丁二酮肟双核铜配合物与DNA相互作用的电化学研究

用电化学方法研究了丁二酮肟双核铜配合物[Cu2(Hdmg)4]与DNA的相互作用. 考察了pH、温度、离子强度和配合物浓度等因素对配合物与DNA相互作用的影响, 初步探讨了配合物与DNA相互作用的机理. 实验结果表明, 配合物与DNA的碱基结合形成非电活性物质, 使溶液中游离配合物的浓度降低, 配合物的峰电流减小. 单链DNA(ssDNA)充分暴露的碱基使其与配合物的结合能力大于双链DNA(dsDNA). Cu2(Hdmg)4与ssDNA和dsDNA的结合比分别为2:1和1:1, 结合常数分别为3.56×109和2.75×105.     

草酸根桥联的Cu_2~ⅡFe~Ⅲ、Ni_2~ⅡFe~Ⅲ、Co_2~ⅡFe~Ⅲ异三核配合物的合成、表征及抗菌活性

合成了 7种草酸根桥联的 Cu 2 Fe 、Ni 2 Fe 、Co 2 Fe 异三核配合物 [M2 Fe(C2 O4) 3Lx](Cl O4) ,(M=Cu,L=bpy,Me2 phen,NO2 phen,x=2 ;M=Ni,Co,L=bpy,Me2 phen,x=4 ) .经元素分析、摩尔电导和磁性的测定以及红外光谱和电子光谱等方法对这些配合物进行了表征 ,确定了配合物的组成和结构 .初步生物活性试验表明形成异三核配合物后其杀菌活性明显提高     

Synthesis, characterization and magnetism of binuclear cobalt (II) complexes bridged by tetracarboxylato groups

Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti     

鱼藤中抗肿瘤活性化合物的追踪分离及与DNA的相互作用

采用活性追踪分离的方法, 从鱼藤中分离鉴定出了2个抗肿瘤活性化合物, 即羟基鱼藤素(1)和鱼藤酮(2). 用丽丝胺罗丹明B(SRB)法评价其抗肿瘤活性, 用紫外光谱和荧光光谱等方法探讨了化合物与DNA的相互作用. 结果发现, 羟基鱼藤素(1)与鱼藤酮(2)为鱼藤的抗肿瘤活性成分, 对人大肠癌细胞HCT8、人肝癌细胞BEL7402、人胃癌细胞BGC823、人肺癌细胞A549和人卵巢癌细胞A2780的半数抑制浓度(IC₅₀) 在0.1~90.0 μmol/L之间. 这两种化合物的紫外吸收强度随着HS-DNA的加入均呈现减色效应, 并使EB-HS-DNA复合体系荧光强度减弱, 表明化合物的抗肿瘤活性与DNA以插入方式作用有关.     

Synthesis, characterization and magnetic properties of μ-iodanilato dinuclear oxovanadium (Ⅳ) complexes

Five oxovanadium(Ⅳ) dinuclear complexes described by the overall formula [(VO)2(IA)L2]-SO4, where IA represents the dianion of iodanilic acid and L denotes 2,2'-bipyridine (bpy) ; 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 1,10-phenanthroline (phen); 4,7-diphenyl-1, 10-phenanthroline (Ph2-phen) and 5-nitro-l, 10-phenanthroline (NO2-phen) , have been synthesized and characterized by elemental analyses, molar conductivity and room-temperature magnetic moment measurements, IR and electronic spectral studies. It is proposed that these complexes have IA-bridged structures and consist of two oxovanadium(Ⅳ) ions each in a square- pyramidal environment. The complexes [ ( VO)2 (IA) (bpy )2 ] SO4 (1) and [ ( VO )2 ( IA) ( phen)2 ] -SO4 (2) were further characterized by variable temperature (4.2-300 K) magnetic susceptibility measurements and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method, giving the exchange integral J = -2.15 cm-1 for 1 and J = - 9.88 cm-1 for 2     

Synthesis and magnetism of μ-isophthalato dinuclear lanthanide(Ⅲ) complexes

Seven new μ-isophthalato dinuclear lanthanide(Ⅲ) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln = La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1, 10-phenanthroline (Me2-phen) , IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [Gd2( IPHTA) (Mez-phen)4 (ClO4)2] (ClO4)2 complex were measured in the temperature range of 4-300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2, giving the exchange parameter J =- 0.19 cm-1 . This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(Ⅲ)-Gd(Ⅲ) ions within the complex.     

