超高分子量聚乙烯的辐照效应

通过密度测定和ＤＳＣ热分析，观测了超高分子量聚乙烯的辐射效应。实验结果表明：在吸收剂量０—１．１３ＭＧｙ范围内，密度随吸收剂量的增加而增大，熔化热和熔点也有所增加，特别是在低剂量范围内增加十分明显。以上结果都说明，超高分子量聚乙烯在辐照过程中，结晶在完善或有新的结晶形成     

Cholesterol‐imprinted polymer receptor prepared by a hybrid imprinting method

A novel cholesterol‐imprinted polymer (CMIP‐H) was prepared by a hybrid method of covalent imprinting and non‐covalent imprinting. This approach involves the copolymerization of a template‐containing monomer, cholesteryl 2‐hydroxyethyl methacrylate carbonate, and a cross‐linker, followed by hydrolysis to afford a flexible guest‐binding site accompanied with the easy and efficient removal of a ‘sacrificial spacer’. The effect of solvent on the binding capacity of CMIP‐H towards cholesterol was studied, indicating that a good binding capacity towards cholesterol could be achieved in a less‐polar solvent. The binding experiments of CMIP‐H towards a series of structural analogues of cholesterol, including cholesterol acetate, progesterone and stigmasterol, were carried out in hexane. The results showed that CMIP‐H almost did not bind cholesterol acetate at all because the hydrogen‐bonding site is blocked. It exhibited a similar binding towards both cholesterol and stigmasterol, but much higher binding towards progesterone. Copyright © 2005 Society of Chemical Industry     

β－C_2S固溶体稳定的热力学研究

从热力学理论出发，利用Ｘ射线衍射定性和定量的方法，对β－Ｃ＿２Ｓ固溶体的稳定性进行了分析和研究。经热力学理论推导得出β－Ｃ＿２Ｓ稳定的热力学条件，即掺入的微量元素的化学位μ＿ｉ须小于β－Ｃ＿２Ｓ的反应自由焓△Ｇ＿β，μ＿ｉ＜△Ｇ＿β．并定量地计算出一种微量元素稳定β－Ｃ＿２Ｓ的临界掺加量为；多种微量元素对β－Ｃ＿２Ｓ的稳定性判断条件为：     

部分种子成分的特征X射线在等效生物材料中衰减的测定

用Ｓｉ（Ｌｉ）探测器实现了Ｎａ、Ｍｇ、Ｓ、Ｃｌ的特征Ｘ射线在有机膜中的相对衰减以及与Ｏ、Ｋ元素的特征Ｘ射线能量相当的Ｘ射线或轫致辐射在有机膜中的相对衰减，分别得出了它们减的数学描述，并把实验得到不同能量的Ｘ射线在有机膜中的质量吸收系数与Ｂｅｒｋｅｌｅｙ的ＯＣＧ软件计算出的结果相比，相关都小于３０％。     

Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

Effects of mastication on the distribution of molecular weights and on the mechanical properties of native and commercial dental gutta percha (trans-polyisoprene)

Mastication of gutta percha (trans-polyisoprene) resulted in the selective scission of molecules, producing a narrower distribution of lower molecular weights. The mechanical properties of the samples also underwent a significant change due to mastication. The greater the content of incompatible substances (salts and oxides) in commercial gutta percha. the more substantial were these effects. The atmosphere (air, N₂, O₂) in which the experiments were conducted yielded significantly different results. The decrease in molecular weight was far greater in an O₂ atmosphere than under a current of nitrogen or air, owing to the combination of double bonds with O₂.     

Studies on the synthesis of SAPO-5

Silicoaluminophosphate (SAPO-5) molecular sieves have been synthesised from reaction mixtures having a molar composition of: 0.7–1.0 Al₂O₃:0.7–1.0 P₂O₅:0.01–2.0 SiO₂:xR:40 H₂O (where R = (C₂H₃)₃N or (C₂H₃)₄NOH and x = 1.5–2.5 for (C₂H₅)⁵N and 0.5 for (C₂H₅)₄NOH, at 473 K using various sources of alumina and silica. The effects of (i) varying the crystallinity of the alumina source (boehmite) and (ii) the use of different silica sources such as freshly prepared silica either from sodium silicate or paddy husk extract, silica gel from commercial water-glass, and tetraethyl orthosilicate have been studied. The crystallinity of boehmite has been found to have a strong effect on its reactivity towards the formation of SAPO-5. The activity of boehmite for SAPO-5 formation increased with a decrease in its crystallinity (or with increase in its moisture content). Any silica source devoid of sodium ions could be employed for the synthesis of SAPO-5. The process of crystallisation started as early as within 1.5 h of reaction and incorporation of silicon into the AlPO₄ framework has been noted at this stage. Formation of some tridymite phase as impurity has been observed under conditions such as (i) SiO₂ concentration > 1.7 mole and (ii) x > 2.0 when R = (C²H₅)₃N.     

Prebiotic synthesis of sequential peptides on the Hadean beach by a molecular engine working with nitrogen oxides as energy sources

Addressing the still open question of the prebiotic origin of sequential macromolecules (peptides, nucleic acids) on the primitive Earth, we describe a molecular engine (the primary pump), which works at ambient temperature and continuously generates, elongates and complexifies sequential peptides. This new scenario is based on a cyclic reaction sequence, whose keystep is the activation of amino acids into their N‐carboxyanhydrides (NCA) through nitrosation by NOx. This process could have taken place on tidal beaches; it requires a buffered ocean, emerged land and a nitrosating atmosphere. With the help of geochemical studies and computer simulations of atmosphere photochemistry, we show that the primitive Earth during the Hadean may have satisfied all these requirements. © 2001 Society of Chemical Industry.     

In situ13C NMR study of tert-butanol interaction with moderately concentrated sulfuric acid

An in situ NMR study of tert-butanol dehydration in 95 and 85% sulfuric acid did not indicate the formation of tert-butyl cations as active reaction intermediates. Instead, only NMR lines from oxonium ions under the condition of fast exchange with water and the acid were observed. It is most likely that, in the concentrated acid, the active intermediates of this reaction are represented by tert-butyl sulfuric ester which probably is a precursor of invisible tert-butyl carbenium ions representing short-lived excited or transition states.     

钛酸钾品须填充UHMWPE复合材料的摩擦磨损性能研究

用钛酸钾晶须(PTW)对超高摩尔质量聚乙烯(UHMWPE)进行填充改性,考察了复合材料的摩擦磨损性能,研究了其结晶情况,观察了磨损表面形貌并分析了其机理.结果表明随着PTW用量的增加,复合材料的硬度、结晶度以及维卡软化点都有所增大.PTW提高了复合材料的耐磨性,但摩擦系数有所上升.PTW的加入使得UHMWPE的磨损机理从黏着磨损和塑性变形改变成疲劳磨损和轻微的塑性变形,提高了其抗磨粒磨损的性能.