Hydrothermal Syntheses and Crystal Structures of Zn(Ⅱ) and Co(Ⅱ) Complexes Constructed from 5-Methoxyisophthalic Acid and 1,10-Phenanthroline Ligands

Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature.     

Synthesis and Crystal Structure of a Two-dimensional Cobalt Complex with 5-Tert-butyl Isophthalic Acid

The self-assembly of Co(OAc)·4H2O with H2tbip and bipy (H2tbip = 5-tert-butyl isophthalic acid, bipy = 4,4'-bipyridine) generates one new complex, [Co3(tbip)2(Htbip)2(bipy)]n, which has been characterized by elemental analysis, X-ray diffraction, and IR spectroscopy. Single-crystal X-ray analysis reveals that it crystallizes in the triclinic space group P1 with a = 9.471(6), b = 12.597(8), c = 12.899(8), α = 84.660(7), β = 70.548(7), γ = 81.965(7)o, V = 1435.1(15)3, Mr = 1215.85, Dc = 1.407 g/cm3, Z = 1, F(000) = 629, μ(MoKα) = 0.926 mm-1, the final R = 0.0623 and wR = 0.1724. The complex consists of a tbip bridged trinuclear cobalt() unit and is further linked by 4,4'-bipyridine molecule to form a 2D supramolecular network.     

一维链状锰配位聚合物[Mn(1,5-nds)(Him)_4]_n的合成、晶体结构及热稳定性研究(英文)

The synthesis,structural characterization and thermal behavior of a novel one-dimensional manganese (Ⅱ) complex of formula [Mn(1,5-nds)(Him)4]n [1,5-nds=naphthalene-1,5-disulfonate,Him=imidazole] is reported.The complex crystallizes in the triclinic system,space group P1,with a=0.835 42(13) nm,b=0.983 45(18) nm,c= 0.987 42(19) nm,α=60.523 0(10)°,β=97.748(2)°,γ=87.189(2)° and Z=2.The 1,5-nds ligand assumes the μ2 coordination mode and interlinks Mn(Ⅱ) ions into infinite one-dimensional chain structure along [111] direction,with the adjacent Mn…Mn distance being 1.144 99(12) nm.The chains are assembled into a three-dimensional supramolecular architecture via hydrogen bonds and C-H…π interactions.IR spectra and thermal analysis data are in agreement with the crystal structure.     

对苯二酚在掺Cu(Ⅱ)类普鲁士蓝膜修饰电极上的电化学行为研究

采用循环伏安法在普鲁士蓝膜中掺杂Cu2+,制得掺Cu(Ⅱ)类普鲁士蓝膜(Cu-PB膜)。利用循环伏安法、库仑分析法和电化学阻抗法对Cu-PB膜进行电化学表征,结果显示Cu2+进入普鲁士蓝的内部结构,取代了其中的高自旋铁。该Cu(Ⅱ)类普鲁士蓝膜对对苯二酚具有明显的电催化作用,电极反应过程是扩散控制的准可逆过程,在5.0×10-5~1.0×10-3mol.L-1范围内,还原峰电流与对苯二酚浓度呈良好的线性关系,检出限为1.0×10-6mol.L-1。计算了对苯二酚在Cu-PB膜修饰电极上电极过程的动力学参数。     

水溶性Rh-BISBIS配合物对阿维菌素催化加氢的研究

The hydrogenation of avermectin catalyzed by [RhCl(COD)]_2-BISBIS[COD:1,5-cyclooctadiene,BISBIS:sulfonated 1,1'-bis(diphenylphosphino Methyl-2,2'-biphenyl)] in situ in aquenous/organic two-phase system was studied.The influence of various parameters,such as the surfactant concentration,the molar ratio of rhodium to phosphine,the reaction temperature and pressure on this hydrogenation were investigated.The results showed that the hydrogenation activities of diphosphine was higher that of monophosphine.     

