甲醇和氨对腺嘌呤水解脱氨机理的影响

doi:10.3866/PKU.WHXB20101106

物理化学学报 >> 2010, Vol. 26 >> Issue (11): 3067-3072.doi: 10.3866/PKU.WHXB20101106

甲醇和氨对腺嘌呤水解脱氨机理的影响

刘海英¹, 孟凡翠², 李萍¹, 丁世良³

1. 济南大学理学院, 济南250022;
2. 天津药物研究院, 天津300193;
3. 山东大学物理学院,济南250100

收稿日期:2010-04-27 修回日期:2010-08-10 发布日期:2010-10-29
通讯作者: 刘海英 E-mail:chinayidu@yahoo.com.cn
基金资助:
山东省博士基金(2008BS02014)及济南大学校基金(XKY0809)资助项目

Effects of CH₃OH and NH₃ on the Hydrolytic Deamination Mechanismof Adenine

LIU Hai-Ying¹, MENG Fan-Cui², LI Ping¹, DING Shi-Liang³

1. School of Science, University of Jinan, Jinan 250022, P. R. China;
2Tianjin Institute of Pharmaceutical Research, Tianjin 300193, P. R. China;
3School of Physics, Shandong University, Jinan 250100, P. R. China

Received:2010-04-27 Revised:2010-08-10 Published:2010-10-29
Contact: LIU Hai-Ying E-mail:chinayidu@yahoo.com.cn
Supported by:
The project was supported by the Ph.D. Foundation of Shandong Province, China (2008BS02014) and Scientific Research Foundation of University of Jinan, China (XKY0809).

摘要/Abstract

摘要：

用密度泛函理论在B3LYP/6-311G(d,p)水平上研究了甲醇和氨辅助的腺嘌呤水解脱氨机理, 结果表明该反应首先是在水的亲核进攻下形成一个四面体结构中间体, 然后该中间体通过构象变化得到两个不同构象, 从而找到两条不同反应路径. 在路径a 中, 辅助分子参与了过渡态的形成, 起到转移氢原子的作用;而在路径b 中,辅助分子仅作为介质, 没有参与过渡态的形成. 在氨辅助的情况下, 腺嘌呤在亲核反应前发生了胺-亚胺异构化,而在甲醇辅助机理中则未发生该异构化. 能量结果表明甲醇辅助腺嘌呤脱氨反应具有与水辅助类似的势垒, 而氨辅助反应的势垒则比水辅助的高.

关键词: 腺嘌呤脱氨, B3LYP, G3MP2, 氨辅助, 甲醇辅助

Abstract:

The effects of CH₃OH and NH₃ on the hydrolytic deamination mechanism of adenine were studied by density functional theory at the B3LYP/6-311G(d,p) level. The results reveal that a tetrahedral intermediate is formed after a nucleophilic attack by a water molecule. Two intermediates are formed through conformational changes and different pathways are responsible. In pathway a, an assistant molecule takes part in the formation of the transition state and acts as a bridge to transfer a hydrogen atom, while in pathway b the assistant molecule is not involved in the creation of the transition state and acts only as a medium. The adenine takes place an amine-imine tautomerization before the nucleophilic attack under NH₃, which is not the case for the methanol-assisted mechanism. Energy results indicate that the energy barrier of the methanol-assisted adenine deamination is similar to that of the water-assisted reaction while the ammonia-assisted reaction has amuch higher energy barrier compared with the water-assisted reaction.

Key words: Adenine deamination, B3LYP, G3MP2, Ammonia-assistance, Methanol-assistance

刘海英, 孟凡翠, 李萍, 丁世良. 甲醇和氨对腺嘌呤水解脱氨机理的影响[J]. 物理化学学报, 2010, 26(11), 3067-3072. doi: 10.3866/PKU.WHXB20101106

LIU Hai-Ying, MENG Fan-Cui, LI Ping, DING Shi-Liang. Effects of CH₃OH and NH₃ on the Hydrolytic Deamination Mechanismof Adenine[J]. Acta Phys. -Chim. Sin. 2010, 26(11), 3067-3072. doi: 10.3866/PKU.WHXB20101106

