反式阿魏酸钌配合物的合成、表征、荧光光谱及其与DNA/蛋白作用
Synthesis, Characterization, Fluorescence and Interactions with DNA/BSA Properties of Ruthenium Ferulate Complexes
作者单位E-mail
陶钦 南京师范大学化学与材料科学学院, 南京 210023  
吴健 南京师范大学化学与材料科学学院, 南京 210023  
葛超 南京师范大学化学与材料科学学院, 南京 210023  
王萌萌 南京师范大学化学与材料科学学院, 南京 210023  
吕梦迪 南京师范大学化学与材料科学学院, 南京 210023  
薛旭玲 南京师范大学化学与材料科学学院, 南京 210023 xuexuling87@163.com 
刘红科 南京师范大学化学与材料科学学院, 南京 210023 liuhongke@njnu.edu.cn 
摘要: 对天然产物反式阿魏酸进行化学修饰,设计、合成了2种单核钌配合物[Ru(cym)(L)Cl]Cl(Ru-1)与[Ru(bpy)2(L)]Cl2Ru-2)(cym=对伞花烃,bpy=2,2'-联吡啶,L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4'-methyl-(2,2'-bipyridin)-4-yl)methyl)acrylamide),通过核磁共振氢谱和碳谱、电喷雾质谱对配合物进行了结构表征。利用荧光、紫外-可见光谱等方法研究了配合物的溶解性和光学性质。配合物均具有良好的亲水性。Ru-2有良好的荧光性能,其发射波长达到近红外的631 nm,且可以在pH值为8~10之间实现响应。Ru-2还具有较高的单线态氧量子产率(φ=0.70),有望成为一类高效的光敏剂。2种配合物都与CT-DNA发生嵌入作用(Kb分别为1.210×104和1.233×103 L·mol-1);均与BSA有一个结合位点,使其荧光发生静态淬灭(Ka值分别为1.94×104,2.45×104)。
关键词: 钌配合物  pH响应  与BSA/DNA的作用  单线态氧
基金项目: 国家自然科学基金重点国际合作项目(No.21420102002)、国家自然科学基金(No.21771109,21778033,21807060)、江苏省333工程人才专项基金、江苏省六大人才高峰和江苏省自然科学基金(No.BE2013716,BK20171472)和中国博士后基金(No.2019M651874)资助
Abstract: We synthesized two novel mononuclear ruthenium complexes,[Ru(cym)(L)Cl]Cl (Ru-1) and[Ru(bpy)2(L)] Cl2 (Ru-2) (cym=cymene, bpy=2,2'-bipyridine, L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4'-methyl-(2,2'-bipyridin)4-yl)methyl)acrylamide), with the modified natural product trans-ferulic acid. Their structures were determined by 1H NMR, 13C NMR and ESI-MS techniques. Optical properties and lipophilicity of complexes were characterized by using the fluorescence and UV-visible spectra. The results suggested that both complexes exhibited high water solubility. Ru-2 showed good fluorescence performance with the maximum emission wavelength at 631 nm in the near infrared area and had pH responsive ability (pH=8~10). Additionally, Ru-2 exhibited high singlet oxygen quantum yield (φ=0.70), which might be expected to become an efficient photosensitizer. Both of the complexes binded to CT -DNA through intercalation mode (Kb:1.210×104 L·mol-1 for Ru-1; 1.233×103 L·mol-1 for Ru-2) and interacted with BSA with one site, causing static quenching of their fluorescence (Ka:1.94×104 for Ru-1; 2.45×104 for Ru-2).
Keywords: ruthenium complex  pH responsive  interaction with BSA/DNA  singlet oxygen species
投稿时间:2020-02-18 修订日期:2020-06-09
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陶钦,吴健,葛超,王萌萌,吕梦迪,薛旭玲,刘红科.反式阿魏酸钌配合物的合成、表征、荧光光谱及其与DNA/蛋白作用[J].无机化学学报,2020,36(10):1853-1864.
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