Cu2＋和铜锌超氧化物歧化酶作用的光谱学研究

利用邻苯三酚自氧化法监测在磷酸盐缓冲体系中Cu^2＋对猪肝铜锌超氧化物歧化酶(CuZnSOD)活力的影响, 认为Cu^2＋与猪肝CuZnSOD存在直接相互作用. 通过荧光光谱方法研究了这种相互作用, 内源荧光的猝灭实验表明Cu^2＋与CuZnSOD形成1∶1型稳定配合物; 荧光猝灭的动力学分析表明配合物形成过程由两个独立步骤完成: 第一步是双分子快速缔合过程, 形成了结合疏松的配合物, 第二步是单分子慢速过程, 即松散的配合物“异构化”成为结合紧密的配合物. FTIR和CD证实相互作用过程伴随了蛋白分子构象的变化.     

DNA为模板的铂纳米团簇沉积

Platinum nanoclusters were deposited along the supercoiled DNA strands after incubation of cis-(trans-1R，2R-diaminocyclohexane)(dl-camphorato)platinum(Ⅱ) (Cdp)， an analogue of the anti-tumor drug-carboplatin， with DNA and K₂PtCl₄ for 600 min and then through reduction of dimethylaminoborane (DMAB). The decrease of absorption of DNA at 260 nm indicates the coordination of Cdp and DNA. TEM and AFM were employed to characterize the morphologies and structures of platinum nanoclusters.     

1,2-丁二醇共聚对聚对苯二甲酸乙二醇酯结晶行为及力学性能的影响

为了探索生物基乙二醇中的1,2-丁二醇(1,2-BDO)作为共聚单体对生物基聚对苯二甲酸乙二醇酯(PET)的结晶行为和力学性能的影响。 本文合成了生物基PET均聚物和不同1,2-BDO共聚单元摩尔分数的系列生物基PET共聚物(共聚单体摩尔分数分别为2.0%、2.7%和5.6%),并采用傅里叶变换红外光谱仪(FTIR)、差示扫描量热仪(DSC)和力学测试等技术手段研究了其结晶行为和力学性能。 结果表明,随着1,2-BDO共聚单元摩尔分数的增加,PET共聚物的熔融温度、结晶速率及结晶度均明显降低,表明1,2-BDO共聚单体的引入破坏了PET分子链的规整性,阻碍了PET链段的结晶。 PET材料的拉伸强度随着1,2-BDO共聚单元摩尔分数的增加而降低,而弯曲强度和弯曲模量略有升高。     

纳米二氧化锆在甲醇合成催化剂Cu/Ga2O3/ZrO2中的作用

The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesoporous volume and more uniform diameter, more surface metal atoms and oxygen vacancies than the catalyst prepared with the conventional coprecipitation method. The modification of microstructure and electronic effect could result in the change of the reduced chemical state and decrease of reducuction temperature of copper, donating the higher activity and methanol selectivity to the catalyst. The results of methanol synthesis demonstrate that the Cu^＋ is the optimum active site. Also, the interaction between the copper and zirconia shows the synergistic effect to fulfil the methanol synthesis.     

Syntheses and Crystal Structures of 4,4‘—Diformyl—diphenoxyethane and 4,4’,4‘’—Triformyl—triphenoxytriethylamine

Two title compounds, 4,4'-diformyl-diphenoxyethane (compound 1, C16H14O4)and 4,4',4'-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris2-chloroethylamine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ', = 105.823(6)o, V = 675.7(2)'3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, (MoK = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ', = 99.505(1)°, V = 2383.5(3) '3, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, (MoK = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 dialdehyde is located at the crystallographic inversion center nearby the midpoint of C8-C8A single bond. The three chains in the molecule of compound 2 trialdehyde are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.     

