杨梅酮的抗氧化活性

doi:10.3866/PKU.WHXB201304222

摘要/Abstract

摘要：

采用密度泛函理论(DFT)方法, 研究了杨梅酮的分子结构、电子结构和羟基离解焓, 并探讨了杨梅酮与OOCH₃·自由基发生反应的抗氧化机理. 自由基发生反应的抗氧化机理. 在M06-2X/6-31++G(d,p)的计算水平下, 得到了杨梅酮脱氢后各种自由基的相对能量、羟基离解焓、氢原子提取的活化能垒和速率常数. 计算结果表明杨梅酮的4'-OH位置具有最高的抗氧化活性. 杨梅酮4'-OH位置的高活性, 主要是由于4'位上脱氢后生成的羰基与相邻的羟基之间形成了稳定的氢键. 分子中的原子(AIM)理论分析表明, 这种氢键相互作用能够稳定氢提取过程中产生的自由基. 对杨梅酮抗氧化性机理的理论研究, 可为今后设计合成新型的具有更强活性的抗氧化物提供坚实的理论基础.

关键词: DFT计算, 反应机理, 杨梅酮, 抗氧化活性, 离解焓

Abstract:

Density functional theory (DFT) calculations have been performed to explore the molecular structure, electronic structure, and O－H bond dissociation enthalpy of myricetin. Possible antioxidation mechanisms between lipid peroxide radical CH₃OO· and myricetin have been discussed. DFT calculations at the M06-2X/6-31++G(d,p) level indicated that the 4'-OH group of myricetin is the most active site on the basis of the stability of dehydrogenated myricetin radicals, O－H bond dissociation enthalpy, and hydrogen abstraction activation barrier, as well as kinetic data for myricetin determined at different temperatures. The relatively high activity of the 4'-OH site can be ascribed to weak hydrogen-bonding interactions between the oxygen radical of the reactive OH group and the adjacent OH group in the B-ring, which is retained upon going from free myricetin to reactant complex to product according to atoms in molecule (AIM) analysis. The hydrogen-bond helps to stabilize the electronic deficiency generated on the oxygen radical during the hydrogen abstraction reaction. All calculations are in agreement with the structure-activity relationship previously established for myricetin by considering its antioxidant activity. Present calculations provide theoretical basis for the designing new antioxidants.

Key words: DFT calculation, Reaction mechanism, Myricetin, Antioxidant activity, Bond dissociation enthalpy

谢湖均, 牟望舒, 林芙蓉, 徐结慧, 雷群芳, 方文军. 杨梅酮的抗氧化活性[J]. 物理化学学报, 2013, 29(07), 1421-1432. doi: 10.3866/PKU.WHXB201304222

XIE Hu-Jun, MOU Wang-Shu, LIN Fu-Rong, XU Jie-Hui, LEI Qun-Fang, FANG Wen-Jun. Radical Scavenging Activity of Myricetin[J]. Acta Phys. -Chim. Sin. 2013, 29(07), 1421-1432. doi: 10.3866/PKU.WHXB201304222