草酸根桥联的CuⅡ2FeⅢ、NiⅡ2FeⅢ、CoⅡ2FeⅢ异三核配合物的合成、表征及抗菌活性

合成了7种草酸根桥联的CuⅡ2FeⅢ、NiⅡ2FeⅢ、CoⅡ2FeⅢ异三核配合物[M2Fe(C2O4)3Lx](ClO4),(M=Cu,L=bpy,Me2phen,NO2phen,x=2;M=Ni,Co,L=bpy,Me2phen,x=4).经元素分析、摩尔电导和磁性的测定以及红外光谱和电子光谱等方法对这些配合物进行了表征,确定了配合物的组成和结构.初步生物活性试验表明形成异三核配合物后其杀菌活性明显提高.     

配合物稳定性和配体酸碱强度之间的直线自由能关系──铜(Ⅱ)、锌(Ⅱ)-芬布芬-α-氨基酸三元配合物体系

在25±0.1℃,I=0.1mol·dm^-3KNO₃条件下,80%(v/v)DMSO-H₂O混合溶剂中,应用pH法测定了甘氨酸,L一缬氨酸,L-异亮氨酸,L-脯氨酸,L-丝氨酸,DL-苯丙氨酸等六种α-氨基酸(缩写为α-AA,记为B配体)的酸离解常数,铜(Ⅱ)-α-氨基酸。锌(Ⅱ)-α-氨基酸二元配合物的稳定常数及铜(Ⅱ)-芬布芬-α-氨基酸(芬布芬缩写为Fen,记为A配体)和锌(Ⅱ)-芬布芬-α-氨基酸三元配合物的稳定常数。实验发现,在下面三对参数之间,即logβ₁₀₂与pK₂^B,lOgβ₁₁₁;与pK₂^B及10gβ₁₁₁与logβ₁₀₂,均存在良好的直线自由能关系。用△logK_M和△logβ₁₁₁两个参量描述了三元配合物相对于母体二元配合物的稳定性。讨论了溶剂的性质,配合物分子内配体之间的疏水作用,芳环之间的堆积作用对配合物稳定性的影响。     

Cu（Ⅱ）－Ln（Ⅲ）双核配合物的合成、磁性和抗菌活性

合成和表征了６种以草酰胺为桥联的异双核配合物Ｃｕ（ｏｘｅｎ）Ｌｎ（ｐｈｅｎ）２（ＣｌＯ４）３（ｏｘｅｎ代表Ｎ，Ｎ′－双（２－氨乙基）草酰胺根阴离子；ｐｈｅｎ为１，１０－邻菲咯琳；Ｌｎ表示Ｙ、Ｌａ、Ｃｅ、Ｎｄ、Ｇｄ和Ｙｂ）．测定了Ｃｕ（ｏｘｅｎ）Ｇｄ（ｐｈｅｎ）２（ＣｌＯ４）３·Ｈ２Ｏ的变温磁化率（４～３００Ｋ）；井用最小二乘法和从自旋Ｈａｍｉｌｔｏｎｉａｎ算符导出的磁方程拟合，求得交换积分Ｊ＝２．３ｃｍ－１；表明配合物中Ｃｕ（Ⅱ）和Ｇｄ（Ⅲ）离子间存在弱的铁磁性超交换作用。测试了配合物的抗菌活性。     

草酰胺桥联双核铜配合物金属胶束催化BNPP水解的动力学和机理研究

合成了草酰胺桥联双核铜配合物(RCu2(H2O)2(ClO4)2)(A)和(R′Cu2(H2O)2(ClO4)2)(B)。研究了A、B与表面活性剂LSS和CTAB形成的金属胶束催化二(对硝基苯酚)磷酸二酯(BNPP)水解机理,建立了动力学模型。结果表明在25℃、pH=7的条件下,该类金属胶束对BNPP水解有催化作用,BNPP催化水解速率比其自水解速率提高1×106倍,这是由于双核铜配合物中两个铜离子的协同作用、表面活性剂胶束的浓聚效应和pH效应所致。因此含双水的草酰胺桥联双核铜配合物金属胶束是一较好的磷酸二酯水解酶的模拟模型。