含胆汁酸和胆固醇的双亲性聚合物的研究进展

胆固醇和胆汁酸是广泛存在于自然界中的天然物质 ,生物相容性好 ,被广泛地用于高分子的疏水性改性 ,得到的双亲性聚合物 ,在水相中可以自组装或自聚集成纳米粒子。本文综述了含胆固醇或胆汁酸的双亲性聚合物的最新研究进展以及它们在药物载体系统中的应用。     

配体形状对多吡啶铜(Ⅱ)配合物与DNA作用的影响

合成了一系列含有平面配体的Cu(Ⅱ)多吡啶配合物[Cu(IP)₂]²⁺、[Cu(PIP)₂]²⁺、[Cu(DPPZ)₂]²⁺和[Cu(HPIP)₂]²⁺，用吸收光谱、CD光谱和粘度等方法研究了这些配合物与小牛胸腺DNA的作用。结果表明配体上的取代基及配体的平面性对这些四面体配合物与DNA的结合强弱产生一定的影响。[Cu(DPPZ)₂]²⁺与DNA的结合较强，而[Cu(HPIP)₂]²⁺与DNA的结合较弱。CD光谱显示配合物[Cu(DPPZ)₂]²⁺、[Cu(PIP)₂]²⁺和[Cu(HPIP)₂]²⁺的加入会导致DNA的CD光谱减弱。而[Cu(IP)₂]²⁺的加入则会使DNA的CD光谱增强。同时，[Cu(IP)₂]²⁺与DNA结合后，还会引起一定程度的DNA构型转换，即DNA从B型转换成Z型。     

四氟苯基宽带隙聚合物给体光伏材料的研究

设计并通过Stille缩聚方法合成了一种基于四氟苯和4,8-双(5-(2-乙基己基)噻吩-2-基)-苯并[1,2-b:4,5-b’]二噻吩单元的推拉电子型宽带隙聚合物(PBDT4F)作为聚合物太阳能电池的给体材料。用核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、热重分析、紫外-可见吸收光谱和循环伏安法等对其进行了表征。结果表明:PBDT4F对400～600 nm短波长光具有强吸收能力,并且具有低的最高占有轨道(HOMO)能级和适合的最低未占有轨道(LUMO)能级。基于PBDT4F为给体、有机小分子(5Z,5’Z)-5,5’-((7,7’-(4,4,9,9-四辛基-4,9-二氢-s-茚并[1,2-b:5,6-b’]二噻吩-2,7-二基)双(苯并[c][1,2,5]噻二唑-7,4-二基)双(亚甲叉))双(3-乙基-2-硫代-4-噻唑烷二酮)(O-IDTBR)为受体的共混活性层的光伏器件取得了0.986 V的开路电压和2.58%的光电转化效率。     

三种马来二腈基二硫烯镍(Ⅲ)离子对配合物的制备和结构表征

合成了3种离子对配合物 [1-benzyl-3-bromopyridium]⁺[Ni(mnt)₂]^- (1)，[1-(4′-flurobenzyl)-3-bromopyridiunm]⁺[Ni(mnt)₂]^- (2)，[1-(4′-cholorobenzyl)-3-bromopyridium]⁺[Ni(mnt)₂]^- (3)，(mnt=马来二腈基二硫烯，maleonitrile dithiolate)获得了单晶并解析了它们的单晶结构。     

壳寡糖与镧、铈配合物的合成、表征及应用

合成了壳寡糖，镧和壳寡糖，铈配合物，用红外光谱和紫外光谱进行了表征，并证实了氮，金属(N-M)键的形成，元素分析证实配合物中各元素C：H：N：La或Ce的原子个数比分别接近于24：44：4：1，即相当于配位数为4。壳寡糖一镧和壳寡糖一铈较未配位的镧或铈具有更强的催化氧化能力。配合物除去废液中磷[(PO)^3-4]的效果比未配位的镧和铈提高10％。配合物可提高蔬菜、水稻种子的发芽率，促进作物的营养生长，提高水稻产量3，3％，提高黄瓜产量12％～15％，对十字花科蔬菜的病毒有一定的抑制作用。     

异亚硝基乙酰乙酸乙酯亚胺Pd(Ⅱ)配合物的合成、表征和tran Pd(p-CH3C6H4-IEAI)2的晶体结构

Six palladium(Ⅱ) complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R-IEAI)₂, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p-CH₃C₆H₄-IEAI)₂ (2) cry- stallizes in the monoclinic system, space group P2₁/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm^-1. The final R and wR are 0.0244 and 0.0625 for 2620 ob-served reflections with I≥2σ(I), respectively. The geometry around the Pd(Ⅱ) ions in those complexes has a distorted PdN₄ square plane, the Schiff base ligands R-IEAI^- being coordinated through their oximino-nitrogen atoms and imino-nitrogen atoms.     

Cu2(μ-dppb)2(μ-Cl)2的合成、晶体结构及非线性光学性质

The complex Cu₂(μ-dppb)₂(μ-Cl)₂ has been synthesized from the reaction of CuCl， dppb and (n-Bu)₄NCl. The crystal belongs to the triclinic with space group P1. The unit cell parameters are: a=9.939(4)?， b=10.083(6)?， c=14.104(5)?， α=76.46(3)°， β=71.02(2)°， γ=70.87(5)°. The single crystal X-ray diffraction analysis reveals that it has a bi-ring structure with a symmetry center at the middle of two Copper atoms. The outer ring is a 14-membered ring of Cu-dppb-Cu-dppb， and the inner ring is a 4-membered ring composed of two Cl^- and two Cu(Ⅰ). Investigation of third-order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α₂=1.75×10^-13m·W^-1 and n₂=3.19×10^-18m²·W^-1. CCDC: 193113.     

铽-噻吩甲酰三氟丙酮-聚丙烯酸的结构及荧光性质

将铽的有机配合物NaTb(TTA)4与聚丙烯酸反应获得铽配位聚合物（Tb-TTA-PAA)。此配位聚合物是褐色固体，不溶于大部分有机溶剂，只能溶于丙三醇和异丙醇的混合溶剂。采用红外光谱、紫外光谱、X射线光电子能谱、电导率、元素分析和荧光光谱等手段对其结构进行表征，确定其配位组成和结构即每个铽离子分别与一个TAA^-离子和PAA分子中二个链节羧基发生配位，得到该配合物的结构。Tb^3 离子在配合物Tb-TTA-PAA中含量为29.98%。荧光光谱表明，常温下配合物在紫外光下发出强荧光，主要是Tb离子的^5D4→^7F5的能量传递。     

Nonlinear Optical Properties of Tri—nuclear Transition Metal Clusters M—（μ—S）s—M′（M=Mo,W;M′=Cu,Ag,Au）

The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation.     

1，4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-(1，4)合双铜(Ⅱ)配合物的合成、表征、非等温热分解反应动力学及电化学性质

The paper reported the synthetic procedure and character of Copper(Ⅱ) binuclear coordination compound of 1,4-bis-(1′-phenyl-3′-methyl-5′-pyrazolone-4′)-1,4-butanedione. The non-isothermal kinetic of the thermal decomposition of the complex has been studied from the TG-DTG curves by means of the Achar et al and Coats-Redfern methods. The electrochemical characterization of the complex were studied by means of powder microelectrodes technique.