原子转移自由基聚合法合成磺胺类片段印迹聚合物及其表征

采用原子转移自由基聚合与片段印迹技术相结合的方法,以磺胺类物质的结构类似物4,6-二氯嘧啶为模板合成印迹聚合物。以4,6-二氯嘧啶(模板)︰甲基丙烯酸缩水甘油酯(功能单体)︰2,2'-联吡啶(配体)的摩尔比为10︰180︰1合成印迹聚合物。控制反应温度为60℃,反应时间为5 h。印迹聚合物的吸附量为1.48 mg/g,非印迹聚合物的吸附量为0.73 mg/g。以合成的聚合物为新型材料,对样品中的兽药残留进行选择性分离、富集,结果表明印迹聚合物的选择吸附能力明显优于非印迹聚合物。通过电镜扫描对聚合物的表面形态进行了表征。     

Reactivity of N-Phenyl-1-Aza-2-Cyano-1,3-Butadienes in the Diels-Alder Reaction

It is found that N-phenyl-2-cyano-1-azadiene 4, prepared via a two-step, one-pot, sequence from acrylanilide, undergoes efficient [4 + 2] cycloaddition with a complete range of electron rich, electron poor, and neutral dienophiles under remarkably mild thermal conditions (90-120 degrees C for 20-48 h). Regiospecific formation of the alpha-cycloadduct wherein the dienophile substituent is alpha to nitrogen is observed for vinyl ethers and styrene, whereas the Diels-Alder reactions with methyl acrylate and methyl vinyl ketone (MVK) produce alpha/beta mixtures in which the alpha-cycloadduct is the major regioisomer (approximately 4-5:1). An essentially identical reaction pattern was observed in the Diels-Alder reaction of N-(p-methoxyphenyl)-2-cyano-1-azadiene 18 and the 4-methyl-substituted azadiene 27. For compound 19 derived from cycloaddition of 18 with ethyl vinyl ether, facile conversion to the dihydropyridine 21 through loss of EtOH on brief acid treatment was also noted. The 2,4-cis-disubstitution pattern confirmed by X-ray diffraction for the major cycloadduct 29 isolated from the reaction of 27 with styrene provides evidence for the endo mode of cycloaddition in the Diels-Alder reaction of N-phenyl(aryl)-2-cyano-1-azadienes. Calculation of the frontier orbital energies and coefficients, as well as the transition state geometries for the [4 + 2] cycloaddition of N-phenyl-2-cyano-1-azadiene 4 with methyl vinyl ether, styrene, and MVK were carried out at the RHF AM1 level (MOPAC, Version 5.0). The FMO treatment indicates that the reaction of 4 with methyl vinyl ether occurs under LUMO(diene) control, whereas in contrast, the corresponding cycloaddition with MVK occurs preferably under HOMO(diene) control. A high degree of asynchronicity is observed in the calculated transition states for reaction of 4 with the three representative dienophiles. In all cases the transition states leading to the alpha-cycloadducts are lower in energy than those giving the beta-products. However, at the AM1 level the exo cycloaddition mode is found to be the preferred, this result contrasting with experimental results for azadiene 27.     

_f-A_aD_d氢键体系的统计特征

基于氢键的形成和缩聚反应机理在统计意义下的相似性,利用高分子反应统计理论和反应动力学理论对氢键溶液的一个模型体系进行了相关讨论.给出了体系的溶胶分数和发生溶胶-凝胶相变的条件,指出质子受体基团间的竞争作用对溶胶凝胶相变点的影响,进而讨论了体系的数量分布函数和相关问题.     

AB_3型超支化聚(酰胺-酯)的合成及缩聚动力学研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料 ,在冰水浴条件下 ,合成AB3型单体 ,然后进行熔融缩聚制得超支化聚 (酰胺 酯 ) ,没有出现凝胶现象 .采用Fourier变换红外谱仪 (FTIR)、粘度测试、端基分析等方法对其结构、特性粘数进行了表征 .同时对AB3型超支化聚 (酰胺 酯 )的缩聚反应动力学进行了研究 ,得出了130℃、14 0℃和 15 0℃时的缩聚反应速率常数 ,并进一步得出了缩聚反应活化能 .实验结果证明缩聚过程为自催化过程 ,且为三级反应     

Studies on constituents of Abies grandis: The structures and absolute stereochemistry of cyclograndisolide and epicyclograndisolide,novel cyclopropane triterpene lactones

The light petroleum extract of grand fir [Abies grandis (Dougl.) Lindl.] was found to contain two novel triterpene lactones. The first compound, named cyclograndisolide, was shown by chemical and spectroscopic considerations and finally confirmed by X-ray analysis to be (23 R)-3α-methoxy-9,19-cyclo-9β-lanost-24-ene-26,23-olide (6). The second component, epicyclograndisolide was isomeric with the first and was assigned as (23 S)-3α-methoxy-9,19-cyclo-9β-lanost-24-ene-26,23-olide (10).     

阴离子型微乳液对火焰原子吸收法测铅增敏作用的研究与应用

研究了在空气－乙炔火焰中，阴离子型表面活性剂十二烷基硫酸钠（ＳＤＳ）组成的微乳液对铅原子化行为的影响。结果表明：在ＳＤＳ组成的微乳液存在下，铅的灵敏度提高了近６０％，比ＳＤＳ胶束存在下灵敏度也提高了２０％。方法用于黄铅和工业废水中铅的测定，结果令人满意。     

异质Stackelberg寡头竞争下创新产品技术许可策略研究

基于异质产品Stackelberg寡头竞争模型,建立了拥有新产品创新技术在位厂商与潜在竞争对手间的技术许可博弈模型.模型中假设潜在竞争对手可以接受许可,也可通过自我研发创新技术进入市场参与竞争.根据潜在竞争对手研发成本的高低,研究了创新厂商的最优两部制收费策略.研究结果表明:潜在竞争者总会接受创新技术许可,最优许可策略依赖于研发成本、市场参数以及产品的替代系数.     

养护条件对UHPC强度和毛细吸水性的影响

为优化超高性能混凝土(UHPC)预制构件养护工艺,研究了不同养护条件对UHPC强度和毛细吸水性的影响,并采用孔结构测试、热重分析和扫描电镜观察,对其机理进行了分析.结果表明:热养护显著提高了UHPC的7 d强度,这与加速火山灰反应有关,但高温和干热养护对其后期强度增大不利,甚至出现约3％的强度倒缩;不论何种养护,UHP...     

Statistical theory for hydrogen bonding fluid system of AaDd type (Ⅲ): Equation of state and fluctuations

The equation of the state of the hydrogen bonding fluid system of AaDd type is studied by the principle of statistical mechanics. The influences of hydrogen bonds on the equation of state of the system are obtained based on the change in volume due to hydrogen bonds. Moreover, the number density fluctuations of both molecules and hydrogen bonds as well as their spatial correlation property are investigated. Furthermore, an equation describing relation between the number density correlation function of "molecules-hydrogen bonds" and that of molecules and hydrogen bonds is derived. As application,taking the van der Waals hydrogen bonding fluid as an example, we considered the effect of hydrogen bonds on its relevant statistical properties.