气相中疏水氨基酸的单电子氧化还原性质

引用本文: 李伟伟, 侯若冰, 孙彦丽. 气相中疏水氨基酸的单电子氧化还原性质[J]. 物理化学学报, 2010, 26(10): 2772-2778. doi: 10.3866/PKU.WHXB20101004 shu

Citation: LI Wei-Wei, HOU Ruo-Bing, SUN Yan-Li. Characteristics of One Electron Redox Behavior of Hydrophobic AminoAcids in Gas Phase[J]. Acta Physico-Chimica Sinica, 2010, 26(10): 2772-2778. doi: 10.3866/PKU.WHXB20101004 shu

气相中疏水氨基酸的单电子氧化还原性质

基金项目:
广西研究生创新计划项目(2009106020703M48)资助 (2009106020703M48)

摘要:

采用密度泛函理论在B3LYP/DZP++ 水平上研究气相中疏水氨基酸的单电子氧化还原性质. 计算表明: 发生单电子氧化反应时, 侧链较小的甘氨酸、丙氨酸、脯氨酸、缬氨酸、亮氨酸、异亮氨酸丢失电子的主要部位是氨基、α-碳和羧基, 对应着相对较大的绝热电离能(8.52-9.15 eV); 而半胱氨酸、甲硫氨酸、苯丙氨酸、酪氨酸、色氨酸因侧链丢失较多负电荷, 其电离能有所降低. 气相中疏水氨基酸从外界捕获的电子主要驻留在羧基或氨基的氢原子外侧以及分子的骨架上, 形成具有偶极边界结构和价键结构的混合状态阴离子, 绝热电子亲和势在-0.08 至-0.63 eV 之间. 由于氨基酸的电离能较大且电子亲和势为负值, 所以在气相中它们既不容易被氧化也难以被还原.

关键词:

English

Characteristics of One Electron Redox Behavior of Hydrophobic AminoAcids in Gas Phase

1.
College of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, Guangxi Province, P. R. China
Received Date: 26 May 2010
Available Online: 27 September 2010
Fund Project:
广西研究生创新计划项目(2009106020703M48)资助

Abstract:

Characteristics of the one electron redox behavior of hydrophobic amino acids in gas phase were calculated with density functional theory at the B3LYP/DZP++ level. For glycine, alanine, proline, valine, leucine, and isoleucine with small side chains, the computational results indicate that the negative charges are removed from the atoms of their amino, α-carbon, and carboxy moieties in one electron oxidation reactions. This yields large adiabatic ionization potentials (AIP) of 8.52-9.15 eV. The AIPs of cysteine, methionine, phenylalanine, tyrosine, and tryptophan decrease because of the larger amount of negative charge removed from the atoms in their side chains. The attachment of one electron to the molecules of hydrophobic amino acids leads to anions in which the extra electron is bound to the H atoms of the carboxyl or amino groups and to their valence orbitals, reflecting the double nature of the dipole -bound state and the valence state. The electron affinities (EA) for the amino acids are small and negative ranging from -0.08 to -0.63 eV. The molecules of the hydrophobic amino acids are oxidized or reduced with difficulty in gas phase because of their high VIPs and negative EAs.

Key words:

1. [1]
  
