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71.
WANG Rui DA Chao-Shan LIU Da-Xue YANG Xiao-wu XIN Zhuo-Qun DONG Shou-Liang ShEN Jan-Heng SU Wu WANG Heng-shan WANG Quan ZHANG Li-Chen CHAN Albert S.C 《高等学校化学研究》2001,17(3)
Catalytic asymmetric carbon-carbon bond formation is one of the most important reactions and have attracted much attention to develop more efficient enantioselective C-C formation methods in organic synthesis. In this field, asymmetric addition of diethylzinc to aldehydes[1] and conjugate addition to enones[2] have drawn special interests and have been greatly developed. Regardless of it, much spaces in these areas still exist, so it needs more extensive and intensive researches for the purpose of as follows: (1) attaching ligands to a polymer for the easy separation of the catalysts so as to be able to allow very efficient recovery and reuse of the catalysts, and the possibility of carrying out the desired transfomation in continuous mode in a flow reactor, etc., (2) searching for novel chiral catalysts with such features as more suitable for more extensive substrates varieties, and more convenient and economical as well as possessing applicable prospect, and so on. Here we report some works in these areas done in our laboratory. 相似文献
72.
掺杂和未掺杂氧化锌薄膜的拉曼光谱 总被引:2,自引:0,他引:2
利用拉曼光谱分别对不同衬底上,未掺杂和掺杂以及掺杂浓度不同的ZnO薄膜进行了系统的分析研究。其中ZnO薄膜均由溶胶-凝胶法制得,掺杂源为LiCl。测得的拉曼光谱显示,Pt/Ti/SiO2/Si衬底上生长的ZnO薄膜的拉曼特征峰(437cm-1)的强度明显高于SiO2/Si衬底上ZnO薄膜的拉曼特征峰的强度,说明Pt/Ti/SiO2/Si衬底上ZnO的晶化程度比SiO2/Si上ZnO的晶化程度高;但ZnO拉曼特征峰的位置和半高宽并没有发生变化,说明两种衬底上ZnO薄膜中应力大小没有发生变化。掺Li+后,580cm-1处的峰位向高频方向移动,且掺杂浓度越大频移量越大,说明掺杂已经在不同程度上引起了ZnO晶体中自由载流子浓度的变化。此外,还分析了掺Li+未在很大程度上引起ZnO晶格畸变的原因。 相似文献
73.
Burshtain D Wu J Melman A Mandler D Scherson DA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(11):4498-4502
Various aspects of the adsorption of Cd2+ on self-assembled monolayers (SAMs) of 4-heptadecylpyridine (HDpy) and 7-tridecyl-4-methyl-1,10-bipyridine (TMbipy) supported on an octadecylsilane (ODS)-modified Ge prism have been examined both ex situ (dry) and in situ (in the presence of aqueous solutions) using attenuated total reflection Fourier transform infrared spectroscopy. In direct analogy with the behavior found for a variety of genuine pyridine (py) and bipyridine (bipy) metal ion complexes, Cd2+ binding to both SAMs led to shifts in the skeletal vibrational modes of the corresponding uncoordinated ligands in the region 1650-1400 cm(-1), toward higher energies. Analysis of spectra acquired ex situ for HDpy/ODS/Ge and TMbipy/ODS/Ge before and after exposure to 0.1 mM [Cd2+] yielded values for the fraction of uncoordinated py, theta(py(un)), and uncoordinated bipy, theta(bipy(un)), of about 0.5 and about 0.1, respectively. The features attributed to the py(un) groups for spectra collected for HDpy/ODS/Ge in situ and ex situ were found to be virtually identical, making it possible to isolate by graphical means the most prominent band of py(co) centered at about 1615 cm(-l) for HDpy/ODS/Ge collected in situ. The resulting bands for pure py(co) and pyun in situ were then used to deconvolute spectra recorded in situ for HPpy/ODS/Ge in contact with Cd2+containing solutions in the range 10 nM < [Cd2+] < 0.1 mM, from which information regarding the adsorption isotherm was obtained. 相似文献
74.
甘氨酸衍生化β-环糊精键合硅胶液相色谱固定相的合成与评价 总被引:1,自引:0,他引:1
β-环糊精键合硅胶经对甲苯磺酰化后,与甘氨酸反应得到甘氨酸衍生化β-环糊精键合硅胶固定相(GCDS)。考察了GCDS对位置异构体、丹磺酰化氨基酸异构体、苯丙酸类药物等的分离性能,研究了流动相中甲醇浓度、pH以及柱温对色谱保留行为的影响。 相似文献
75.
