【摘要】 以（E）-莰烯醛缩氨基硫脲（1a）、（E）-莰烯醛缩-4-甲基氨基硫脲（1b）为原料,分别与氯化钴、氯化镍、氯化锌、氯化铜反应合成了7种金属配合物,通过IR、¹H NRM、¹³C NMR和HRMS分析方法表征了它们的结构。采用菌丝生长速率法测试了7种配合物对8种植物病原真菌的抑制活性;采用DPPH和ABTS法测定了7种化合物对自由基的清除能力以比较各化合物的抗氧化活性;采用CCK-8法测试了7种化合物对结肠癌细胞（HCT-116）和人体乳腺癌细胞（MCF 7）的抑制增殖能力。测试结果表明:7种金属配合物中,（E）-莰烯醛缩氨基硫脲镍配合物（2c）对所试8种植物病原菌的抑制活性最强且范围较广,对水稻纹枯病菌（A）、西瓜枯萎病菌（B）、松枯梢病菌（C）枇杷炭疽病菌（E）、油茶果生刺盘孢病菌（G）、彩绒革盖病菌（H）的抑制效果明显,且超过它的配体（1a）,其中对B、E、H 3种病菌的抑制作用还强于阳性对照百菌清。在对DPPH自由基和ABTS自由基的清除实验中,多数配位化合物的效果强于阳性对照Trolox与L-抗坏血酸,两项测试中以（E）-莰烯醛缩-4-甲基氨基硫脲Cu²⁺配合物（2g）效果最好,2c、2d、2f、2g的效果均超过它们的配体1a和1b。抗肿瘤活性测试中,在200μM浓度下,（E）-莰烯醛缩氨基硫脲钴、铜配合物（2a、2f）和（E）-莰烯醛缩-4-甲基氨基硫脲锌、铜配合物（2e、2g）均有较好的抑制结肠癌细胞（HCT-116）和人体乳腺癌细胞（MCF 7）增殖能力,其细胞存活率范围在5.42～18.71%,远远强于阳极对照5-氟尿嘧啶（59.29%）,它们对人体乳腺癌细胞（MCF 7）的抑制作用还强于索拉非尼（24.16%）,2a对结肠癌细胞（HCT-116）增殖能力抑制的存活率（11.46%）低于索拉非尼（14.84%）,效果更好。更多还原

【Abstract】 Seven metal complexes were synthesized from ω-formylcamphene thiosemicarbazone（1a） and ω-formylcamphene-4-methylthiosemicarbazide（1b） with cobaltous chloride,nickel chloride,zinc chloride and copper chloride,respectively.Their structures were characterized by IR,¹H NRM,¹³C NMR and HRMS.The inhibitory activities of 7 compounds against 8 plant pathogenic fungi were tested by mycelium growth rate method.DPPH and ABTS methods were used to determine the free radical scavenging ability of7 compounds to compare the antioxidant activities of each compound.The inhibitory effects of seven compounds on the proliferation of colon cancer cells and human breast cancer cells were assessed using the CCK-8 method.The results indicated that,among these metal complexes,the ω-formylcamphene thiosemicarbazone nickel complex（2c） exhibited potent inhibitory activity against eight plant pathogens tested and a broad spectrum.The inhibitory effect on Rhizoctonia solani（A）,Fusarium oxyporum f.sp.Niveum（B）,Sphaeropsis sapinea（C）,Colletotrichum acutatum（E）,Colletotrichum fructico（G）,and Coriolus versicolor（H） exhibited greater prominence compared to its ligand（1a）.Furthermore,the inhibitory effect on B,E,and H surpassed that of chlorothalonil.In both the DPPH radical and ABTS radical scavenging tests,the coordination compounds exhibited superior efficacy compared to the positive control Trolox and L-ascorbic acid.Notably,among all tested compounds,the ω-formylcamphene-4-methylthiosemicarbazide Cu²⁺complex（2g） demonstrated exceptional performance in both assays.The effects of 2c,2d,2f and 2g all outperformed those of their ligands 1a and 1b.In the anti-tumor activity test,the ω-formylcamphene thiosemicarbazone cobalt,copper complex（2a,2f）and the ω-formylcamphene-4-methylthiosemicarbazide zinc,copper complex（2e,2g） had better inhibitory effects on the proliferation of colon cancer cells and human breast cancer cells at the concentration of 200 μM.The cell survival rate ranged from 5.42 to18.71%,which was much stronger than that of anodal control 5-fluorouracil（59.29%）.The inhibitory effect of 2a on human breast cancer cells was also stronger than that of sorafenib（24.16%）,and the inhibitory rate of 2a on colon cancer cell proliferation was lower than that of sorafenib（11.46%）,and the effect was better.更多还原