  1. Guo, Z. F.; An, Q. R. Journal of Hebei University: Natural Science Edition, 1997, 17: 73 [郭志峰, 安秋荣.河北大学学报(自然科学版), 1997, 17: 73]
  1. Guo, Z. F.; An, Q. R. Journal of Hebei University: Natural Science Edition, 1997, 17: 73 [郭志峰, 安秋荣.河北大学学报(自然科学版), 1997, 17: 73]
2. [2]
  2. Campbell, S.; Beauchamp, J. L.; Rempe, M.; Lichtenberger, D. L. Int. J. Mass Spectrom. Ion Processes, 1992, 117: 832. Campbell, S.; Beauchamp, J. L.; Rempe, M.; Lichtenberger, D. L. Int. J. Mass Spectrom. Ion Processes, 1992, 117: 83
3. [3]
  3. Dehareng, D.; Dive, G. Int. J. Mol. Sci., 2004, 5: 3013. Dehareng, D.; Dive, G. Int. J. Mol. Sci., 2004, 5: 301
4. [4]
  4. Millefiori, S.; Alparone, A.; Millefiori, A.; Vanella, A. Biophys. Chem., 2008, 132: 1394. Millefiori, S.; Alparone, A.; Millefiori, A.; Vanella, A. Biophys. Chem., 2008, 132: 139
5. [5]
  5. Kishora, S.; Dhayalb, S.; Mathurc, M.; Ramaniah, L. M. Mol. Phys., 2008, 106: 22895. Kishora, S.; Dhayalb, S.; Mathurc, M.; Ramaniah, L. M. Mol. Phys., 2008, 106: 2289
6. [6]
  6. Wright, L. R.; Borkman, R. F. J. Am. Chem. Soc., 1980, 102: 62076. Wright, L. R.; Borkman, R. F. J. Am. Chem. Soc., 1980, 102: 6207
7. [7]
  7. Rai, A. K.; Song, C.; Lin, Z. J. Spectrochim. Acta A, 2009, 73: 8657. Rai, A. K.; Song, C.; Lin, Z. J. Spectrochim. Acta A, 2009, 73: 865
8. [8]
  8. Rienstra-Kiracofe, J. C.; Tschumper, G. S.; Schaefer, H. F.; Nandi, S.; Ellison, G. B. Chem. Rev., 2002, 102: 2318. Rienstra-Kiracofe, J. C.; Tschumper, G. S.; Schaefer, H. F.; Nandi, S.; Ellison, G. B. Chem. Rev., 2002, 102: 231
9. [9]
  9. Hou, R. B.; Gu, J. D.; Xie, Y. M.; Yi, X. H.; Schaefer, H. F. J. Phys. Chem. B, 2005, 109: 220539. Hou, R. B.; Gu, J. D.; Xie, Y. M.; Yi, X. H.; Schaefer, H. F. J. Phys. Chem. B, 2005, 109: 22053
10. [10]
  10. Richardson, N. A.; Gu, J.; Wang, S.; Xie, Y.; Schaefer, H. F. J. Am. Chem. Soc., 2004, 126: 440410. Richardson, N. A.; Gu, J.; Wang, S.; Xie, Y.; Schaefer, H. F. J. Am. Chem. Soc., 2004, 126: 4404
11. [11]
  11. Gu, J.; Xie, Y.; Schaefer, H. F. Nucleic Acids Res., 2007, 35: 516511. Gu, J.; Xie, Y.; Schaefer, H. F. Nucleic Acids Res., 2007, 35: 5165
12. [12]
  12. Gu, J.; Xie, Y.; Schaefer, H. F. J. Phys. Chem. B, 2010, 114: 122112. Gu, J.; Xie, Y.; Schaefer, H. F. J. Phys. Chem. B, 2010, 114: 1221
13. [13]
  13. Bao, X. G.; Wang, J.; Gu, J. D.; Leszczynski, J. Proc. Natl. Acad. Sci. U. S. A., 2006, 103: 565813. Bao, X. G.; Wang, J.; Gu, J. D.; Leszczynski, J. Proc. Natl. Acad. Sci. U. S. A., 2006, 103: 5658
14. [14]
  14. Hou, R. B.; Li,W. W.; Shen, X. C. Acta Phys. -Chim. Sin., 2008, 24: 269 [侯若冰,李伟伟,沈星灿. 物理化学学报, 2008, 24: 269]14. Hou, R. B.; Li,W. W.; Shen, X. C. Acta Phys. -Chim. Sin., 2008, 24: 269 [侯若冰,李伟伟,沈星灿. 物理化学学报, 2008, 24: 269]
15. [15]
  15. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al., Gaussian 03. Revision B.03. Pittsburgh, PA: Gaussian Inc., 200315. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al., Gaussian 03. Revision B.03. Pittsburgh, PA: Gaussian Inc., 2003
16. [16]
  16. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys., 1985, 83: 73516. Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys., 1985, 83: 735
17. [17]
  17. Reed, A. E.; Weinhold, F. J. Chem. Phys., 1985, 83: 173617. Reed, A. E.; Weinhold, F. J. Chem. Phys., 1985, 83: 1736