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201304222

https://www.whxb.pku.edu.cn/CN/Y2013/V29/I07/1421

参考文献

(1) Kuhnau, J. World Rev. Nutr. Diet. 1976, 24, 117.
(2) Miean, K. H.; Mohamed, S. J. Agric. Food Chem. 2001, 49,3106. doi: 10.1021/jf000892m
(3) Li, M. J.; Zhang, L. M.; Liu,W. X.; Lu,W. C. Chin. J. Chem. Phys. 2011, 24, 173.
(4) Rüfer, C. E.; Kulling, S. E. J. Agric. Food Chem. 2006, 54,2926. doi: 10.1021/jf053112o
(5) Amat, A.; Clementi, C.; De Angelis, F.; Sgamellotti, A.;Fantaccia, S. J. Phys. Chem. A 2009, 113, 15118. doi: 10.1021/jp9052538
(6) Horvath, C. R.; Martos, P. A.; Saxena, P. K. J. Chromatogr. A2005, 1062, 199. doi: 10.1016/j.chroma.2004.11.030
(7) Nenadis, N.; Sigalas, M. P. J. Phys. Chem. A 2008, 112, 12196.doi: 10.1021/jp8058905
(8) Rashid, U.; Anwar, F.; Moser, B. R.; Knothe, G. Bioresour. Technol. 2008, 99, 8175. doi: 10.1016/j.biortech.2008.03.066
(9) Gunesekaran, R.; Ubeda, A.; Alcaraz, M. J.; Jayaprakasam, R.;Nair, A. G. R. Pharmazie 1993, 48, 230.
(10) Mehrdad, M.; Zebardast, M.; Abedi, G.; Koupaei, M. N.;Rasouli, H.; Talebi, M. J. Aoac. Int. 2009, 92, 1035.
(11) Burda, S.; Oleszek,W. J. Agric. Food. Chem. 2001, 49, 2774.doi: 10.1021/jf001413m
(12) Mira, L.; Fernandez, M. T.; Santos, M.; Rocha, R.; Florencio,M. H.; Jennings, K. R. Free Radic. Res. 2002, 36, 1199.doi: 10.1080/1071576021000016463
(13) Ko, C. H.; Shen, S. C.; Lee, T. J.; Chen, Y. C. Mol. Cancer Ther.2005, 4, 281.
(14) Morales, P.; Haza, A. I. J. Appl. Toxicol. 2012, 32, 986.doi: 10.1002/jat.v32.12
(15) Rasulev, B. F.; Abdullaev, N. D.; Syrov, V. N. Leszczynski, J.QSAR Comb. Sci. 2005, 24, 1056.
(16) DeToma, A. S.; Choi, J. S.; Braymer, J. J.; Lim, M. H.ChemBioChem 2011, 12, 1198. doi: 10.1002/cbic.v12.8
(17) Delgado, M. E.; Haza, A. I.; Garcia, A.; Morales, P. Toxicolin. In Vitro 2009, 23, 1292. doi: 10.1016/j.tiv.2009.07.022
(18) Oyama, Y.; Fuchs, P. A.; Katayama, N.; Noda, K. Brain Res.1994, 635, 125. doi: 10.1016/0006-8993(94)91431-1
(19) Gordon, M. H.; Roedig-Penmanm, A. Chem. Phys. Lipids 1998,97, 79. doi: 10.1016/S0009-3084(98)00098-X
(20) Lalas, S.; Tsaknis, J. J. Am. Oil. Chem. Soc. 2002, 79, 677.doi: 10.1007/s11746-002-0542-2
(21) Shahidi, F.;Wanasundara, U. Dev. Food Sci. 1995, 37A, 469.
(22) Robak, J.; Gryglewski, R. J. Biochem. Pharmacol. 1988, 37,837. doi: 10.1016/0006-2952(88)90169-4
(23) Angelone, T.; Pasqua, T.; Di Majo, D.; Quintieri, A. M.; Filice,E.; Amodio, N.; Tota, B.; Giammanco, M.; Cerra, M. C. Nutr. Metab. Cardiovas. 2011, 21, 362. doi: 10.1016/j.numecd.2009.10.011
(24) Wang, Z. H.; Kang, K. A.; Zhang, R.; Piao, M. J.; Jo, S. H.;Kim, J. S.; Kang, S. S.; Lee, J. S.; Park, D. H.; Hyun, J.W.Environ. Toxicol. Phar. 2010, 29, 12. doi: 10.1016/j.etap.2009.08.007
(25) Moser, B. R. Eur. J. Lipid Sci. Technol. 2008, 110, 1167.doi: 10.1002/ejlt.v110:12
(26) Justino, G. C.; Vieira, A. J. S. C. J. Mol. Model. 2010, 16, 863.doi: 10.1007/s00894-009-0583-1
(27) Mendoza-Wilson, A. M.; Sotelo-Mundo, R. R.; Balandran-Quintana, R. R.; Glossman-Mitnik, D.; Santiz-Gomez, M. A.;Garcia-Orozco, K. D. J. Mol. Struct. 2010, 981, 187.doi: 10.1016/j.molstruc.2010.08.005
(28) Leon-Carmona, J. R.; Galano, A. J. Phys. Chem. B 2011, 115,4538. doi: 10.1021/jp201383y
(29) Anouar, E.; Calliste, C. A.; Kosinova, P.; Di Meo, F.; Duroux, J.L.; Champavier, Y.; Marakchi, K.; Trouillas, P. J. Phys. Chem. A2009, 113, 13881. doi: 10.1021/jp906285b
