SrTi0.9M0.1O3-δ钙钛矿型氧化物催化剂甲烷氧化偶联反应性能的研究

The structure and catalytic properties of SrTi_0.9M_0.1O_3-δ (M=Mg，Al， Zr) perovskite-type catalysts for ox-idative coupling of methane (OCM) have been studied by using X-ray diffraction (XRD)，X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of oxygen(O₂-TPD) methods. It has been shown that doping the cations of lower valence (e.g. Mg²⁺， Al³⁺) to the B site of SrTi_0.9M_0.1O_3-δ perovskite-type catalysts results in the higher content of adsorbed oxygen species on the surface of catalysts and thus higher C₂-selectivity for OCM reaction. It is suggested that the oxygen vacancies of SrTi_0.9M_0.1O_3-δ (M=Mg， Al， Zr) perovskite-type catalysts are the sites responsible for oxygen activation， and the adsorbed oxygen species on the surface of SrTi_0.9M_0.1O_3-δ catalysts are the main active species for OCM reaction.     

Electrochemical Impedance Analysis of Thermogalvanic Cells

Thermogalvanic cells(also known as thermo-electrochemical cells) that convert waste heat energy to electricity are a new type of energy conversion device. However, the electron transfer kinetics and mass transfer of redox couples have not been thoroughly studied. Here, the ion reaction and charge transport in thermogalvanic cells are investigated by electrochemical impedance analysis. We first propose the detailed impedance model followed experimental verification on three types of electrode materials. Parameters including kinetic rate constants and ion diffusion coefficients for the electrodes are obtained by fitting the impedance data. Our study shows explicitly that impedance analysis can provide useful information on selecting suitable electrode materials for thermogalvanic cells.     

Synthesis and X-ray crystal structure of oxamido-bridged heterobinuclear Ni(Ⅱ)-Cu(Ⅱ) complexes

The two complexes [Ni(oxen)Cu(L)2](ClO4)2.xH2O (L=2,2'-bipyridyl(bpy), 1,10-phenanthroline(phen)) have been synthesized, where oxen is N,N'-bis(2-aminoethyl)oxamido di-anion. The crystal structure of [Ni(oxen)Cu(bpy)2](ClO4)2.CH3OH has been determined by X-ray diffraction method. The crystal is triclinic system, space group P1 with a=12.179(1),b=12.298(2), c=11.476(2) A, a=97.57(1), B=97.52(1), 7=80.29(2), V=1669.04(67) A3, Z=2, Dcalcd=1.667 g/cm3. The structure has been refined to final R of 0.076 and Rw of 0.080, respectively. The complexes have an extended oxamido-bridged structure and consist of Ni(Ⅱ) ion in a square planar environment and Cu(Ⅱ) ion in a distorted octahedral environment.     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

本文通过对TiCl_3-Al(C_2H_5)_3聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-l-phenyl-l-propanone with borane catalyzed by (S)-4-benzyl-5,5-diphenyl-l,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step Ⅲ exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-l-phenyl-l-propanone spontaneously, resulting in the need of 2 tool BH3 in the reaction.     

CHEMOTHERAPEUTIC POLYMERS Ⅻ. SYNTHESIS AND ANTITUMOR ACTIVITY OF POLYAMIDES CONTAINING 5-FLUOROURACILS AS PENDANT GROUP

Six polyamides with pendant 5-fluorouracil group were synthesized by the polycondensation ofdi-p-nitrophenyl N-(5-fluorouracil-1-acetyl)glutamate with a series of polymethylene diamines.All of the new polyamides obtained are soluble in water. Their chemical structures were confirmedby ~1H NMR, UV and IR spectra as well as elemental analyses. The antitumor activity of some ofthese polyamides were tested against Ehrlich Ascites Carcinoma in mice, III_a showed an inhibitionrate of 43%.     

植物光诱导延迟发光介导的酸性环境污染监测

酸雨和大气污染会对植物叶片内叶绿体的结构和功能产生影响，而植物光诱导延迟发光（DLE）被认为主要产生于叶绿体的PSⅡ中。利用自制的弱光探测系统，以生长周期长、叶片面积大的紫荆花叶片作为实验材料，研究了模拟酸雨和SO2对其DLE特性的影响。结果发现，绿色植物叶片光诱导DLE强度的变化能很好地反映植物叶片中叶绿体完整性以及叶绿体功能的变化。凶此，可以用DLE强度的变化来表征环境对植物的胁迫程度，有望为环境污染监测及生物学评价提供新的手段。     

爆炸冲击的激光多普勒远距离测量技术的研究

利用激光多普勒效应和数字信号处理方法,获取爆炸冲击过程中的高速变形参数,以此作为对爆炸强度分析的依据。根据爆炸变形的特点,设计了外差式纵向激光多普勒测量系统,提出了相应的数字滤波和频谱分析的信号处理方法,实现了爆炸变形的动态测量。系统测量的位移量程为±30mm,速度量程为-10~+20m/s,测量距离为4.5m。与振动台的试验对比,位移测量相对误差小于1%。给出了圆筒钢制爆炸容器在300gTNT当量炸药爆炸过程中弹性变形的测量结果。     

基于极坐标中蛇模型的类圆目标轮廓提取技术研究

提出了转化到极坐标中的蛇模型.通过把蛇模型转化到极坐标中,使轮廓的候选点得以更有序的排列.由于采用了动态规划法并在整个能量空间中搜索能量泛函的极值,算法对能量泛函的局部极值有较强的鲁棒性.所提出的模型不需要确定初始轮廓,可以用非迭代方法直接求解.与传统的动态规划法和贪婪算法进行了比较实验.结果表明,所提出的算法对极坐标中极点的位置不是很敏感.