18. [18]
  18. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev., 1988, 88: 89918. Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev., 1988, 88: 899
19. [19]
  19. Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc., 1990, 112: 143419. Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc., 1990, 112: 1434
20. [20]
  20. Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO Version 3.120. Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO Version 3.1
21. [21]
  21. Pacios, L. F.; mez, P. C. J. Mol. Struct. -Theochem, 2001, 544: 23721. Pacios, L. F.; mez, P. C. J. Mol. Struct. -Theochem, 2001, 544: 237
22. [22]
  22. Lu, J. F.; Zhu, S. L.; Zhou, Z. Y.; Wu, Q. Y.; Zhao, G. Pol. J. Chem., 2006, 80: 47122. Lu, J. F.; Zhu, S. L.; Zhou, Z. Y.; Wu, Q. Y.; Zhao, G. Pol. J. Chem., 2006, 80: 471
23. [23]
  23. Wilke, J. J.; Lind, M. C.; Schaefer III, H. F.; Csaszar, A. G.; Allen, W. D. J. Chem. Theory Comput., 2009, 5: 151123. Wilke, J. J.; Lind, M. C.; Schaefer III, H. F.; Csaszar, A. G.; Allen, W. D. J. Chem. Theory Comput., 2009, 5: 1511
24. [24]
  24. Czinki, E.; Csazar, A. G. Chem. Eur. J., 2003, 9(4): 100824. Czinki, E.; Csazar, A. G. Chem. Eur. J., 2003, 9(4): 1008
25. [25]
  25. Dokmaisrijan, S.; Lee, V. S.; Nimmanpipug, P. J. Mol. Struct. - Theochem, 2010, 953: 2825. Dokmaisrijan, S.; Lee, V. S.; Nimmanpipug, P. J. Mol. Struct. - Theochem, 2010, 953: 28
26. [26]
  26. Armentrout, P. B.; Gabriel, A.; Moision, R. M. Int. J. Mass Spectrom., 2009, 283: 5626. Armentrout, P. B.; Gabriel, A.; Moision, R. M. Int. J. Mass Spectrom., 2009, 283: 56
27. [27]
  27. Huang, Z. J.; Yu, W. B.; Lin, Z. J. J. Mol. Struct. -Theochem, 2006, 758: 19527. Huang, Z. J.; Yu, W. B.; Lin, Z. J. J. Mol. Struct. -Theochem, 2006, 758: 195
28. [28]
  28. Zhang, M. L.; Huang, Z. J.; Lin, Z. J. J. Chem. Phys., 2005, 122: 13431328. Zhang, M. L.; Huang, Z. J.; Lin, Z. J. J. Chem. Phys., 2005, 122: 134313
29. [29]
  29. Huang, Z. J.; Lin, Z. J. J. Phys. Chem. A, 2005, 109: 265629. Huang, Z. J.; Lin, Z. J. J. Phys. Chem. A, 2005, 109: 2656
30. [30]
  30. Vorsa, V.; Kono, T.; Willey, K. F.;Winograd, N. J. Phys. Chem. B, 1999, 103: 788930. Vorsa, V.; Kono, T.; Willey, K. F.;Winograd, N. J. Phys. Chem. B, 1999, 103: 7889
31. [31]
  31. Diken, E. G.; Hammer, N. I.; Johnson M. A. J. Chem. Phys., 2004, 120: 989931. Diken, E. G.; Hammer, N. I.; Johnson M. A. J. Chem. Phys., 2004, 120: 9899
32. [32]
  32. Abouaf, R. Chem. Phys. Lett., 2008, 451: 2532. Abouaf, R. Chem. Phys. Lett., 2008, 451: 25
33. [33]
  33. Hou, R. B.; Li,W. W. Journal of Guangxi Normal University: Natural Science Edition, 2009, 27: 78 [侯若冰,李伟伟. 广西师范大学学报(自然科学版), 2009, 27: 78]
  33. Hou, R. B.; Li,W. W. Journal of Guangxi Normal University: Natural Science Edition, 2009, 27: 78 [侯若冰,李伟伟. 广西师范大学学报(自然科学版), 2009, 27: 78]

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沈阳化工大学材料科学与工程学院沈阳 110142

气相中疏水氨基酸的单电子氧化还原性质

English

Characteristics of One Electron Redox Behavior of Hydrophobic AminoAcids in Gas Phase

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

气相中疏水氨基酸的单电子氧化还原性质

English

Characteristics of One Electron Redox Behavior of Hydrophobic AminoAcids in Gas Phase

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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