用低温溶剂热法合成了2种分立结构的有机杂化硫代碲(Ⅳ)酸盐化合物(H2en)TeS3(1)和[Ni(en)3]TeS3(2)(en=乙二胺),通过X-射线单晶衍射,红外光谱,元素分析等手段对它们的结构进行了表征。晶体结构解析结果表明:2个化合物均属单斜晶系,空间群分别为P21和P21/c。化合物1和2具有孤立三角锥[TeS3]2-阴离子,化合物1的平衡阳离子为双质子化乙二胺[H2en]2+,阴离子基团[TeS3]2-和阳离子基团[H2en]2+之间通过N-H…S氢键连接。化合物2的阳离子基团为过渡金属Ni与乙二胺的配合物[Ni(en)3]2+。另外,对该2种晶体进行了紫外-可见漫反射光谱测试和热重分析。 相似文献
76.
语音是一种短时平稳时频信号,因此大多数的研究者都通过分帧来提取情感特征。然而,分帧后提取的特征为局部特征,无法准确反应情感语音动态特性,故单纯采用局部特征往往无法构建鲁棒的情感识别系统。针对这个问题,先在不分帧的语音信号里通过多尺度最优小波包分解提取语句级全局特征,分帧后再提取384维的语句级局部特征,并利用Fisher准则进行降维,最后提出一种弱尺度融合策略来将这两种语句级特征进行融合,再利用SVM进行情感分类。基于柏林情感库的实验结果表明本文方法较单纯使用语句级局部特征最后识别率提高了4.2%到13.8%,特别在小样本的情况下,语音情感识别率波动较小。 相似文献
77.
78.
用十二胺-N乙酸-N亚甲基膦酸(DAPA)改性氧化锆制备了一种新的锆基质色谱固定相(DAPAZ),研究发现,DAPA在氧化锆表面有两种结合方式:红外光谱中1611cm^-1处的特征吸收表明羧基主要与胺基形成偶极离子,以羧酸根离子形式存在,大部分的DAPA分子通过膦酸基团与氧化锆结合;而与钼酸的显色反应则表明有少量DAPA以羧居与氧化锆结合,另外,对固定相的屏蔽效应、碱性条件(pH9.5)下的稳定性等色谱性能的研究也证实这两种吸附方式同时存在,但以膦酸基结合为主。 相似文献
79.
P. A. S. JORGE P. CALDAS J. C. G. ESTEVES DA SILVA C. C. ROSA A. G. OLIVA J. L. SANTOS 《Fiber and Integrated Optics》2013,32(3-4):201-225
Abstract A scheme for the simultaneous determination of temperature and analyte concentration for application in luminescence-based chemical sensors is proposed. This scheme is applied to an optical oxygen sensor, which is based on the quenching of the fluorescence of a ruthenium complex. Temperature measurement is performed using the excitation radiation and an absorption long-pass filter. Preliminary results are presented that show the viability of an oxygen measurement that is independent of temperature and optical power level. The possibility of self-referenced temperature measurements with semiconductor nanoparticles is also investigated. In order to optimize the sensor design, several different optical fiber probe geometries for oxygen sensing are tested and compared, including different methods of coupling radiation into the optical fiber system. Polyvinyl alcohol (PVA) and polyacrylamide membranes are tested as supports for sensor immobilization in fiber-optical pH sensing devices in aqueous solution. Some results are presented that show the feasibility of using fiber-optical pH indicators for remote monitoring. 相似文献
80.
RUTE DA FONSECA MARIA CRISTINA MENZIANI ANDRÉ MELO MARIA JOÃO RAMOS 《Molecular physics》2013,111(17):2731-2741
Cytochrome P450 (CYP) is a family of enzymes responsible for organism detoxification. However, some of the members of the CYP1A subfamily also catalyse the activation of heterocyclic amines (HAs), present in cooked meat, to carcinogenic compounds which have been shown to increase the risk of breast, colorectal and lung cancer. In humans, CYP1A2 is the enzyme with the most significant action in HA metabolism but in rodents CYP1A1 is also important in this biotransformation. Understanding the metabolic action of these enzymes is essential to predict the factors that enable the formation of the carcinogenic products. We have built two models of CYP1A2, one for the human enzyme and one for the rat homologue. The templates chosen include the only X-ray structure published to date for a mammal CYP, a quimeric C2A5 from rabbit, as well as CYPs belonging to Bacillus megaterium (CYPBm-3), Pseudomonas putida (CYPcam), Pseudomonas sp. (CYPterp), and Saccharopolyspora erythraea (CYPeryf). Two HAs, MeIQ (2-amino-3,4-dimethylimidazo[4,5-?]quinoline) and MeIQx (2-amino-3,8-dimethylimidazo[4,5-?]quinoxaline), known substrates of human and rat CYPIA2, were docked in the active site of the models, providing information regarding the different catalytic rates associated with the metabolisms in both enzymes. This is important for analysing the behaviour of animal models concerning the testing of anticancer drugs. 相似文献