线性唯象传热定律下光驱动发动机的最优路径

以存在热漏、摩擦等不可逆性,以双分子反应系统2SO3FS2O6F2为工质的光驱动发动机为研究对象,考虑工质与环境之间传热服从线性唯象传热定律[q∝Δ(T-1)],分别以输出功最大和熵产生最小为目标对整个循环活塞运动的最优路径进行研究.利用最优控制理论得出了活塞运动路径及工质温度的最优构型,给出了最优构型的数值算例,并与牛顿传热定律[q∝Δ(T)]下的最优构型进行了比较.     

电泳技术在纳米颗粒分离中的应用

合成纳米颗粒常在尺寸和形状方面具有广泛分布.在很多实验中,需要利用一定大小及形状的纳米颗粒的独特物理化学性质,因此,简便快速的纳米颗粒分离技术越来越受到诸多科学领域的重视.电泳技术以其高分辨率,被广泛用于多种生物大分子如核酸、蛋白质等的分离纯化.纳米颗粒在尺寸上与生物体中的蛋白复合物、细胞器和微生物等十分接近,考虑到带电纳米颗粒与生物分子在电场中的运动行为的相似性,运用电泳技术进行纳米颗粒的鉴定、分离和纯化是一种新的思路,并取得了良好的实验结果.本文主要介绍了琼脂糖凝胶电泳、毛细管电泳以及其他一些电泳技术在纳米颗粒分离中的研究进展.     

What is the nature of polyacetylene neutral and anionic chains HC(2n)H and HC(2n)H(-) (n = 6-12) that have recently been observed?

The optimized geometries, adiabatic electron affinities, and IR-active vibrational frequencies have been predicted for the long linear carbon chains HC(2n)H. The B3LYP density functional combined with the DZP basis set was used in this theoretical study. The computed physical properties are discussed. The predicted electron affinities form a remarkably regular sequence: 1.78 (HC(12)H), 2.08 (HC(14)H), 2.32 (HC(16)H), 2.53 (HC(18)H), 2.69 (HC(20)H), 2.83 (HC(22)H), and 2.95 eV (HC(24)H). The predicted structures display an alternating triple and very short single bond pattern, with the degree of bond alternation significantly less for the radical anions.     

A facile approach to architecturally defined nanoparticles via intramolecular chain collapse

A novel approach is presented for the controlled intramolecular collapse of linear polymer chains to give well-defined single-molecule nanoparticles whose structure is directly related to the original linear polymer. By employing a combination of living free radical polymerization and benzocyclobutene (BCB) chemistry, nanoparticles can be routinely prepared in multigram quantities with the size being accurately controlled by either the initial degree of polymerization of the linear chain or the level of incorporation of the BCB coupling groups. The latter also allows the cross-link density of the final nanoparticles to be manipulated. In analogy with dendritic macromolecules, a significant reduction of up to 75% in the hydrodynamic volume is observed on going from the starting random coil linear chains to the corresponding nanoparticles. The facile nature of the living free radical process also permits wide variation in monomer selection and functional group incorporation and allows novel macromolecular architectures to be prepared. Furthermore, the use of block copolymers functionalized with benzocyclobutene groups in only one of the blocks gives, after intramolecular collapse, a hybrid architecture in which a single linear polymer chain is attached to the globular nanoparticle.     

Li(NTO)(H2O)2的热分解行为及其结构与性质的关系研究

摘要在水中合成了3-硝基-1,2,4．三唑-5-酮(NTO)的锂盐Li(NTO)(H2O)2,利用DSC,TG／DTG和IR方法研究了其金属配合物的热分解机理,并用Kissinger法、Ozawa法、积分法和微分法对标题配合物进行了非等温动力学研究,得到了热分解反应的动力学参数,确定了热分解第一阶段的动力学方程及配合物的热爆炸临界温度(Tb)为289．33℃．采取RHF／6-31G,DFT-RB3LYP／6-31G方法对标题化合物进行了几何全优化,并对其成键情况、电荷分布和化合物的稳定性进行了分析．