阳离子聚合的进展

首先介绍了阳离子聚合的简史,由于阳离子高活性的特点使其发展较慢,阳离子聚合研究的突破来自对引发反应的深入理解,而近代阳离子聚合的要点则在于使链引发、链增长和链终止成为可控。阳离子聚合的进展密切与大分子工程相关。本文对活性阳郭聚合做了较详细的讨论。并举遥爪聚人事物及嵌段聚合物的研究成就。最后,提出了阳离子聚合是发展中的问题供参考。     

β-葡萄糖醛酸苷酶荧光底物试卤灵葡萄糖醛酸苷的高效制备

以猴肝微粒体(Cy LM)为酶源,采用生物制备法实现了荧光底物试卤灵(Resorufin)向试卤灵葡萄糖醛酸苷(Resorufinβ-D-glucuronide)的高效转化,同时借助新型色谱分离材料C18WAX及固相萃取技术实现了Resorufinβ-D-glucuronide的高效富集及选择性洗脱,最终获得纯度大于98%的目标产物.所得产物结构经LC-MS,1H NMR和13C NMR等手段进行了表征.在此基础上,以该葡萄糖醛酸产物为探针底物建立了β-葡萄糖醛酸苷酶活性检测及抑制剂高通量筛选的方法.     

Al激光等离子体Stark加宽光谱观测

用YAG脉冲激光器产生的1.06μm激光,在高真空下轰击Al靶,观测到9条AlⅠ,AlⅡ和AlⅢ的等离子体谱线。利用高分辨率双光栅单色仪和光学多道分析仪(OMA),对谱线的Stark加宽和线型进行了测量。得到Al等离子体的电子密度沿靶面法向的分布,测得电子密度在1.0×l017～1.l×l018cm-3范围。利用谱线峰值法估算了等离子体的温度约为1.5×l05K。测量结果与半经典理论的计算基本符合     

Effect of overdrive voltage on PBTI trapping behavior in GaN MIS-HEMT with LPCVD SiN_x gate dielectric

The effect of high overdrive voltage on the positive bias temperature instability(PBTI)trapping behavior is investigated for GaN metal–insulator–semiconductor high electron mobility transistor(MIS-HEMT)with LPCVD-SiNx gate dielectric.A higher overdrive voltage is more effective to accelerate the electrons trapping process,resulting in a unique trapping behavior,i.e.,a larger threshold voltage shift with a weaker time dependence and a weaker temperature dependence.Combining the degradation of electrical parameters with the frequency–conductance measurements,the unique trapping behavior is ascribed to the defect energy profile inside the gate dielectric changing with stress time,new interface/border traps with a broad distribution above the channel Fermi level are introduced by high overdrive voltage.     

用一稀土催化剂合成高分子量聚苯乙烯

由Nd(oct)3(Nd)、Al(i-Bu)3(Al)和C4H9Cl(BCL)三组分组成稀土催化体系,催化苯乙烯(St)在环己烷溶剂中进行配位聚合,考察Al/Nd摩尔比、BCL/Nd摩尔比、陈化温度、陈化时间、催化剂用量、聚合温度与时间等因素对苯乙烯聚合、催化活性以及聚苯乙烯产物(PS)分子量与分子量分布的影响.当Al/Nd=8-12(摩尔比),BCL/Nd=5-25(摩尔比),Ta=40-50℃,ta=6-20 h,Tp=40-50℃时,可以得到高分子量聚苯乙烯,其中重均分子量可高达7.6×105.聚合产物中不溶于丁酮的聚苯乙烯的熔点高达268℃,主要含有间规结构聚苯乙烯和少量等规结构聚苯乙烯;偏光显微镜观察结果表明,可溶于丁酮的聚苯乙烯也是含有部分立构规整链段的聚合物.     

精密半微量滴定热量计的建立和胶束生成焓测定

为研究两亲分子自组合的弱相互作用,在LKB-8700精密量热系统的基础上设计和建立了精密半微量滴定热量计。实验数据的采集和处理由在线微机自动完成。利用本热量计测定量热基准物质三羟甲基氨基甲烷(Tris)和盐酸的反应热,实验结果与文献值一致,精度为±0.2%。对阴离子表面活性剂十二烷基硫酸钠(SDS),阳离子表面活性剂十二烷基三甲基溴化铵(DTAB)和非离子表面活性剂TritonX-100的胶束生成焓和临界胶束浓度(cmc)的测定结果也与文献报道值一致。     

A titration microcalorimeter and the vesicle of mixed surfactants

A titration microcalorimeter with the sample cells of 1 mL and 3 mL volume was constructed by combining LKB-2107 ampule microcalorimeter with an improved Thermometric titration microcalorimeter. Its sensitivity and precision were tested with the baseline noise and stability, the measurement of energy equivalent, and the linear relation of electric energy and integral area as the function of voltage (V)-time (f). Its accuracy was demonstrated by measuring the dilution enthalpy of a concentrated sucrose solution and the micelle-forming enthalpy of sodium dodecyl sulfate (SDS) in aqueous solution respectively. At the same time, the enthalpy of interaction between SDS and didodecyldimethylammonium bromide (DDAB) was measured by using the titration microcalorimeter, and the phase behavior of SDS-DDAB aqueous mixture was discussed. The microcalorimetric results show that the enthalpy of interaction between SDS and DDAB micelles is -29.53 kJ/mol, the enthalpy of formation of 1:1 SDS-DDAB salt is -125.8 kJ/mol,     

Ni(naph)_2/A1R_3/BF_3·OEt_2/DMEA/OctOH体系催化丁二烯配位聚合

在Ni(naph)2-AlR3-(BF3·OEt2)催化体系(简称Ni-Al-B)用于丁二烯(Bd)/己烷进行配位聚合体系中引入N,N-二甲基乙醇胺(DMEA)和辛醇(OctOH),研究了DMEA/Ni摩尔比、B/Ni摩尔比和Al/Ni摩尔比对Bd聚合转化率、聚丁二烯(PB)产物的特性黏数、分子量、分子量分布及微观结构的影响,进一步探讨聚合反应动力学.结果表明,在镍系催化丁二烯聚合体系中引入一定量的DMEA和OctOH后,可以提高顺-1,4微观结构含量至97.8%,降低1,2-微观结构含量至约1.3%,提高分子量,使分子量分布变窄,并降低凝胶含量.进一步通过调节B/Ni及Al/Ni摩尔比值,可得到[η]为2.0～4.0dL/g的高顺式PB.聚合速率对单体浓度呈现一级动力学关系,表观增长活化能为43.7kJ·mol-1。     

球形液膜动态特性的研究

对球形液膜内气体沿细管排出过程中，球形液膜的动态特性进行了模拟和验证。