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB20101106

https://www.whxb.pku.edu.cn/CN/Y2010/V26/I11/3067

参考文献

1. Glaser, R.; Rayat, S.; Lewis, M.; Son, M. S.; Meyer, S. J. Am. Chem. Soc., 1999, 121: 6108
2. Almatarneh, M. H.; Flinn, C. G.; Poirier, R. A.; Sokalski,W. A. J. Phys. Chem. A, 2006, 110: 8227
3. Almatarneh, M. H.; Flinn, C. G.; Poirier, R. A. J. Chem. Inf. Model., 2008, 48: 831
4. Labet, V.; Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A, 2008, 112: 11487
5. Labet, V.; Morell, C.; Cadet, J.; Eriksson, L. A.; Grand, A. J. Phys. Chem. A, 2009, 113: 2524
6. Labet, V.; Grand, A.; Cadet, J.; Eriksson, L. A. ChemPhysChem, 2008, 9: 1195
7. Zhang, A.; Yang, B.; Li, Z. J. Mol. Struct. -Theochem, 2007, 819: 95
8. Zhu, C.; Meng, F. Struct. Chem., 2009, 20: 685
9. Zheng, H.; Meng, F. Struct. Chem., 2009, 20: 943
10. Kim, H. S.; Ahn, D. S.; Chung, S. Y.; Kim, S. K.; Lee, S. J. Phys. Chem. A, 2007, 111: 8007
11. Gu, J.; Leszczynski, J. J. Phys. Chem. A, 1999, 103: 2744
12. Matsubara, T.; Ishikura, M.; Aida, M. J. Chem. Inf. Model., 2006, 46: 1276
13. Danilov, V. I.; van Mourik, T.; Kurita, N.; Wakabayashi, H.; Tsukamoto, T.; Hovorun, D. M. J. Phys. Chem. A, 2009, 113: 2233
14. Haranczyk, M.; Rak, J.; Gutowski, M.; Radisic, D.; Stokes, S. T.; Bowen, K. H. J. Phys. Chem. B, 2005, 109: 13383
15. Kabelác, M.; Hobza, P. J. Phys. Chem. B, 2006, 110: 14515
16. Shukla, M. K.; Dubey, M.; Zakar, E.; Namburu, R.; Leszczynski, J. Chem. Phys. Lett., 2010, 493: 130
17. Becke, A. D. J. Chem. Phys., 1993, 98: 5648
18. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B, 1988, 37: 785
19. Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett., 1989, 157: 200
20. Baboul, A. G.; Curtiss, L. A.; Redfern, P. C. J. Chem. Phys., 1999, 110: 7650
21. Curtiss, L. A.; Raghavachari, K. J. Chem. Phys., 1998, 109: 7764
22. Tang, Y. Z.; Sun, J. Y.; Sun, H.; Pan, Y. R.;Wang, R. S. Theor. Chem. Acc., 2008, 119: 297
23. Cancès, M. T.; Mennucci, B.; Tomasi, J. J. Chem. Phys., 1997, 107: 3032
24. Cossi, M.; Barone, V.; Mennucci, B.; Tomasi, J. Chem. Phys. Lett., 1998, 286: 253
25. Mennucci, B.; Tomasi, J. J. Chem. Phys., 1997, 106: 5151
26. Rappé, A. K.; Casewit, C. J.; Colwell, K. S.; Goddard III, W. A.; Skiff,W. M. J. Am. Chem. Soc., 1992, 114: 10024
27. Rappé, A. K.; Goddard III,W. A. J. Phys. Chem., 1991, 95: 3358
28. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03. Revision D.01. Wallingford, CT: Gaussian Inc., 2004

[1]	杨树, 杨晓梅, 谢小光. YS⁺(¹Σ⁺, ³Φ)与COS气相反应: YS⁺+COS→YS₂⁺+CO的理论研究[J]. 物理化学学报, 2012, 28(08): 1892 -1898 .
[2]	冯丽霞, 靳玲侠, 王渭娜, 王文亮. C₂H₃与CH₃F氢抽提反应机理与动力学性质[J]. 物理化学学报, 2012, 28(07): 1623 -1629 .
[3]	李文佐, 洪杰, 程建波, 李庆忠, 宫宝安. 三重态类硅烯HB=SiLiF的结构及其与R—H(R=F, OH, NH₂)的插入反应[J]. 物理化学学报, 2010, 26(09): 2543 -2548 .
[4]	张家虎, 王秀军. 结合神经网络方法和扩大训练基组构建新B3LYP泛函[J]. 物理化学学报, 2010, 26(01): 188 -192 .
[5]	FARMANZADEH Davood, AMIRAZAMI Abolfazl. 电场对(4, 0)Zigzag模型单壁碳纳米管的影响[J]. 物理化学学报, 2009, 25(11): 2343 -2349 .
[6]	刘艳珠, 张玲, 李霞, 李永绣. 水杨酸甲酯及其与硝酸铁硝化产物光谱性质的比较[J]. 物理化学学报, 2009, 25(10): 2118 -2122 .
[7]	曹育才, 李猷. 液态石油烃的脱砷及砷化物与亚铜探针的相互作用[J]. 物理化学学报, 2009, 25(08): 1495 -1503 .
[8]	李文佐;程建波;李庆忠;宫宝安;孙家钟. 溶液中类锗烯H₂GeClMgCl的结构与异构化反应[J]. 物理化学学报, 2009, 25(01): 121 -125 .
[9]	李文佐;程建波;宫宝安;于健康;孙家钟. 类硅烯H₂SiClBeCl的结构及异构化反应[J]. 物理化学学报, 2008, 24(05): 901 -904 .
[10]	陈思聪;王宇;陈珏晓;滕启文. 苯乙烯桥联的三苯烯的电子结构和荧光光谱[J]. 物理化学学报, 2008, 24(02): 187 -192 .
[11]	张成根;李文佐;黄明宝. 溶液中甲醇和二氯亚砜的化学反应[J]. 物理化学学报, 2007, 23(03): 399 -403 .
[12]	韦文美;郑仁慧;田燕;何天敬;陈东明;刘凡镇. 过氧硝酸乙酰酯分解反应的速率常数[J]. 物理化学学报, 2006, 22(01): 53 -58 .
[13]	孟祥军. 二水合甘氨酸两性离子复合体的结构和性能的理论研究[J]. 物理化学学报, 2006, 22(01): 98 -101 .
[14]	王勇;李浩然;王从敏;许映杰;韩世钧. 单重态二溴卡宾和甲醛环加成反应的量化研究[J]. 物理化学学报, 2004, 20(11): 1339 -1344 .
[15]	李文佐;黄明宝. 氟代乙烯阳离子的理论研究[J]. 物理化学学报, 2004, 20(01): 21 -26 .

甲醇和氨对腺嘌呤水解脱氨机理的影响

Effects of CH₃OH and NH₃ on the Hydrolytic Deamination Mechanismof Adenine

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0

甲醇和氨对腺嘌呤水解脱氨机理的影响

Effects of CH3OH and NH3 on the Hydrolytic Deamination Mechanismof Adenine

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0

Effects of CH₃OH and NH₃ on the Hydrolytic Deamination Mechanismof Adenine