CH2XH→CH3X (X＝O, S, Se)异构化的量子拓扑研究

利用从头算和量子拓扑方法讨论了CH₂XH→CH₃X (X＝O, S, Se)异构化过程的反应机理. 着重从电子密度拓扑分析计算了反应进程中的各点, 讨论了反应进程中键的断裂和生成, 上述反应都经历了三元环过渡结构, 找到了这类反应的"能量过渡态"和"结构过渡态", 且结构过渡态均在能量过渡态之后出现. 三元结构过渡态结构出现的范围与反应热成正比.     

Construction of Two Coordination Polymers Based on Two New 5-Substitued Tetrazole-based Ligands: Structures and Luminescent Properties

Two new coordination polymers(CPs) based on two new tetrazole-based ligands, namely, [Cu(TPP)]n(HTTP = 4-(3-(2 H-tetrazol-5-yl)phenyl)pyridine, 1) and {[Cd_2(TBCA)_2(H_2O)_2]·-H_2O}n(H_2TBCA = 3?-(2 H-tetrazol-5-yl)biphenyl-4-carboxylic acid, 2), were synthesized via solvothermal reactions. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a(3,6)-connected rtl network topology based on binuclear secondary building units(SBUs). Compound 2 presents a 2D framework composed of 1D SUBs formed by both carboxyl and tetrazole groups. The 2D network is linked into a 3D framework via various hydrogen bonds. They represent two examples of CPs construct from rigid 5-substitued tetrazole-based ligands with relatively longer spacer. The thermal stabilities and luminescent properties of compounds 1 and 2 were also explored.     

OCS分子的共振多光子电离光谱

OCS分子的真空紫外吸收光谱早有研究,但有关OCS分子的多光子电离光谱尚未见报导。我们利用可调脉冲激光器,研究了OCS分子的共振多光子电离光谱。首次观察到OCS分子在277—285nm波长范围内的多光子电离光谱。OCS由硫氰酸铵和硫酸反应制取,经多次低温蒸馏纯化。产物通过FT-IR红外光谱和     

硒芳香杂环化合物的光谱和电化学性质

用紫外光谱，荧光光谱和循环伏安法研究了含硒芳香杂环化合物（苤硒脑）在不同溶剂中的谱学和电化学性质，对不同分子结构或取代基的苤硒脑化合物的性质进行了比较，并初步探讨了溶剂对苤硒脑化合物谱学性质的影响规律。     

关于Aa-Bb型缩聚物网络结构的研究——溶胶凝胶分配理论

溶胶凝胶分配理论是在分子水平上表征交联网络结构的有效工具。由Flory等建立和发展起来的这一理论,由于引用了溶胶相无分子内环化反应的假定,特别是在理论推导中将分子内交联反应与分子间的链增长反应对两相分配的贡献未能加以区别,致使理论与实验不符。本文充分考虑了经典理论的这些缺欠,建立了更为符合客观实际的理论模型。同时,用十分简便的方法推导了反应溶胶分数,溶胶反应程度,分子内和分子间总反应程度等量宏观联系的参数方程组。以聚酯为模型化合物的实验研究与本文所得理论结果基本相符。     

呋喃丹的极谱法测定研究及应用

用循环伏安法(CV)、线性扫描伏安法(LSV)对呋喃丹的极谱伏安行为及其测定进行了研究。在0.2mol/L NH3-NH4Cl底液中(pH 8.8),对其进行扫描,发现于-1.21V(vs.SCE)处产生一灵敏的还原峰,其峰电流与呋喃丹的浓度在5.0×10-6-1.0×10-mol/L范围内呈良好的线性关系(r=0.9995)。对5.0×10-5mol/L呋喃丹溶液进行6次平行实验,RSD为0.2％。实验结果表明,呋喃丹在极谱电极上有吸附性质。同时对电极反应机理进行了研究。该方法对微生物降解呋喃丹进行监测取得满意的结果,96 h内呋喃丹的降解率为98％。     

Synthesis of Fullerene-Acrylamide Copolymer Nanoball and Its Lubrication Properties

A novel fuUerene-acrylamide copolymer was synthesized via radical polymerization. It is soluble in polar solvents such as water, dimethyl sulfoxide etc. The product was characterized by FTIR, UV-Vis and GPC. TEM analysis shows that the average particle diameter is about 46 nm. Four-ball tests show that the addition of a certain concentration of the fullerene copolymer to base stock (2 wt% triethanolamine and 0.5 wt% OPZ aqueous solution) can effectively raise the load-carrying capacity (PB value) and the antiwear ability. SEM analysis shows that the addition results in reducing diameter of wear scar and decreasing wear.     

聚合物载体-稀土金属配合物的研究ⅩⅠⅤ.聚(苯乙烯-丙烯酰胺)载体-氯化钕配合物对丁二

研究了聚（苯乙烯－丙烯酰胺）（ＰＳＡＣ）载体－氯化钕配合物催化丁二烯聚合的规律，考察了ＰＳＡＣ载体及ＰＳＡＣ．ＮｄＣｌ３配合物的组成与催化活性间的关系，ＰＳＡＣ载体的收率不影响配合物的活性，而配合物的活性却随ＰＳＡＣ载体中Ｃ（Ｏ）ＮＨ２功能团含量的高低而改变，含量低时活性高，ＰＳＡＣ载体与配合物的组成不影响所得聚丁二烯的微观结构。     

基于5-芳基乙内酰脲类化合物的CoMFA和HQSAR研究

用CoMFA和HQSAR两种QSAR方法研究了50个乙内酰脲类分子的定量构效关系.本研究从构象搜索所得的低能结构出发构建化合物分子的构象, 建立CoMFA模型,并进行了全空间搜索. HQSAR本质上是一种二维的QSAR方法,与CoMFA方法相比,该方法在数据处理方面,比CoMFA方法快捷,并且可重复性好.两种方法均得到了较好分析结果, CoMFA的交叉验证相关系数q2 值为0.815, HQSAR的q2值为0.893.这些方程有力地说明了该类分子在(R,R)-N-3,5-dinitrobenzoyl-1,2-diamine型手性固定相上拆分过程中的影响因素,对今后类似拆分的实验研究提供了理论支持.     

溶剂化金属原子浸渍法制备Pd-Cu/γ-Al2O3低温CO氧化催化剂

Nano-particle Pd/γ-Al₂O₃ monometallic and Pd-Cu/γ-Al₂O₃ bimetallic catalysts were prepared by solvated metal atom impregnation (SMAI) method. The results of XRD measurement indicated that Pd- Cu alloy was formed in the bimetallic catalysts and the crystalline particle size of the alloy increased as Cu contents increased with av-erage diameters < 6.0nm for all the samples. XPS and Auger spectra showed that Pd was in zero- valent state, Cu existed mainly in zero- valent state and partially in monovalent state Cu⁺. The Pd/γ-Al₂O₃ and Pd-Cu/γ-Al₂O₃ catalysts exhibited higher activity for CO oxidation at low temperature. The activity of Pd-Cu/γ-Al₂O₃ bimetallic catalyst was higher than that of Pd/γ-Al₂O₃ monometallic catalyst. The Pd-Cu/γ-Al₂O₃ catalyst with Pd/Cu atomic ratio of 1∶1 showed the highest activity.