[2+2] Photocycloaddition Reaction Dynamics of Triplet Pyrimidines
文献类型：期刊论文
| 作者 | Yang, Chunfan; Yu, Youqing; Liu, Kunhui; Song, Di; Wu, Lidan; Su, Hongmei |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2011-06-02 |
| 卷号 | 115期号:21页码:5335-5345 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp201418r |
| 英文摘要 | Taking the 266 nm excited pyrimidine (uracil or thymine) with cyclopentene as model reaction systems, we have examined the photoproduct formation dynamics from the [2 + 2] photocycloaddition reactions of triplet pyrimidines in solution and provided mechanistic insights into this important DNA photodamage reaction. By combining two compliment methods of nanosecond time-resolved transient IR and UV-vis laser flash-photolysis spectroscopy, the photoproduct formation dynamics as well as the triplet quenching kinetics are measured. Characteristic IR absorption bands due to photoproduct formation have been observed and product quantum yields are determined to be similar to 0.91% for uracil and similar to 0.41% for thymine. Compared to the measured large quenching rate constants of triplet uracil (1.5 x 10(9) M(-1)s(-1)) or thymine (0.6 x 10(9) M(-1)s(-1)) by cyclopentene, the inefficiency in formation of photoproducts indicates competitive physical quenching processes may exist on the route leading to photoproducts, resulting in very small product yields eventually. Such an energy wasting process is found to be resulted from T(1)/S(0) surface crossings by the hybrid density functional calculations, which compliments the experiments and reveals the reaction mechanism. |
| 语种 | 英语 |
| WOS记录号 | WOS:000290914500012 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/71325]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Su, Hongmei |
| 作者单位 | Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing Natl Lab Mol Sci BNLMS, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yang, Chunfan,Yu, Youqing,Liu, Kunhui,et al. [2+2] Photocycloaddition Reaction Dynamics of Triplet Pyrimidines[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2011,115(21):5335-5345. |
| APA | Yang, Chunfan,Yu, Youqing,Liu, Kunhui,Song, Di,Wu, Lidan,&Su, Hongmei.(2011).[2+2] Photocycloaddition Reaction Dynamics of Triplet Pyrimidines.JOURNAL OF PHYSICAL CHEMISTRY A,115(21),5335-5345. |
| MLA | Yang, Chunfan,et al."[2+2] Photocycloaddition Reaction Dynamics of Triplet Pyrimidines".JOURNAL OF PHYSICAL CHEMISTRY A 115.21(2011):5335-5345. |
入库方式： OAI收割
来源：化学研究所
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