Understanding electron attachment to the DNA double helix: The thymidine monophosphate-adenine pair in the gas phase and aqueous solution

doi:10.1021/jp064852i

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	Understanding electron attachment to the DNA double helix: The thymidine monophosphate-adenine pair in the gas phase and aqueous solution
	Gu, Jiande; Xie, Yaoming ; Schaefer, Henry F., III
刊名	JOURNAL OF PHYSICAL CHEMISTRY B
	2006-10-05
卷号	110 期号:39 页码:19696-19703
ISSN号	1520-6106
DOI	10.1021/jp064852i
文献子类	Article
英文摘要	Electron attachment to the 2'-deoxythymidine-5'-monophosphate-adenine pairs (5'-dTMPH-A and 5'-dTMP-A) has been investigated at a carefully calibrated level of theory (B3LYP/DZP++) to investigate the electron-accepting properties of thymine ( T) in the DNA double helix under physiological conditions. All molecular structures have been fully optimized in vacuo and in solution. The adiabatic electron affinity of 5'-dTMPH-A in the gas phase has been predicted to be 0.67 eV. Solvent effects greatly increase the electron capture ability of 5'-dTMPH-A. In fact, the adiabatic electron affinity increases to 2.04 eV with solvation. The influence of the solvent environment on the electron-attracting properties of 5'-dTMPH-A arises not only from the stabilization of the corresponding radical anion through charge-dipole interactions, but also by changing the distribution of the unpaired electron in the molecular system. The unpaired electron is covalently bound even during vertical attachment, due to the solvent effects. Solvent effects also weaken the pairing interaction in the thymidine monophosphate-adenine complexes. The phosphate deprotonation is found to have a relatively minor influence on the capture of electrons by the 5'-dTMPH-A species in aqueous solution. The electron distributions, natural population analysis, and geometrical features of the models examined illustrate that the influence of the phosphate deprotonation is limited to the phosphate moiety in aqueous solution. Therefore, it is reasonable to expect that electron attachment to nucleotides will be independent of monovalent counterions in the vicinity of the phosphate group in aqueous solution.
WOS关键词	DENSITY-FUNCTIONAL THEORY ; THYMINE BASE-PAIR ; MOLECULAR-ORBITAL CALCULATIONS ; DISTANCE CHARGE-TRANSPORT ; GLYCOSIDIC BOND-CLEAVAGE ; THEORETICAL AB-INITIO ; WATER-CLUSTER ANIONS ; LOW-ENERGY ELECTRONS ; NUCLEIC-ACID BASES ; STRAND BREAKS
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000240825900090
内容类型	期刊论文
源URL	[http://119.78.100.183/handle/2S10ELR8/273471]
专题	药物发现与设计中心
通讯作者	Gu, Jiande
作者单位	1.CAS, Shanghai Inst Biol Sci, Shanghai Inst Mat Med, Drug Design & Discovery Ctr, Shanghai 201203, Peoples R China 2.Univ Georgia, Ctr Computat Chem, Athens, GA 30602 USA
推荐引用方式 GB/T 7714	Gu, Jiande,Xie, Yaoming,Schaefer, Henry F., III. Understanding electron attachment to the DNA double helix: The thymidine monophosphate-adenine pair in the gas phase and aqueous solution[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2006,110(39):19696-19703.
APA	Gu, Jiande,Xie, Yaoming,&Schaefer, Henry F., III.(2006).Understanding electron attachment to the DNA double helix: The thymidine monophosphate-adenine pair in the gas phase and aqueous solution.JOURNAL OF PHYSICAL CHEMISTRY B,110(39),19696-19703.
MLA	Gu, Jiande,et al."Understanding electron attachment to the DNA double helix: The thymidine monophosphate-adenine pair in the gas phase and aqueous solution".JOURNAL OF PHYSICAL CHEMISTRY B 110.39(2006):19696-19703.