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Laser Flash Photolysis on Electron Transfer Reactions between 1,8-Dihydroxyanthraquinone with Adenine and Cytosine
Xiang Liu,Lin Chen,Qiao-hui Zhou,Xiao-guo Zhou*,Shi-lin Liu
Author NameAffiliationE-mail
Xiang Liu Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Lin Chen Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Qiao-hui Zhou Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Xiao-guo Zhou* Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China xzhou@ustc.edu.cn 
Shi-lin Liu Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Abstract:
Electron transfer (ET) reactions between 1,8-dihydroxyanthraquinone (DHAQ) and two DNA bases, adenine (A) and cytosine (C), have been investigated in CH3CN/H2O solution with nanosecond time-resolved laser flash photolysis. After irradiation at 355 nm, the triplet DHAQ is produced via intersystem crossing and reacts with two nucleobases. ET processes for both reactions have been definitely identified, in which two bases play a significant role of electron donor. Based on the measured decay dynamics of various intermediates and the corresponding quenching rates, an initial ET process followed by a secondary proton-transfer reaction is suggested for both the overall reactions. By plotting the observed quenching rate against the concentration of two DNA bases, the bimolecular quenching rate constants are determined as 9.0×108 L/(mol·s) for the 3DHAQ*+C reaction and 3.3×108 L/(mol·s) for the 3DHAQ*+A reaction, respectively.
Key words:  Electron transfer, Proton transfer, 1,8-dihydroxyanthraquinone, Laser flash photolysis, Adenine, Cytosine
FundProject:
激光闪光光解研究二羟基蒽醌和腺嘌呤/胞嘧啶的电子转移反应
刘香,陈琳,周巧慧,周晓国*,刘世林
摘要:
采用纳秒时间分辨的激光闪光光解技术研究了乙腈/水混合溶液中二羟基蒽醌和腺嘌呤或胞嘧啶之间的电子转移反应. 在355 nm紫外光作用下,经由系间窜跃产生的三重态二羟基蒽醌与两碱基分别发生电子转移反应,其中碱基作为典型的电子给体. 基于测量到的反应瞬态中间体的动力学淬灭速率,两个反应过程被认为分步进行,先电子转移之后发生质子转移反应. 通过研究表观淬灭速率与两个碱基浓度的依赖关系,分别得到了两个双分子间电子转移反应的速率常数,分别是9.0×108 L/(mol·s) (胞嘧啶)、3.3×108 L/(mol·s) (腺嘌呤).
关键词:  电子转移,质子转移,激光闪光光解,二羟基蒽醌,腺嘌呤,胞嘧啶
DOI:10.1063/1674-0068/26/05/498-503
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