOL-RT and GEPOL-AS that generate near continuous potential energy surfaces are proposed for PCM geometry optimization. The combined use of these new techniques leads to efficient and convergent geometry optimizations with the PCMs.     

有机小分子染料和聚阳离子分子超薄膜的制备及其摩擦学性能研究

制备了以有机小分子染料酸性红 1 8为阴离子、以聚烯丙基氯化铵和聚乙烯亚胺为聚阳离子的分子沉积膜 ,用紫外可见分光光度计、接触角测定仪和椭圆偏振光测厚仪对所制备的超薄膜进行了表征 .用DF PM型动 静摩擦系数精密测定装置考察了超薄膜的摩擦学性能 ,采用扫描电子显微镜对薄膜的磨痕表面进行了观察 .结果表明 ,所制备的超薄复合沉积膜具有良好的减摩和耐磨性能     

Chromatographic molecular recognition for catechol-related compounds using thiacalix[4]arene as an effective selector

Thiacalix[4]arene (5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiacalix[4]arene) is an amphiphilic molecule comprising four p-tert-butylphenol-like groups ortho-linked by single sulfur atoms. This molecule has a high electron density area owing to the close proximity of the hydroxyl groups and sulfur atoms. We studied the applicability of this interesting compound as a selector for high-performance liquid chromatography (HPLC) thereby presumably exploiting this feature. Firstly, uniformly sized polymer particles were prepared by using a multi-step swelling and polymerization method with ethylene glycol dimethacrylate (EDMA) as a cross-linker. Methacrylic acid (MAA) was introduced onto the surface of the resulting polymer particles through a new modification method. Thiacalix[4]arene was chemically bonded through the MAA group by using 1,4-dibromobutane as a spacer to reduce steric hindrance around the MAA and the polymer particle itself. The performance of the prepared polymer-based thiacalix[4]arene-modified stationary phase was evaluated with HPLC. Specific chromatographic retention behavior was observed for catechol relative to positional isomers of xylene, cresol, and benzene-diol. Catecholamine and catechol showed specific chromatographic retention behavior.