Ho(III)希夫碱大环配合物的合成、晶体结构及对DNA的切割活性

本文合成一个新的希夫碱大环配体硝酸Ho(III)配合物 [Ho(H2L)(NO3)2](NO3) (H2L表示大环配体Fig. 1),并进行了系统的物理表征. 晶体结构研究表明: 配合物晶体结构属六方晶系,P 3(1)21空间群,晶胞参数a=1.47213(7) nm,c=2.8998(3) nm,α=90°,γ=120°,V=5.4424(7) nm 3,Z=6,R＝0.0331, wR＝0.0928。中心离子Ho3+位于隔室大环配体的一侧并于希夫碱大环上的两个酚基氧原子和三个氮原子配位,两个双齿配位硝酸根分别从希夫碱大环平面的两侧与中心离子配位使中心离子形成扭曲的九配位三冠三棱柱配位构型。并通过凝胶电泳实验初步研究了该配合物对pBR322质粒DNA的切割作用。     

A Novel Mononuclear Copper（Ⅱ） Complex：Crystal Structure and DNA Cleavage Ability

The reaction of N-tosylatirdine with 1,2-diaminopropane in dry benzene solution yields an intermediate H2L, N,N,N',N'-tetrakis(2-(p-tolylsulfonyl)aminoethyl) propane-1,2-diamine. The mononuclear copper(Ⅱ) complex, [CuLH2O]·H2O, was synthesized by the reaction between the intermediate and copper(Ⅱ) in absolute methanol. The complex has been characterized by IR, UV-vis and X-ray diffraction technology, and its crystal crystallizes in the orthorhombic system, space group Pbca with a = 15.589(1), b = 21.897(2), c = 27.645(2) , V = 9436.4(1) 3, Dc = 1.352 g/cm3, Z = 8, Mr = 960.68, F(000) = 4040, μ(MoKa) = 0.698 mm-1, S = 0.98, R = 0.0537 and wR = 0.1180 for 5804 observed reflections (I > 2σ(I)). In the crystal structure, a one-dimensional chain is formed by abundant hydrogen bond interactions. The interaction of the complex with DNA was monitored using agarose gel electrophoresis. The result shows that the complex can transform the supercoiled to nicked and liner forms, and has a concentration-dependent cleavage activity.     

Gd(Ⅲ)-Cu(Ⅱ)杂核大环配合物的合成、表征和磁性

报道了Gd(Ⅲ)-Cu(Ⅱ)杂核大环配合物的合成. 元素分析、红外光谱、电喷雾质谱等数据证明杂核配合物的存在. 变温磁性研究结果表明分子内Gd(Ⅲ)和Cu(Ⅱ)成铁磁性偶合.     

双酚大环配体硝酸铕三元配合物的合成、晶体结构与荧光性质

在硝酸铕模板下用丙二胺和2,6-二甲酰基-4-甲基苯酚通过[2＋2]缩合反应, 合成了一个新的双酚亚胺大环配体硝酸铕三元配合物[Eu(H2L)(NO3)3] (L表示大环配体), 并进行了系统的物理表征. 晶体结构研究表明: 配合物为中性分子, 由一个Eu3＋, 一个中性大环配体(H2L)和三个配位硝酸根组成. 晶体结构属单斜晶系, P21/c 空间群, 晶胞参数a＝1.57296(11) nm, b＝0.96957(7) nm, c＝1.91196(13) nm, β＝104.445(1)°, V＝2.8237(3) nm3, Z＝4, R＝0.0507, wR＝0.1168, Eu3＋为10配位, 呈扭曲的双冠四方反棱柱配位构型. 在低温下(77 K), 配合物在甲醇溶液中以紫外光激发产生了Eu3＋离子特征的荧光发射.     

