1-烃基-1-硅杂环丁烷的合成及其Si—H键伸缩振动频率与结构关系的研究

硅杂环丁烷在有机硅化学中是一类非常重要的小分子环系化合物。由于硅杂环丁烷和环丁烷的环张力相似,因而显示出较高的反应活性。例如能与某些试剂作用,生成开环产物;在光解或热解条件下,产生具有Si=C结构的高活性中间体,可用以合成多种有机硅化合物。     

Cl/Ag体系研究 Ⅱ.Cl吸附引起的表面结构变化

运用LEED,UPS和HREELS等表面技术研究了氯吸附至(c)阶段的Ag(111)表面结构.结果表明,表面上有三维的AgCl(111)生成,其生长按修正的Stranski-Krastanov模式进行.伴随着AgCI(111)生长的同时,表面上产生缺陷.这种缺陷只有在氯吸附至(c)阶段时表面上形成三维AgCI的过程中才能产生,它一旦在表面上形成后,表面上氯的存在与否对其不产生影响.本文提出了一个(c)阶段时的Cl/Ag(111)体系的结构模型.     

(TiNi)_x(x=2~4)团簇结构和电子结构

从团簇角度对TiNi形状记忆合金进行了量子化学从头算研究。设计并优化了等原子比(TiNi)x(x=2~4)簇的多种可能几何结构,并对较稳定构型进行电子结构的分析。结果表明,等原子比的(TiNi)n团簇以TiNi成键为主要分子骨架,小团簇有较多能量接近的异构体,TiTi成键对能量降低有较大贡献。     

表面包覆改性对纳米CeO2分散性的影响

了改善纳米CeO2在Zn-Al类共晶合金中的分散性,采用超声液相包覆法对纳米CeO2进行表面活性剂表面包覆改性,并用AES测定了包覆层的厚度,用TEM研究了CeO2的团聚状况,用TGA分析了有机物包覆层的炭化温度范围,最后用FE-SEM观察了CeO2在复合材料中的分散情况。结果表明,包覆在纳米CeO2表面的厚度约为20 nm的表面活性剂层提高了微粒的分散性,而且该包覆层在495℃时已经炭化。热力学计算的结果也表明,炭化层能与氧化膜反应,该反应提高了CeO2与基体间的润湿性,并使其均匀分布在基体合金中。     

液固流化床内床层动态特性的CFD模拟

在对液固流化床内流动特性进行理论分析的基础上，采用多相流CFD方法模拟了二维矩形流化床内水和玻璃球体系的流体动力学特性。实验结果表明，流体速度突变后，液固流化床从一个平衡状态向另一个平衡状态过渡。当液体速度减小时，床层表面及分隔界面的变化与理论模型预测一致；由于重力不稳定性的影响，当液体速度增大时，床层表面稳定上升但与时间不呈线性关系，且分隔界面难以分辨。进而膨胀后停留时间的长短对收缩过程的影响也可以忽略。尽管床层收缩时间明显小于实际膨胀时间，但是与预报的理想膨胀时间比较接近。模拟结果与前人的实验研究和理论分析相吻合，表明多相流CFD模拟可以很好地预测液固流化床的床层动态行为。     

原子荧光光谱法测定小麦粉中汞若干经验

原子荧光光谱分析是一种非常实用的痕量分析技术。酸化过的小麦粉溶液中的汞与还原剂硼氢化钾反应,生成氢化物;过量氢气和气态氢化物与载气混合,进入原子化器,汞空心阴极灯激发氩氢焰中的汞原子,跃迁回基态时发出的荧光信号被日盲光电倍增管接收,然后经放大、解调、再由数据处理系统得到结果。在使用AFS2202E型原子荧光光度计检测小麦粉中汞时,应注意以下几个问题。1试样消解以微波消解最为理想,但消解装置价格太高;常压回流消解耗时太长;与单体高压消解罐相比较经济、省时。(1)消解时应注意烘箱温度的控制,以120℃为宜,3 h即可;温度高些,…     

Preparation and characterization of C16 monolithic columns for capillary electrochromatography

A series of methacrylamide-based C16 monolithic columns were prepared and characterized to determine how their porous structural properties and chromatographic behavior are affected by the percentages of functional monomer, base monomer, and cross-linker in the polymerization solution. Baseline separation of 6 neutral compounds can be readily obtained in an optimized column. Furthermore, the effects of organic additive in the mobile phase, operating voltages, and temperature on retention behaviors and separation efficiencies were also studied. The separation mechanism is also discussed. High column efficiency and good reproducibility indicate that the monolithic columns hold considerable promise.     

Metal- and acid-free,TBN-mediated direct CH nitration of arenes

A metal-free, acid-free, direct and eco-friendly nitration methodology has been developed. A tert-butyl nitrite efficiently promotes the direct CH nitration of electron-rich arenes with good to excellent yields and regioselectivities. The practical utility of this protocol has been demonstrated in gram-scale nitration of crown ether and mono nitration of Sesamin. A plausible free radical mechanism is proposed based on detailed experimental observations.     

Characterization of low molecular weight components of [(ViMe2SiO1/2)x(PhSiO3/2)y(SiO4/2)z], [(ViMe2SiO1/2)x(SiO4/2)y], and [(SiO4/2)x(HO1/2)y(tBuO1/2)z] silsesquioxanes by electrospray ionization fourier transform mass spectrometry (ESI-FTMS)

This paper describes the characterization of low molecular weight components of four materials using electrospray ionization Fourier transform mass spectrometry (ESI-FTMS). The materials in the current study are [(ViMe₂SiO_1/2)_x(PhSiO_3/2)_y(SiO_4/2)_z] (MTQ), [(ViMe₂SiO_1/2)_x(SiO_4/2)_y] (MQ), and [(SiO_4/2)_x(HO_1/2)_y(^tBuO_1/2)_z] (Q) silsesquioxanes. Accurate mass measurements coupled with knowledge of resin chemistry afforded siloxane composition determination that was used to propose specific structures for the oligomers. Branched or linear (T_nQ_mM_n+2m+2), and monocyclic (T_nQ_mM_n+2m) structures are predominant structures for the low molecular weight species in MTQ. For MQ and Q, more condensed structures, such as partially opened cage structures (Q_mM_2m?6 and Q_mM_2m?8), were identified. The differences between MQ, Q, and MTQ are likely attributed to differences in intrinsic structure and reactivity of T and Q building blocks. The structural information obtained for these oligomeric species will ultimately provide a better understanding of new resin materials and their associated physical properties.     

超临界二氧化碳在高分子合成及加工领域的应用

重点概述了近年来超临界二氧化碳作为环境友好介质在高分子合成与加工方面研究的新进展,具体介绍了在超临界二氧化碳中丙烯酸的合成及疏水改性方面所做的工作,并在此基础上,展望超临界二氧化碳作为高分子合成介质的前景。