Solvothermal Synthesis, Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)2(2,2''-bipy)(H2O)]·(H2O)

One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

喹喔啉—2,3—二甲酰胺与3d过渡金属配合物的合成及性质研究

首次合成了喹喔啉－２，３－二甲酰胺（Ｑｘｄａ）与３ｄ过渡金属的三种固体配合物：Ｍ（Ｑｘｄａ）２ｃｌ２（Ｍ＝Ｃｏ（Ｉ），Ｎｉ（Ｉ），Ｃｕ（Ⅱ）。通过元素分析，摩尔电导，红外光谱，电子光谱，磁化率，热分析等手段对配合物的组成和性质进行了研究。     

A new method for the direct calculation of resonance parameters with application to the quasibound states of the H2X1Σ g + system

A new method for the direct calculation of resonance parameters is presented. It is based upon searching for poles of the scattering matrix at complex energies. This search is expedited by the use of analytic derivatives of the scattering matrix with respect to the total energy. This procedure is applied initially to a single channel problem, but is generalizable to more complicated systems. Using the most accurate available potential energy data, we calculate resonance parameters for all of the physically important quasibound states of the ground electronic state of the hydrogen molecule. Corrections to the Born-Oppenheimer potential are included and assessed. The new method has no difficulty locating resonances with widths greater than about 1×10^–7 cm^–1. It is easier to find narrow resonances by monitoring the dependence of the imaginary part of the reactance matrix on the real part of a complex energy than to monitor the dependence of the eigenphase sum on energy at real energies.     

辣根过氧化物酶自组装多层膜结构形貌与活性的研究

用分子沉积自组装作制备了阳离子化和阴离子化的辣根过氧化物酶自组装膜；并用原子力显微镜（AFM）研究了不同离子化辣根过氧化物酶单层及多层自组装膜的形貌结构与自组装膜的活性变化关系。结果表明：阴离子化的辣根过氧化物酶自组装膜的表面形貌比较粗糙，均方根粗糙度（RMS）及酶分子粒径较大，且组装膜的活性比较大。     

Atomic structure of InAs quantum dots on GaAs

In recent years, the self-assembled growth of semiconductor nanostructures, that show quantum size effects, has been of considerable interest. Laser devices operating with self-assembled InAs quantum dots (QDs) embedded in GaAs have been demonstrated. Here, we report on the InAs/GaAs system and raise the question of how the shape of the QDs changes with the orientation of the GaAs substrate. The growth of the InAs QDs is understood in terms of the Stranski–Krastanow growth mode. For modeling the growth process, the shape and atomic structure of the QDs have to be known. This is a difficult task for such embedded entities.

In our approach, InAs is grown by molecular beam epitaxy on GaAs until self-assembled QDs are formed. At this point the growth is interrupted and atomically resolved scanning tunneling microscopy (STM) images are acquired. We used preparation parameters known from the numerous publications on InAs/GaAs. In order to learn more about the self-assemblage process we studied QD formation on different GaAs(0 0 1), (1 1 3)A, and ( )B substrates. From the atomically resolved STM images we could determine the shape of the QDs. The quantum “dots” are generally rather flat entities better characterized as “lenses”. In order to achieve this flatness, the QDs are terminated by high-index bounding facets on low-index substrates and vice versa. Our results will be summarized in comparison with the existing literature.     

高分子钯络合物催化的亚胺化合物的加氢反应

制备了一系列以二氧化硅为载体的侧链上含有各种氮配位基团的聚硅氧烷-钯络合物,这些高分子钯络合物能够在常温常压下催化亚胺化合物的加氢反应并表现出不同程度的催化活性.对其中聚-(N,N-二乙酰基)-γ-氨丙基硅氧烷-钯络合物催化的亚苄基苯胺的加氢反应做了比较深入的研究,发现该催化剂在反应中是稳定的并给出唯一的加氢产物,络合物中的N/Pd原子比、反应温度以及不同底物对反应速度的影响也被报道.     

COCl2…NH3和COCl2…H2S体系的理论研究

在MP2水平上,用aug-cc-pVTZ基组对COC l2…NH3和COC l2…H2S体系进行几何优化和频率计算,同时使用Counterpoise技术进行BSSE校正,分别得到4个COC l2…NH3和2个COC l2…H2S无虚频的稳定结构:N(S)…C连接的构型(Ⅰ,Ⅱ,Ⅴ)和N(S)…C—lC直线型连接的构型(Ⅲ,Ⅳ,Ⅵ).第一类构型比第二类构型相互作用能更大、更稳定.在得到的6个稳定络合物中,络合物Ⅰ是最稳定的.     

某些多氮杂大环的合成与应用

多氮杂大环与许多金属离子能形成稳定的络合物。由于氮原子是三价的,因而多氮杂大环比冠醚具有更有利的结构;如果再导入羧基、膦酸基以及其他的亲水基团,则可得到一系列能形成水溶性金属络合物的配体。其中某些金属(如铜、钇等)的络合物在人体生理条件下表现出很好的稳定性,结合单原抗体技术的应用,这炎络合物在医疗、诊断方面有实用性。本文简单介绍某些代表性络合物的制备方法、物理性能和可能的应用。     

溶液中N—乙酸基取代氮氧杂大环的构象及其配合物的NMR研究

用~1HNMR方法研究了溶液中大环化合物1,12-二氮杂-3,4:9,10-二本并-5,8-二氧杂环十五烷-N,N’-二乙酸盐的构象.NMR变温实验表明,在溶液中大环与Zn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)的配合物环上醚氧不参与配位,其中Ni(Ⅱ)配合物为低自旋反磁性的平面四方形配位.     

钒、铬、锰磷桥络合物中31P NMR化学位移的研究

ISSIe山和W6flSChllh山子1960年首次用pdCI。和二苯基磷合成出黄色的二聚络合物，后被H。yieY＊确认为具有pRZ的桥式结构．此后一系列该类结构的化合物被合成并引起了广泛的兴趣．磷可以和两个甚至多个金属原子络合构成多核金属络合物，在催化反应中有重要应用．磷原子存在多种电子态，其3d空轨道也能参与成键．P乃1的NMR谱是研究含磷化合物立体结构的有力工具．P－31与其它核素之间的耦合常数以及P－31的化学位移对阐明化合物的立体构象以及电子结构具有重要作用．近年来，West饲用计算机神经网络技术预测P－：if的化学位移，但仅…