二十四元六氮大环双核铜(Ⅰ)配合物的氧化去甲基作用--单加氧酶的模拟

以5-溴-2-甲氧基-1,3-苯二甲醛与二乙烯三胺通过[2+2]缩合,合成了一个新的六氮杂二十四元大环配体,并在[Cu(CH3CN)4]ClO4存在下生成Cu(Ⅰ)大环配合物,然后在空气(或氧气)中氧化,得到了新的大环双核Cu(Ⅱ)配合物,用多种方法对其进行了表征,用1H NMR谱等方法鉴定了氧化产物.实验结果证明:在Cu(Ⅰ)配合物氧化过程中,能使配体环上的一个甲氧基发生断裂,形成苯氧桥和水桥联的Cu(Ⅱ)配合物.在木质素酶等单加氧酶的氧化过程中也伴随着氧化去甲基作用.本文首次用大环配合物对这一过程进行了模拟,并测定了氧化反应中的吸氧量和吸氧速率常数.     

配合物[Tb(p-ClBA)3(phen)]2的结构和性能

Terbium p-chlorobenzoate complex with 1,10-phenanthroline, [Tb(p-ClBA)₃(phen)]₂(1) has been obtained in the ethanol solution, where p-ClBA=p-chlorobenzoate and phen=1,10-phenanthroline. It crystallizes in the triclinic system, space group P1, a=1.008 1(2) nm, b=1.185 7(2) nm, c=1.431 1(3) nm, α=110.826(4)°, β=96.436(4)°, γ=101.737(4)°, Z=2. The two Tb(III) ions are linked by four carboxylate groups through their bidentate bridging modes, forming a dimeric unit with crystallographic inversion center. Each terbium ion has an eight-coordinate geometry with four of the coordination sites occupied by four oxygen atoms from the four bridging carboxylates, respectively, two oxygen atoms from bidentate carboxylate, and the remaining positions occupied by two nitrogen atoms from a 1,10-phenanthroline molecule. The Tb(III) ion adopt a distorted square antiprism coordination geometry. The excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The result of thermal analysis indicates the complex [Tb(p-ClBA)₃(phen)]₂ is quite stable to heat. CCDC: 221921.     

Meso-四(4-N-苄基吡啶基)卟啉合镍(II)的溶液配位化学研究

Beer's law experiment, variable-temperature spectral experiment of UV-Vis absorption, 1H NMR, and measurement of magnetic moment were conducted for NiTMPyP in aqueous solution. It was found that Beer's law was obeyed in concentration range 8× 10-7-2×10-5.mol•dm-3.With the temperature increasing from 0 ℃ to 95 ℃, the isosbestic point appeared at 435 nm and the lowest downfield 1H NMR peak narrowed gradually and shifted to upfield. The magnetic moment is 2.07 BM in D2O at 30 ℃, but in the D2O-CD3COCD3 mixed solvent there was no evidence for the existance of paramagnetic species. These results show that NiTMPyP exists in aqueous solution as an equilibrium mixture of diamagnetic, four-coordinate nickel (Ⅱ) and paramagnetic, sir-coordinate nickel (Ⅱ) complexed by water molecules in the axial position. The thermodynamic parameters of the axial-coordinated reaction were △S?=-178.6 J•K-1•mol-1, △G298K?=-1.6 kJ•mol-1.     

