四乙酰哌嗪苯氧基酞菁锌及其蛋白质复合物的制备、表征与光动力活性  

Tetra-(acetyl piperazine phenoxy) Phthalocyaninato Zinc Complexes and Their Proteins Conjugates: Synthesis, Characterisation and Photodynamic Activities

作　　者：黄剑东[1] 刘丰冉[1] 陈燕梅[1] 孙建成[2] 江舟[1] 

机构地区：[1]福州大学化学化工学院福州大学功能材料研究所,福州350002 [2]福建医科大学药理系,福州350004

出　　处：《无机化学学报》2006年第3期435-442,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.20201005);福建省自然科学基金(No.C0410005);高等学校骨干教师资助计划的资助项目。

摘　　要：合成了2个酞菁锌配合物,即α-四(4-(4-乙酰哌嗪)苯氧基))酞菁锌(C80H72N16O8Zn)(1)和"-四(4-(4-乙酰哌嗪)苯氧基)酞菁锌(C80H72N16O8Zn)(2),并通过1HNMR,MS,IR和元素分析等手段进行表征。配合物1、2在N,N-二甲基甲酰胺、四氢呋喃和正辛醇等有机溶剂中呈现出典型的酞菁的单体吸收光谱特征,Q带分别位于693￣698nm和681￣682nm,相对于β位取代者,α位取代的配合物的Q带明显红移。在含水溶剂中的吸收光谱测试显示,α位取代较β位取代更能有效地阻止配合物在含水溶剂中形成聚集体。通过吸收光谱和荧光光谱研究了2个配合物与血清白蛋白(BSA,HSA)和转铁蛋白(apoTf)的相互作用,结果表明,结合常数在(1￣20)×105mol-1·L之间,相对而言,β位取代的配合物与白蛋白的结合能力强于α位取代者。同时,制备了1-BSA、2-BSA、1-HSA、1-apoTf和1-FeTf等非共价键结合的酞菁-蛋白质复合物。对MCF-7乳腺癌细胞的光动力杀伤作用的测试初步表明,复合物的活性较高,活性顺序为:1-BSA>1-FeTf>1-HSA,1-apoTf>2-BSA>1>2。Two zinc phthalocyanines, tetra-α-[4-（4-acetyl piperazine） phenoxy] phthalocyaninato zinc （C80H72N16O8Zn） （1） and tetra-β-[4-（4-acetyl piperazine） phenoxy] phthalocyaninato zinc （C80H72N16O8Zn） （2）, have been synthesised and characterised with ^1H NMR, MS, IR and elemental analysis. The electronic absorption spectra of two complexes in common organic solvents （N,N-dimethyl formamide, tetrahydrofuran, n-octanol） were typical for non- aggregated phthalocyanines, showing a Q band at 693-698 nm for 1 and 681-682 nm for 2. This indicates that the Q band of zinc phthalocyanine with the substituted groups located in the α position is largely red shifted than that in the β position. The spectral features of complexes 1 and 2 in aqueous media suggest the α-substituted groups are more effective than β-substituted groups to hinder the aggregation of phthalocyanine molecule. The interactions between two complexes with serum albumin and transferrin （BSA, HSA and apoTf） were investigated by absorption and fluorescence spectroscopy. The binding constants were found to be （1-20） × 10^5 mol^-1·L. By comparison,β-substituted 2 had stronger combining ability with albumin than that of α-substituted 1. The non-covalent conjugates （1-BSA, 2-BSA, 1-HSA, 1-apoTf and 1-FeTf） with the molar ratio of about 1：1 have also been prepared. The photodynamic activities of two complexes and their bioconjugates against MCF-7 mammary tumor cells were examined. The result shows that the photocytotoxicities of conjugates are higher than that of complexes 1-2 and follows the order 1-BSA 〉 1-FeTf 〉 1-HSA, 1-apoTf 〉 2-BSA 〉 1 〉 2.

关 键 词：酞菁 合成 蛋白质 光动力治疗 

分 类 号：O614.241[理学—无机化学] O627.23[理学—化学]