Li^＋／MgO上乙烷氧化脱氢制乙烯的研究（Ⅱ）：催化作用机理

借助ＸＲＤ、ＩＲ、ＴＧ等技术对Ｌｉ＾＋／ＭｇＯ进行了表征，结果表明，酸、碱中心的数目，强度、催化性与Ｌｉ＾＋的添加量相关 ，起酸碱作用的表面金属离子、表面低配位氧集团、Ｏ（Ｌ ｉ＾＋Ｏ＾－）是其反应的活性物种，反应机理可能由离子基、游离基协同完成。     

固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.     

一种计算稀土材料陷阱深度的新方法

表征陷阱材料的主要物理量是陷阱深度, 准确计算出陷阱深度对于研究陷阱材料具有重要的意义. 从能带模型出发, 利用速率方程分析了整个热释光过程, 提出了一种计算稀土材料陷阱深度的新方法, 替代以往利用单分子或双分子近似计算陷阱深度的方法. 以SrAl2O4：Eu^2＋, Dy^3＋及Sr4Al14O25：Eu^2＋, Dy^3＋材料为研究对象, 计算了陷阱深度. 研究表明, 这种计算方法能更准确、真实地描述其物理过程.     

球等鞭金藻生长抑制物的高效液相色谱分析

采用硅烷化键合相C18反相色谱柱,以V(乙腈)∶V(水)=63∶37为流动相,0.3mL/min恒流洗脱,检测波长UV-235nm等条件,建立了一种利用反相高效液相色谱分析球等鞭金藻生长抑制物的粗提物、Sepha-dexG-15凝胶柱层析分离获得的3个组分、硅胶G薄层层析分离获得的4个组分等8个分离纯化产物中具有抑制活性组分的方法,并确定了具有抑制活性组分的保留时间。通过乙酸乙酯萃取球等鞭金藻老化培养液,得到了具有抑制活性的粗提物;粗提物经SephadexG-15凝胶柱层析分离后,获得3个具有抑制活性的组分;通过硅胶G薄层层析对此3个组分进行分离,在获得的4个组分中,仅有一个组分具有抑制活性。将粗提物与SephadexG-15凝胶柱层析分离获得组分的高效液相色谱进行对比,确定具有抑制活性组分的保留时间在3.827~6.002min范围内;通过与硅胶G薄层层析分离获得组分的高效液相色谱的再次对比,发现仅具有抑制活性的组分Ⅱ(Rf为0.637)中出现保留时间为4.875min的峰,并且相同保留时间的峰同样出现在具有抑制活性的粗提物以及SephadexG-15凝胶柱层析分离获得的3个组分的高效液相色谱中。结果表明:在优化的实验条件下,高效液相色谱中保留时间为(4.872±0.005)min的峰对应的组分正是具有抑制活性的组分。     

同位素稀释结合固相萃取快速测定动物组织中β2-兴奋剂

本文采用同位素稀释结合固相萃取技术,测定动物组织中特布他林、克伦特罗、沙丁胺醇、莱克多巴胺4种β2-兴奋剂。动物组织加同位素内标D3-沙丁胺醇和D9-克伦特罗,经甲醇提取后,正己烷脱脂,过SLS离子交换固相萃取柱净化,用BSTFA 1%(φ)TMCS衍生,采用GC/MS进行测定,内标法定量。实验表明,动物组织中添加2.0~10.0μg/kg浓度水平的β2-兴奋剂,方法回收率在72.5%~97.9%,相对标准偏差1.0%~11.4%,线性范围为12.5~500μg/L,样品中特布他林、克伦特罗、沙丁胺醇、莱克多巴胺最低检出限分别为0.5μg/kg、1.0μg/kg、0.5μg/kg和1.0μg/kg。     

Crystallization and Preliminary Crystallographic Studies of Luffaculin 1,a Ribosome-inactivating Protein from the Seeds of Luffa Acutangula

1 INTRODUCTION The ribosome-inactivating proteins (RIPs) are RNA N-glycosidases[1, 2] which inactivate ribosomes by cleaving a single N–C glycosidic bond between adenine and ribose at A4324 in the 28s rRNA of rat. Because of the removal of one adenine from rRNA, elongation factorⅡ(EF-2) can not bind to the 60S subunit, so RIPs can arrest protein synthesis. RIPs can be classified into three types based on the struc- tures of genes and mature proteins[3]. Type 1 RIPs with molec…     

Preparation and electrochemistry of azobenzene self-assembled monolayers on gold--long range tunneling and end-group hydrogen bonding effect

A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.     

Optical studies of pulsed-laser fragmentation of biliary calculi

The fragmentation of gallstones and kidney stones using pulsed visible laser radiation has recently been demonstrated; however, the fragmentation mechanism is not well understood. The temporal and spectral characteristics of the bright flash of light accompanying fragmentation of gallstones were studied using 0.8 and 360-s-long, 690-nm-wavelength, dye-laser pulses. Time-resolved visible emission spectra show a broad continuum upon which line spectra are superimposed. The continuum emission is due to free-free and free-bound electron transitions indicative of a plasma and the line spectra are due to neutral and ionized calcium. Initiation of this plasma is fluence rather than intensity dependent. A model is proposed in which laser energy is coupled to the plasma, which then impulsively expands, generating intense acoustic transients which fracture the stone.     

Hydrogen-bonded assembly and binding affinity of the multi-point acceptor and isophthalic acid

Supermolecular complexes formed by oligophenyleneethynylene derivatives and isophthalic acid were studied using AM1 method to obtain binding energy. Electronic spectra and IR spectra of the complexes were calculated by INDO/CIS and AM1 methods based on AM1 geometries. Results indicated that the dimer could be formed by the monomers via hydrogen bonding because of the negative binding energy. Binding energy of the complexes was affected by electronegativity and steric effects of the substituents. The first UV absorptions and IR frequencies of N-H bonds of the complexes were both red-shifted compared with those of the monomers. The complexes could bind small molecules via hydrogen bonds, resulting in the change in UV absorptions and an increase in IR frequencies of N-H bonds.     

Synthesis of Fullerene-end Functionalized Poly（methyl methacrylate） via Reverse Atom Transfer Radical Polymerization

The use of the reverse atom transfer radical polymerization （RATRP） to end-functionalize poly（methyl methacrylate） （PMMA） with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60（C70） terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques.