1．为了深入研究第一个确定结构的化学核酸酶[Cu(phen)2]＋结构与性质的关系，本研究合成了配合物[Cu(phen)2Cl]Cl•4H2O•CH3CH2OH，通过元素分析、IR光谱、UV–Visible光谱、热分析、循环伏安测试对其进行了表征。测定了配合物的晶体结构，结果表明5配位的配离子[Cu(phen)2Cl]＋接近于三角双锥，其通过C－H┅Cl弱氢键和phen平面间的π堆积作用形成二聚体，两个二聚体通过同时与未配位Cl原子形成C－H┅Cl弱氢键构成一维链状结构，一维链通过链内、链间的phen平面的π堆积作用形成二维层状结构。在B3LYP/6–31G*(LanL2DZ)水平上，对[Cu(phen)2Cl]＋、[Cu(phen)2Cl]22＋和[Cu(phen)2]＋进行了单点计算，结果表明平行phen平面的重叠区域靠相反电荷产生吸引力，致使[Cu(phen)2Cl]＋聚集为层状结构；[Cu(phen)2Cl]+的氧化还原稳定性比[Cu(phen)2]+好，前者的单电子氧化反应活性位点为配位Cl原子，后者为中心Cu+离子，而二者的单电子还原活性位点都是离子中的一个phen平面。经对接计算获得配合物[Cu(phen)2]+与DNA的Ki值为1.85×10–7，表明二者产生较强的结合作用。2．为了扩展本课题组抗肿瘤配合物的研究，本研究合成了4个未见报道的Cu－水杨醛氨基酸Schiff碱－phen(或bipy) 三元配合物，通过元素分析、IR光谱、UV-Visible光谱、热分析、电导率和循环伏安测试对其进行了表征。利用紫外－可见光谱、荧光光谱、EB竞争、循环伏安和粘度等实验手段研究了4个配合物与DNA分子的键合。紫外－可见光谱获得的键合常数Kb都在104数量级，表明它们与DNA的键合能力都较强。键合常数出现顺序2＞4＞3＞1，2的键合能力是1的1.6倍。由EB竞争实验求出的表观平衡数Kapp（数量级为104级 ）和淬灭常数Kq（数量级为103级）都存在变化趋势4＞3＞1＞2。循环伏安测试表明4个配合物均涉及沟面或静电结合方式，但是结合方式并不典型；1、3、4的Cu(Ⅱ)形态与DNA结合的趋势比还原态的大，而2的则差不多。由粘度测量推测配合物与DNA分子以部分插入模式与DNA作用。利用琼脂糖凝胶电泳实验研究了配合物的化学核酸酶活性，4个配合物在还原剂H2A存在下都表现出不同程度的DNA剪切作用；当羟基自由基清除剂DMSO存在时（条带4），4个配合物的剪切活性出现不同的变化。其中，2的剪切能力消失，表明它是几乎完全以羟基自由基机理发生剪切作用；3的剪切活性大大减弱，表明它的剪切作用主要通过羟基自由基机理实现，也包含其他的氧化还原机理；而1和4的剪切活性只是略微减弱，说明这2个配合物的剪切DNA过程是以其他氧化还原机理为主，羟基自由基反应只是稍有涉及。1、3、4的表观速率常数k（10–5 s–1数量级）的顺序为1＞3＞4，而2的反应速率高达1的10倍。在B3LYP/6–31G*(LanL2DZ)水平上对4个配合物进行了理论模拟，揭示中心铜原子为四方锥构型，配合物的稳定性存在顺序1＞3＞4＞2，Schiff碱配体形成的配位键比中性配体形成的配位键更强，氧化还原活性非常接近，单电子氧化和还原过程时分别主要涉及Schiff碱配体的苯环和phen（或bipy）共轭体系。运用半柔性对接原理，将模拟了4个配合物与DNA的作用模型。模拟结果显示4个配合物都进入DNA的小沟，结合强度存在顺序2＞4＞3＞1。结果证实了Schiff碱配体和中性配体的差异对配合物与DNA的作用产生影响。

1．In order to get deep understanding of the relationship between structure and property of the first structurally determined chemical nuclease [Cu(phen)2]＋, [Cu(phen)2Cl]Cl•4H2O•CH3CH2OH was synthesized and characterized by UV spectra, IR spectra, thermal analysis, CV and elemental analysis, and its crystal structure was structurally characterized by X-ray crystallography in this dissertation. The copper atom was five-coordinated by four nitrogen atoms of two phen ligands and one chlorine atom resulting in a distorted trigonal bipyramid. A dimer of [Cu(phen)2Cl]＋ions were constituted by the weak C—H┅Cl hydrogen bondings and π–stacking between phen planes that from adjacent molecules. The dimers were connected into one-dimensional chain by the other C—H┅Cl weak hydrogen bonds with the noncoordinated chlorine atom. The π–stacking between phen rings inside or outside the chains assembled the chains into two-dimensional layer. Single point calculation of [Cu(phen)2Cl]＋, [Cu(phen)2Cl]22＋and [Cu(phen)2]＋ were performed at B3LYP/6-31G* (LanL2DZ) level. An electrostatic contraction between each pair of the parallel phen planes was revealed by their opposite charges, which should be the intrinsic force of the layer structure. The redox stability of [Cu(phen)2Cl]＋ was more better than [Cu(phen)2]＋. For single-electron oxidation, the active site of the former was the coordinated Cl atom, and that of the latter is the center Cu+ ion. For single-electron reduction, the active sites of both the species were one phen plane. The value of Ki for [Cu(phen)2]＋ (1.85×10–7) was getted from the docking calculation, which showed a strong combination between [Cu(phen)2]+ and DNA. 2．For expanding the research of the antitumor copper(II) complexes in our group, four Cu-salicylidene-amino acid Schiff base-phen (or bipy) ternary complexes were synthesized and characterized by elemental analysis, thermal analysis, UV spectra, IR spectra, CV and conductivity measurement.The binding of the four complexes to DNA was studied by means of UV spectra, fluorescence spectra, competitive binding with EB, viscosity and cyclic voltammetry measurement. The binding constants (Kb, ~104) obtained from UV spectra showed a strong DNA affinity of the four complexes. The affinity decreased in the order of 2 > 4 > 3 > 1, and 2 is 1.6 times as strong as 1. The apparent binding constants (Kapp, ~104) with DNA and quenching constants (Kq, ~103) were obtained from EB-DNA competition experiment, and both were in the trend of 4 > 3 > 1 > 2. CV experiments indicated that the four complexes interact with DNA in a non-classical mode, which involved both electrostatic and groove binding. The DNA binding of Cu(II) form of 1, 3 and 4 was stronger than that of the reduced Cu(I) form, but both forms of 2 exhibit the same tendency. Viscosity measurements suggested that the DNA binding involved a partial intercalation (i.e. non-classical) mode. The nuclease activity of the four complexes was explored by using gel electrophoresis techniques, and the result showed different nuclease activities in the presence of H2A (ascorbic acid) at pH 7.4 and 37 °C. Complex 2 cleaved pBR322 DNA almost entirely via hydroxyl radical mechanism, 3 acted patialy through the hydroxyl radical mechanism, but 1 and 4 mainly involved other redox-scavenging mechanism. The apparent rate constants (k, ~10–5 s–1) of 1, 3 and 4 were in the order of 1 > 3 > 4, and the value of 2 was 10 times as high as 1.The geometry optimizations were carried out at B3LYP/6-31G* (LanL2DZ) level for the four complexes. The results reavaled that the center copper atoms showed distorted square-pyramidal configuration, and the stability of four complexes were in the order of 1 > 3 > 4 > 2. The coordination bonds formed by Schiff base ligands were stronger than that of the neutral ligands. The redox activity was very close for four complexes, and the single-electron oxidation process and reduction process were primarily concerned with the benzene ring of Schiff base and phen (or bipy) conjugating plane, respectively. The binding between the four complexes and DNA was simulated with semi-flexible docking principle, and the minor groove binding mode as well as Ki (in the order, 1 > 3 > 4 > 2) were revealed.