新型锌酞菁衍生物的合成及其光物理性质

以锌酞菁为母核,设计并合成了新型锌酞菁衍生物(1),其结构经UV-Vis, ¹H NMR和HR-MS(ESI)表征。以DMSO为溶剂,对化合物1的光物理性质进行了检测。结果表明：化合物1的紫外-可见吸收光谱Q-带最大吸收峰为682 nm;荧光光谱的最大发射波长为690 nm;以无取代的ZnPc（Φ_F=0.20, Φ_△=0.67）为参照,测得化合物1的荧光量子产率（Φ_F）为0.22,单线态氧量子产率（Φ_△）为0.71;化合物1的光热转换效率为48.8%。     

八苄硫基四氮杂卟啉钴(Ⅱ)对半胱氨酸的催化电氧化

Catalytic property for the electro-oxidation of cysteine (RSH) on modified glassy carbon electrode with octkis(benzylthio)tetraazaporphyrinato cobalt(Ⅱ)［abbr.Co(Ⅱ)OBTP］ has been studied, substantial catalytic effect has been observed. Tafel slope plot gives 121 mV/decade. The reaction order are 1 for RSH; -1 for H⁺ (in acid solution) and 0 (in base solution). Possible mechanism of the reaction was proposed.     

新型β-取代阳离子卟啉光敏剂合成及其与DNA相互作用

在5,10,15,20-四苯基卟啉及其金属配合物的β位引入阳离子型修饰基团溴化吡啶鎓盐, 得到β-[2-(6-吡啶溴化盐)己氧基]萘基-5,10,15,20-四苯基卟啉及其Cu(II), Ni(II), Zn(II)配合物. 通过IR, UV, ¹H NMR, MS以及元素分析对新化合物进行了结构表征. 作为光动力治疗光敏剂与pBR322质粒DNA的相互作用研究表明, 它们对DNA具有良好的光敏切割效果和结合能力, 通过与小牛胸腺DNA相互作用初步研究了它们与DNA的作用模式.     

Characterization and Crystal Structure of a New Holmium(III) Complex with the Macrocyclic Ligand Derived from 2,6-Diformyl-4-methylphenol and Diethylenetriamine

The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.111,15]- triaconta-1(29),2,9,11,13,15(30),16,23,25,27-decaene-29,30-diol-N3,N6,N9,O29,O30)-bis(nitrato-O,O′)- holmium(III) nitrate hydrate has been prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structures were determined by X-ray diffraction methods. The crystal crystallizes in the monoclinic system, space group C2/c with a = 23.737(12), b = 14.237(7), c = 19.801(10) , β = 91.36(1)o, Mr = 831.57, V = 6690(6) 3, Z = 8, Dc = 1.651 g/cm3, F(000) = 3344, R = 0.0482 and wR = 0.0923. The holmium ion is located in one of the compartments of the macrocyclic ligand and presents a distorted tricapped trigonal prismatic coordination geometry. The macrocycle is coordinated with two oxygen and three nitrogen atoms. Two nitrates are chelated in the opposite positions of the macrocycle, and the third one is ionic.     

硅酞菁衍生物的合成、光学性质及对DNA的光切割活性研究

以硅酞菁为母核,设计并合成了衍生物Si Pc1,其结构经UV、~1H-NMR和MS等确证。以DMSO为溶剂,对Si Pc1的光物理性质进行了检测,Si Pc1的Q-带最大吸收峰为682 nm;以Zn Pc(Φ_F=0.20,Φ_△=0.67)为参照,得出Si Pc1的荧光量子产率(Φ_F)为0.25,单线态氧量子产率(Φ_△)为0.78,均大于Zn Pc。采用凝胶电泳法研究了Si Pc1对DNA的光切割活性,结果表明,Si Pc1对p BR322 DNA有良好的光切割活性。     

Ho(Ⅲ)希夫碱大环配合物的合成、晶体结构及对DNA的切割活性

合成了一个新的希夫碱大环配体硝酸Ho(Ⅲ)配合物[Ho(H2L)(NO3)2](NO3)(H2L表示大环配体),并进行了系统的物理表征.晶体结构研究表明,配合物晶体结构属六方晶系,P3121空间群,晶胞参数a=1.47213(7)nm,c=2.8998(3)nm,α=90°,γ=120°,V=5.4424(7)nm3,Z=6,R=0.0331,wR=0.0928.中心离子Ho3+位于隔室大环配体的一侧,并与希夫碱大环上的2个酚基氧原子和3个氮原子配位,2个双齿配位硝酸根分别从希夫碱大环平面的两侧与中心离子配位,使中心离子形成扭曲的九配位三冠三棱柱构型.通过凝胶电泳实验初步研究了该配合物对pBR322质粒DNA的切割作用.