Dynamics of excess-electron transfer via consecutive thymines versus alternating adenine:thymine sequences in DNA
Dynamics of excess-electron transfer via consecutive thymines versus alternating adenine:thymine sequences in DNA
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DNA 中连续胸腺嘧啶与交替腺嘌呤：胸腺嘧啶序列的过量电子转移动力学
DOI：
10.1002/chem.201503115
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发表时间：
2015
影响因子：
4.3
通讯作者：
and Tetsuro Majima
中科院分区：
文献类型：
--
作者：
Shih-Hsun Lin;Mamoru Fujitsuka;and Tetsuro Majima
本文介绍了DNA中序列依赖的过量电子转移（EET）动力学的研究结果，该动力学在DNA损伤/修复中起着重要作用。已有许多关于连续腺嘌呤：胸腺嘧啶（A：T）序列（Tn）中EET的已发表研究，但关于交替A：T序列（ATn）中EET的研究仍然有限。在这里，两个系列的功能化的DNA寡聚物，TnandATn，与强供电子光敏剂，乙烯二氧噻吩（3E）的三聚体，和电子受体，二苯基乙炔（DPA）的合成。激光闪光光解实验表明，由于AT 3中没有Ts的π-堆积，AT 3的EET速率常数比T3的EET速率常数低两倍。因此，表明过量电子跳跃受到核苷酸的LUMO之间的相互作用的影响。
This paper presents the results of an investigation into the sequence‐dependent excess‐electron transfer (EET) dynamics in DNA, which plays an important role in DNA damage/repair. There are many published studies on EET in consecutive adenine:thymine (A:T) sequences (Tn), but those in alternating A:T sequences (ATn) remain limited. Here, two series of functionalized DNA oligomers,TnandATn, were synthesized with a strongly electron‐donating photosensitizer, a trimer of ethylenedioxythiophene (3 E), and an electron acceptor, diphenylacetylene (DPA). Laser flash photolysis experiments showed that the EET rate constant ofAT3is two times lower than that ofT3due to the lack of π‐stacking of Ts inAT3. Thus, it was indicated that excess‐electron hopping is affected by the interaction between LUMOs of nucleotides.