卤代芳香族羧酸与含氮配体合成镧系配合物的结构、热化学和荧光性质（英文）

采用室温溶液挥发法合成了五种结构新颖的镧系配合物,其结构通式为[Ln(2,4-DFBA)₃(phen)]₂ (Ln=Sm 1, Eu2, Er 3, 2,4-DFBA为2,4二氟苯甲酸的简写,phen为1,10-菲啰啉的简写),[Ln(2-Cl-6-FBA)₂(terpy)(NO₃)(H₂O)]₂ (Ln=Tb4, Dy 5, 2-Cl-6-FBA为2-氯-6-氟苯甲酸的简写, terpy为2,2’:6’2’’-三联吡啶的简写)。五个配合物可以分为两个系列,使用不同的镧系离子作为中心离子。通过X射线单晶分析,5种配合物均属于单斜晶系,空间群为P21/n。配合物1,2和配合物3虽然具有相同的分子通式,但配位方式明显不同,形成了前者为9配位的松饼型,后者是8配位的双帽三棱柱几何构型。二维面状超分子结构的形成方式也明显不同,区别在于配合物1和2通过微弱的π-π堆积作用形成。配合物4和5是同构的,结构中引入了硝酸根离子较为有趣,通过C―H···F氢键和π-π堆积作...     

层状钙钛矿化合物 (n-CnH2n+1NH3)2ZnCl4非等温固-固相变动力学的确定

确定了具有层状钙钛矿结构,脂肪链C原子数从12到18四氯合锌酸二烷基铵(C_nH_2n+1NH₃)₂ZnCl₄系列化合物的非等温固-固相变动力学。采用Kissinger和Ozawa两种动力学模型,对不同温度下测定的每个样品DSC热分析曲线进行数据处理,计算固-固相变过程的活化能E_a。实验结果表明,随着C原子数的增加,脂肪链的有序度和刚度降低,导致固-固相变活化能E_a随C原子数的增大而降低。两种模型方法的计算活化能E_a的结果相一致。并且各个化合物的固-固相变反应级数不随升温速率和烷基链长变化而变化,总保持为1。     

Nd∶NaY(WO_4)_2晶体生长与开裂研究

本论文采用提拉法 (CZ)生长了尺寸为1 5mm× 2 0mm的Nd :NaY(WO4) 2 晶体 ,并从理论上讨论了温度梯度、提拉速度、晶体转速和晶体尺寸等工艺参数以及热应变等因素对晶体开裂的影响 ,给出了生长Nd :NaY(WO4) 2 晶体的最佳工艺参数     

A note on Malmquist-Yosida type theorem of higher order algebraic differential equations

In this article, we give a simple proof of Malmquist-Yosida type theorem of higher order algebraic differential equations, which is different from the methods as that of Gackstatter and Laine [2], and Steinmetz [12].     

对氯苯甲酸铕与邻菲咯啉络合物热分解动力学参数及寿命的测定

用TG-DTG技术研究了对氯苯甲酸铕与邻菲咯啉络合物在静态空气中的热分解,用Coats-Redfern(CR)法、Horowitz-Metzger(HM)法、Madhusudanan-Krishnan-NInan(MKN)法、Ozawa法和Kissinger法计算了对氯苯甲酸铕与邻菲咯啉络合物第一步热分解反应的动力学参数活化能（E）、指前因子（A）、反应级数（n)等。用等温TG法得到失重10%的E、A值和寿命方程：lnτ=-23.0189 17974.1/T。     

等温热重法研究新型尾式卟啉季铵盐的热稳定性及寿命

用等温热重技术研究了三种新型尾式卟啉-三乙胺和吡啶季铵盐的热稳定性及寿命。得到了失重10%为寿终指标的寿命方程及稳定性大小的顺序。     

核壳结构PAM-ZnS纳米杂化微球的制备研究

随着高新科技的发展,人们对材料的要求越来越高,纳米材料的研究和材料的杂化已成为材料发展的重点之一.近年来,有彬无机杂化材料因其具有可调的光、电、磁等特性而备受关注．有彬无机杂化材料的杂化尺度通常为纳米级,甚至小到分子水平,因而可实现不同组分性质结合于一体,并产生协同效应．纳米ZnS材料因具有热红外透明、荧光、磷光等特性已引起人们极大的兴趣,例如ZnS纳米颗粒量子点及其掺杂具有独特的光电性质,主要用于传感器和高分辨显示器．