一代树状碳硅烷液晶的光化学研究－－端基含12个4－丁氧基氮苯介晶基元

研究了新的含12个丁氧基偶氮苯介晶基元的五代树状碳硅烷液晶D1及偶氮苯介 晶基元化合物M5在氯仿、四氢呋喃、N，N－二甲基甲酰胺、乙醇和苯等溶剂中的量 子产率、反－顺光异构化、光回复异构、反／顺异构组分比、热回复异构及活化能 。D1和M5的光致变色速率常数为10~(-1)s~(-1)，而含同一偶氮基元的光致变色液 晶聚硅氧烷的光致变色速率常数为10~(-8)s~(-1)，因此，液晶树状物D1的光响应 速度比后者快10~7倍。     

一维链状柔性羧酸镉配位聚合物[Cd(p-BDOA)·2H2O]n的合成、结构与性质研究(英)

A novel 1-D Cd(Ⅱ) coordination polymer, [Cd(p-BDOA)·2H₂O]_n(I) ( p-BDOA^2-=benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR, PL, TG and X-ray single crystal diffraction. The Crystal crystallizes in monoclinic system, the space group is C2/c, with the crystal cell parameters a=1.175 1(1) nm, b=0.551 0(1) nm, c=1.827 7(2) nm, β=96.14(2)°, and V=1.176 6(3) nm^3,, M_r=372.60, R=0.045 9, wR=0.127 9. The Cd(Ⅱ) ion has a trigonal prism coordination configuration that defined by four carboxyl O atoms from two different p-BDOA^2- ligands and two water molecules. Adjacent Cd(Ⅱ) ions are linked by carboxylate groups with the bidentate coordination mode, giving rise to a chain structure with the adjacent Cd…Cd distance of 1.526 3(5) nm. Furthermore, such chains are linked by hydrogen bonds to form supramolecular network. The results of PL and TG show that the complex exhibits intense fluorescent emissions and its chain skeleton is thermally stable up to 419 K. CCDC: 220443.     

立方介孔相含钕氧化硅的合成与表征

以十六烷基三甲基溴化铵为结构导向剂，通过水热法合成了具有立方结构的含钕Nd-MCM-48介孔分子筛材料。XRD和TEM测试表明当n_Nd/n_Si<0.05时可以获得典型的长程有序介孔立方结构相，随n_Nd/n_Si比的增加，晶胞参数的增大和红外吸收光谱(FT-IR)的变化为Nd进入介孔分子筛骨架中提供了有力证据。N₂吸附-脱附实验给出了其BET表面积为1 195 m²·g^-1，BJH平均孔径为3.6 nm。紫外-可见漫反射光谱(UV-Vis)证明钕氧形成一种八面体结构。X射线光电子能谱(XPS)进一步证明钕主要以三价形式存在于立方介孔分子筛骨架中。     

水相法合成二氯二甲茂钛与水杨酸类配合物

Ｃｐ2 ＴｉＣｌ2 具有很好的抗癌活性 ,已成为第三代抗癌药物[1 - 3] 。为了寻求活性更高的抗癌药物 ,探索抗癌机理 ,我们用 (ＭｅＣｐ) 2 ＴｉＣｌ2 、水杨酸或其衍生物 ,按水相法合成了甲茂钛的水杨酸类配合物。合成路线如下图所示 :其中 :Ⅰ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =Ｈ的产物 ;Ⅱ为ｐＨ <4 ,Ｘ =Ｈ ,Ｙ =ＮＯ2 的产物 ;Ⅲ为ｐＨ >6 ,Ｘ =ＮＯ2 ,Ｙ =ＮＯ2 ,Ｚ =Ｏ的产物 ;Ⅳ为ｐＨ >6 ,Ｘ =Ｈ ,Ｙ =Ｈ ,Ｚ =Ｓ的产物。 (Ⅰ～Ⅳ为新化合物 )1　实验部分1 .1　仪器与试剂水杨酸、ＴｉＣｌ4,ＡＲ ;5 -硝基水杨酸、3,5 -二硝基水杨酸、5 -磺基…     

Oxidation of n-Butanol and 2-Pentanol with Molecular Oxygen in Supercritical CO2

Oxidation of n-butanol and 2-pentanol using molecular oxygen in supercritical (SC) CO2 with and without co-solvent is investigated. The results showed that the reaction selectivity is high when the reaction is carried out in SC CO2. It has been observed that co-solvent affects conversion and selectivity of the reaction considerably.