Theoretical Study on the Reaction Mechanism of Ketene CH2CO with Isocyanate NCO Radical

The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD（T） methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO＋CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO＋HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO＋ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations.     

炭气凝胶及其有机气凝胶前驱体的研究进展

介绍了炭气凝胶及其有机气凝胶前驱体的发展概况，着重总结了制备工艺条件(如催化剂及其浓度、反应物总浓度、反应物配比、溶剂、反应温度及时间、超临界干燥工艺条件和炭化工艺条件等)对有机气凝胶及其相应炭气凝胶中孔网络结构的影响，综述了中孔网络结构改性研究的进展．     

季铵盐固相催化使聚氯乙烯脱HCl

通过将季铵盐与聚氯乙烯(PVC)混溶成膜,使其在固相脱HCl,研究了催化剂对PVC脱HCl反应速度和产物结构的影响以及固相反应与温度、时间的关系.发现在催化性能上下基铵盐比乙基铵盐好得多,根据实验结果提出了季铵盐通过分解成叔胺实现催化的机理.     

Fe（acac）3-Al（i-Bu）3-α，α＇-联吡啶催化丙烯腈与苯乙烯共聚合

研究了Fe（acac）3-Al（i-Bu）3-α，α＇-联吡啶（acac=乙酰丙酮）催化体系催化丙烯腈（AN）与苯乙烯共聚合，用元素分析和核磁共振研究了共聚物的结构，在单体比为1：1时共聚物中丙烯腈／苯乙烯含量分别为49．3％和50．7％．用凝胶渗透色谱研究了聚合物分子量和分子量分布，共聚物分子量分布较窄．动力学研究表明共聚合反应对单体浓度呈一级关系，表观活化能为57．8kJ／mol．     

Study on thermal stability of poled non-linear optical polymers

A logarithmic expression is proposed to describe relaxation of the polar order in side chain polymers,together with a new way of plotting temperature dependent relaxation data.This results in a straight line extending even below the glass transition temperature in the case of poled nonlinear optics (NLO) side chain polymers.A simple procedure to determine the rotational diffusion constant Dr is given and Dr values of several polymer systems have been evaluated and compared with each other.It appears that,starting from the conventional and well known poled polymer system currently applied,a further lowering of Dr by about 3 orders of magnitude is necessary in order to reach an acceptable orientational stability or lifetime of poled polymers for practical applications.Attempts have been made to introduce electron push-pull substituents into high thermostable molecular frameworks and results of preliminary measurements are reported.     

EPR Study on the complex formed by charge-transfer process between ground-state acceptor chloranil and nine donors

EPR study showed that the semi-quinone radical anion of chloranil (TCQ) was formed in a charge-transfer process between ground state chloranil as acceptor and each one of the following ground state donors,i.e.,N,N'-diethyl aniline (DEA),phenothiazine (PTZ),carbazole (CBZ),pyrene (PY),ferrocene (FRO),triphenylphosphine (TPP),triethylamine (TEA),anthracene (AN) and N,N-diethyl-3-aminophenyl ester of palmitic acid (DPP).Our results indicate that there is a tunneling effect for the ground-state charge-transfer process between chloranil and the donor.     

气色相谱-质谱法测定化妆品中的氯霉素

氯霉素是一种广谱抗生素,化妆品卫生规范规定氯霉素等抗生素为禁用物质.关于氯霉素的检测多采用高效液相色谱(HPLC)[1]和高效液相色谱-质谱(HPLC-MS)[2] 测定,或者经N,O-双三甲基硅烷基-三氟乙酰胺(BSTFA)、三甲基氯硅烷(TMCS)等硅烷化[3-4]后进行气相色谱(GC)、GC-MS测定.本文建立了采用较为普通的乙酸酐试剂进行衍生化,然后用GC-MS测定的方法.将该法应用于化妆品中氯霉素的检测,取得了较好的效果.     

高速磁浮车-轨耦合系统动态机理与振动响应

对高速磁浮车-轨耦合系统进行动态机理和振动响应研究。首先,对高速磁浮中的各类耦合关系进行建模;其次,分别分析了动态和静态条件下的车-轨耦合作用机理;然后,建立了高速磁浮车-轨耦合动力学有限元模型;最后,对磁浮列车高速通过桥梁时轨道梁、功能件的动力响应和车-轨共振速度进行分析。结果表明：高速运行时车-轨作用频率不同,长时间共振速度下运行时车-轨振动明显增大;若桥梁动力放大系数小于1.2,则基频比最小值为1.16;若桥梁动力放大系数小于1.3,则基频比最小值为1.04。     

基于案例分析的人工湿地尾水处理技术进展

人工湿地技术综合了基质、微生物和植物对水中污染物的协同去除机制,广泛用于提升污水厂尾水水质,是一种绿色低耗的生态修复技术.本文汇总了以人工湿地为核心技术的众多城镇污水处理厂尾水资源化案例,对人工湿地技术的不同工艺运行方式和优缺点进行了分类归纳,提出依据不同水质特征量身设计复合人工湿地工艺的策略,为污水处理厂尾水的资源化利用提供参考.     

带背景激波系的凹腔流动特性研究

凹腔作为超燃冲压发动机的一种火焰稳定器受到广泛关注,凹腔剪切层与背景激波系的相互作用影响凹腔火焰稳定器的性能。为深入分析背景激波系对凹腔流动的影响,设计了长深比为13.3的闭式凹腔,将凹腔模型前缘激波和风洞上壁面干扰激波作为背景激波系,在Ma=2的直连式风洞中开展了背景激波系与凹腔剪切层的相互作用的试验,采用高速纹影系统对瞬态流场进行了捕捉,重点关注背景激波系和凹腔剪切层的动态变化特性。采用纹影序列的本征正交分解来研究流场中的主要相干结构,采用快速傅里叶变换和连续小波变换对流场的频率域特征进行了分析。结果表明：在背景激波与剪切层相互作用下,激波结构产生大尺度振荡,凹腔内流动结构产生小尺度脉动。通过对激波位置的傅里叶变换分析,发现激波振荡的主导频率集中在90～400 Hz的范围内。通过对纹影图像的空间傅里叶变换分析,发现5 kHz以下的流场振荡主要由激波振荡引起,5 kHz以上的流场脉动主要由凹腔内流动结构引起。