自组装超分子膜修饰电极的研制及分析应用

阐述了自组装超分子膜修饰电极的发展概况及超分子体系形成的理论基础，并对自组装超分子膜修饰电极的特点、电化学行为、功能膜的制备和表征方法以及它在电催化、生物传感器、离子选择性电极等方面的应用进行了综述。     

HOD与H选键反应的理论研究

本文采用作者建立的分子内坐标下反应途径的动力学性质理论对HOD与H的选键反应进行了研究。以无选键性的HOH与H的反应和有选态性的H2(v=0,1)与OH的反应为对比,分别给出了每个反应内坐标下的垂直于IRC的振动模式的振动频率及断裂键的振动模式与其它振动模式之间的耦合常数(BKL)。通过它们对各反应选键性的分析,给出了在一定电子态下,为了达到选键反应的目的,该反应的断裂键振动频率和它与自身分子内其它键(键角)的耦合常数在理论上的要求。     

Synthesis,Structure and Thermal Property of a Cobalt Supramolecular Complex Containing N-[（4-Carboxyphenyl）-sulfonyl]glycine

Utilizing N-[(4-carboxyphenyl)-sulfonyl]glycine (abbreviated as cbsglyH3),a new cobalt complex [Co(cbsglyH)(bipy)2]3H2O (bipy = 2,2'-bipyridine) has been synthesized under mild conditions and characterized by IR,elemental analysis,thermogravimetric analysis and X-ray diffraction analysis. It crystallizes in the monoclinic system,space group C2/c with a = 34.978(3),b = 12.0437(11),c = 20.0041(19) ,β = 122.2990(10)°,V = 7123.0(11) 3,Z = 8,C29H28CoN5O9S,Mr = 681.55,μ = 0.593 mm-1,Dc = 1.271 Kg/m3,F(000) = 2816,the final R = 0.0434 and wR = 0.1351. The title complex is a monomeric compound which is further assembled by intermolecular hydrogen bonds into a 3-D supramolecular network. Thermogravimetric analysis illustrates that this complex begins decomposing at 100 ℃ and decompounding completely at 560 ℃.     

NEWS

构建最蛋近白,同质济阵大列学对化生学物系传田感阳器课、题蛋组白报质道组了学一、组种织基工于程蛋学白、质生微物阵电列子,器具件有等选的择发性展吸具附有、原重位要培的养作细用胞。     

烙印分子刚性对分子烙印手性固定手性拆分能力的影响

采用丙烯酰胺＋２－乙烯基吡啶复合功能单体烙印了刚性较小的苯甲氧羰基－Ｌ－丝氨酸、苯甲氧羰基－Ｌ－丙氨酸和具有一定刚性的苯甲氧羰基－Ｌ－脯氨酸，发现丙烯酰胺＋２－乙烯基吡啶体系对于分子刚性较小的分子也具有很好的烙印效果，表明不是烙印分子的刚性而是带有的与功能单体作用的化学功能基团才是实现分子烙印的关键。     

氰基二苯乙烯基超分子聚合物的构筑与光响应行为

通过在氰基二苯乙烯基元上引入氢键识别位点，驱使单体分子之间产生氢键与π-π堆积作用力的高效加合，构建了具有“成核-链增长”机制的超分子聚合物。通过获取组装热力学参数，揭示了酰胺及脲等不同氢键结构对于超分子聚合行为的影响规律。进一步利用超分子聚合态对于氰基二苯乙烯基元的限域效应，光照条件下特异性获得[2+2]环加成产物。与之相比，单体态时氰基二苯乙烯基元倾向于发生Z/E光异构化反应。这一研究结果可为多路径光化学反应的高效调控提供新的思路。     

苯/二联苯为桥的噻吩-吡咯-噻吩结构:分子构型及电致变色性质

A series of multi-branched dithienylpyrrole (SNS) monomers with rigid phenyl (PhSNS) and biphenyl rings (BPhSNS) as bridges were designed and synthesized, and were fabricated to form cross-linked polymers (pPhSNS, pBPhSNS) by electrochemical polymerization. Cyclic voltammetry (CV) results showed that PhSNS and BPhSNS exhibited similar oxidative properties except for one new higher-potential oxidative peak appearing in the curves of PhSNS. Theoretical calculations indicated that it should be attributed to the different steric configuration between the two dithienylpyrrole (SNS) units in PhSNS. One SNS unit possessed a larger twist angle (40.2°) between thiophene and pyrrole rings than the other one (21.2°), which indicated that PhSNS possessed a relatively larger energy gap (~0.4 eV) between HOMO-1 and HOMO than BPhSNS, for which HOMO and HOMO-1 levels were of almost the same energy. However, both PhSNS and BPhSNS showed similar onset oxidation potentials. The CV curves of pPhSNS and pBPhSNS showed that they presented similar oxidative properties, which enabled their corresponding electrochemical polymers to exhibit similar electrochromic properties. The UV-vis spectra of the corresponding polymers showed that both pPhSNS and pBPhSNS possessed similar optical absorption and similar multicolor switching between yellow (-0.8 V), greyish-green (0.9 V) and gray (1.1 V) colors. Besides, pPhSNS and pBPhSNS showed fast switching times of 0.57 s and 0.93 s at 1100 nm, respectively and reasonable contrasts of 46% and 31% at 1100 nm, respectively. These investigations may help understand the relationship between structural configuration and the electrochemistry/electrochromic properties for polymer electrochromic (PEC) materials research.     

Rate effect and coupled evolution of atomic motions and potential landscapes

Since rate effect of materials plays a key role in impact engineering, the microscopic mechanism of rate effect is investigated at molecular level in this paper. The results show that rate effect on the strength of atomic system is closely related to the coupled evolution of atomic motions and potential landscapes. Accordingly, it becomes possible to develop a new algorithm of molecular simulation, which could properly and efficiently demonstrate strain rate effect under a wide range of loading rates and unveil the mecha- nisms underlying the strain rate effects.     

OTS自组装单分子膜在玻璃表面形成程的AFM研究

运用原子力显微镜研究了十八烷基三氯硅烷在玻璃表面自组装形成单分子膜的过程.通过对样品表面的显微图像、表面平均粗糙度及前进接触角的测量分析,揭示了自组装单分子膜在玻璃表面的生长规律,并探索反应初期玻璃表面的吸附特点.