| Theoretical Studies on the Binding of Cd~（2＋） to Uracil and Its Thio-derivatives |
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| 作者姓名： | WANG Min SA Rong-Jian WU Ke-Chen LI Qiao-Hong WEI Yong-Qin |
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| 作者单位： | State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences |
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| 基金项目： | supported by the NNSFC (20973174 and 91122015);the Young Scientist Fund of NSFC (81001403);the Youth Innovation Fund,Institute Key Program (SZD08003) of FJIRSM |
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| 摘 要： | The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase.
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| 关 键 词： | 尿嘧啶 衍生物 硫代 镉 密度泛函理论 硫脲嘧啶 相互作用 贸易壁垒 |
Theoretical Studies on the Binding of Cd2+ to Uracil and Its Thio-derivatives |
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| WANG Min,SA Rong-Jian,WU Ke-Chen,LI Qiao-Hong,WEI Yong-Qin.Theoretical Studies on the Binding of Cd2+ to Uracil and Its Thio-derivatives[J].Chinese Journal of Structural Chemistry,2012,31(4):521-528. |
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| Authors: | WANG Min SA Rong-Jian WU Ke-Chen② LI Qiao-Hong WEI Yong-Qin |
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| Institution: | State Key Laboratory of Structural Chemistry, Fujian Institute of Research on theStructure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China |
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| Abstract: | The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase. |
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| Keywords: | thiouracil tautomerization catalytic effects aromatization |
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