DNA nucleosides and their radical anions: Molecular structures and electron affinities

doi:10.1021/ja030487m

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	DNA nucleosides and their radical anions: Molecular structures and electron affinities
	Richardson, NA ; Gu, JD; Wang, SY ; Xie, YM ; Schaefer, HF
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2004-04-07
卷号	126 期号:13 页码:4404-4411
ISSN号	0002-7863
DOI	10.1021/ja030487m
文献子类	Article
英文摘要	The deoxyribonucleosides have been studied to determine the properties of combinations of 2-cleoxyribose with each of the isolated DNA bases for both neutral and anionic species. We have used a carefully calibrated theoretical method [Chem. Rev. 2002, 102, 231], employing the B3LYP hybrid Hartree-Fock/DFT functional with the DZP++ basis set. Predictions are made of the geometric parameters, adiabatic electron affinities, charge distributions based on natural population analysis, and decomposition enthalpy for the neutral and anionic forms of the four 2'-deoxyribonucleosides in DNA: 2'-deoxyriboadenosine (dA), 2'-deoxyribocytidine (dC), 2'-deoxyriboguanosine (dG), and 2'-deoxyribothymidine (dT). Geometric changes in the anions show that the glycosidic bond exhibits little change with excess charge for the guanosine but significant shortening for the adenosine and for the pyrimidines. The zero-point corrected adiabatic electron affinities in eV for each of the 2'-deoxyribonucleosides are as follows: 0.06, dA; 0.09, dG; 0.33, dC; and 0.44, dT. These values are uniformly greater than those of the corresponding isolated bases (-0.28, A; -0.07, G; 0.03, C; 0.20, T) and the isolated 2-deoxyribose (-0.38) at the same level of theory. The vertical detachment energies of dT and dC are substantial, 0.72 and 0.94 eV, and these anions should be observable. A high VDE, 0.91 eV, is also found for dA but its anion is unlikely to be stable due to the small AEA of 0.06 eV. The high VIDE reflects the fact that the molecular structures of the anions and the corresponding neutral species are quite different. Valence character is displayed for the SOMOs of CIA, dC, and dT, while some component of diffuse character is visible in the SOMO of dG. Further analysis of electronic changes upon electron attachment include an examination of the NPA charges, which show that in the neutral 2'-deoxyribonucleosides the sum of NPA charges for every base is the same, -0.28 with the sum of 2-cleoxyribose charges being positive, +0.28. In the anions, the trend in charge division varies based on the nature of the excess electron in the anions. Thermodynamically, the overall enthalpy change for the reaction of water with the neutral nucleosides to give bases and ribose is approximately zero. The analogous decomposition is exothermic by 8 to 11 kcal mol(-1) for the anions, indicating possible challenges for anionic gas-phase nucleoside exploration in the presence of water.
WOS关键词	TEMPERATURE-DEPENDENT RAMAN ; NUCLEIC-ACID BASES ; DENSITY-FUNCTIONAL CALCULATIONS ; DOUBLE-HELICAL FRAGMENTS ; GROUND-STATE PROPERTIES ; LOW-ENERGY ELECTRONS ; NEGATIVE-ION STATES ; GAS-PHASE ; INFRARED-SPECTRA ; IONIZATION-POTENTIALS
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000220637100068
内容类型	期刊论文
源URL	[http://119.78.100.183/handle/2S10ELR8/274092]
专题	药物发现与设计中心中科院受体结构与功能重点实验室新药研究国家重点实验室
通讯作者	Gu, JD
作者单位	1.Pensacola Christian Coll, Dept Basic Sci Engn, Pensacola, FL 32503 USA 2.Univ Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USA 3.Chinese Acad Sci, Shanghai Inst Biol Sci, State Key Lab Drug Res, Drug Design & Discovery Ctr, Shanghai 200031, Peoples R China
推荐引用方式 GB/T 7714	Richardson, NA,Gu, JD,Wang, SY,et al. DNA nucleosides and their radical anions: Molecular structures and electron affinities[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2004,126(13):4404-4411.
APA	Richardson, NA,Gu, JD,Wang, SY,Xie, YM,&Schaefer, HF.(2004).DNA nucleosides and their radical anions: Molecular structures and electron affinities.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,126(13),4404-4411.
MLA	Richardson, NA,et al."DNA nucleosides and their radical anions: Molecular structures and electron affinities".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 126.13(2004):4404-4411.