(30) Sadasivam, K.; Kumaresan, R. Spectrochim. Acta A 2011, 79,282. doi: 10.1016/j.saa.2011.02.042
(31) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215.doi: 10.1007/s00214-007-0310-x
(32) Zhao, Y.; Truhlar, D. G. Accounts Chem. Res. 2008, 41, 157.doi: 10.1021/ar700111a
(33) Barone, V.; Cossi, M. J. Phys. Chem. A 1998, 102, 1995.doi: 10.1021/jp9716997
(34) Cossi, M.; Rega, N.; Scalmani, G.; Barone, V. J. Comput. Chem.2003, 24, 669. doi: 10.1002/jcc.10189
(35) Frisch, M. J.; Trucks, G..W.; Schlegel, H. B.; et al. Gaussian 09, Revision A.01; Gaussian Inc.:Wallingford, CT, 2009.
(36) Bader, R. F.W. Chem. Res. 1991, 91, 893.
(37) Bader, R. F.W. J. Phys. Chem. A 1998, 102, 7314. doi: 10.1021/jp981794v
(38) Biegler-Konig, F. AIM2000; University of Applied Sciences:Bielefeld, Germany.
(39) Eyring, H. J. Chem. Phys. 1935, 3, 107. doi: 10.1063/1.1749604
(40) Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1935, 31, 875.doi: 10.1039/tf9353100875
(41) Wigner, E. J. Chem. Phys. 1937, 5, 720.
(42) Russo, N.; Toscano, M.; Uccella, N. J. Agric. Food Chem.2000, 48, 3232. doi: 10.1021/jf990469h
(43) Bors,W.; Heller,W.; Saran, M. Methods in Enzymology;Academic Press: San Diego, 1990; Vol. 186, p 343.
(44) Leopoldini, M.; Rondinelli, F.; Russo, N.; Toscano, M. J. Agric. Food Chem. 2010, 58, 8862. doi: 10.1021/jf101693k
(45) Estvez, L.; Mosquera, R. A. J. Phys. Chem. A 2007, 111, 11100.doi: 10.1021/jp074941a
(46) Xie, H. J.; Lei, Q. F.; Fang,W. J. Acta Chim. Sin. 2010, 68,1467.
(47) Markovic, Z. S.; Dimitric, J. M.; Markovic, D.; Dolicanin, C.B. Theor. Chem. Acc. 2010, 127, 69. doi: 10.1007/s00214-009-0706-x
(48) Sadasivam, K.; Kumaresan, R. Comput. Theor. Chem. 2011,963, 227. doi: 10.1016/j.comptc.2010.10.025
(49) Van Acker, S. A. B. E.; DeGroot, M. J.; Van den Berg, D. J.;Tromp, M. N. J. L.; Den Kelder, G. D. O.; Van der Vijgh,W. J.F.; Bast, A. Chem. Res. Toxicol. 1996, 9, 1305. doi: 10.1021/tx9600964
(50) Rice-Evans, C. A.; Miller, N. J.; Paganga, G. Free Radic. Biol. Med. 1996, 20, 933. doi: 10.1016/0891-5849(95)02227-9
(51) Van Acker, S. A. B. E.; Van Den Berg, D. J.; Tromp, M. N. J. L.;Griffioen, D. H.; Van Bennekom,W. P.; Van Der Vijgh,W. J. F.;Bast, A. Free Radic. Biol. Med. 1996, 20, 331. doi: 10.1016/0891-5849(95)02047-0
(52) Guzman, R.; Santiago, C.; Sanchez, M. J. Mol. Struct. 2009,935, 110. doi: 10.1016/j.molstruc.2009.06.048
(53) Chiodo, S. G.; Leopoldini, M.; Russo, N.; Toscano, M. Phys. Chem. Chem. Phys. 2010, 12, 7662. doi: 10.1039/b924521a
(54) Li, M. J.; Li, Y. J.; Peng, C. R.; Lu,W. C. Acta Phys. -Chim. Sin. 2010, 26, 466. [李敏杰, 李亚军, 彭淳容, 陆文聪. 物理化学学报, 2010, 26, 466.] doi: 10.3866/PKU.WHXB20100230
(55) Wright, J. S.; Johnson, E. R.; Di Labio, G. A. J. Am. Chem. Soc.2001, 123, 1173. doi: 10.1021/ja002455u
(56) Trouillas, P.; Fagnere, C.; Lazzaroni, R.; Calliste, C.; Marfak,A.; Duroux, J. L. Food Chem. 2004, 88, 571. doi: 10.1016/j.foodchem.2004.02.009
(57) Aparicio, S. Int. J. Mol. Sci. 2010, 11, 2017. doi: 10.3390/ijms11052017
(58) Zhang, J. H.; Du, F. P.; Peng, B.; Lu, R. H.; Gao, H. X.; Zhou,Z. Q. J. Mol. Struct. -Theochem 2010, 955, 1. doi: 10.1016/j.theochem.2010.04.036
(59) Kosinova, P.; Di Meo, F.; Anouar, E. H.; Duroux, J. L.;Trouillas, P. Int. J. Quantum Chem. 2011, 11, 1131.
(60) Zhang, H. Y.;Wang, L. F.; Sun, Y. M. Bioorg. Med. Chem. Lett.2003, 13, 909. doi: 10.1016/S0960-894X(03)00013-1
(61) Zhang, I. Y.;Wu, J. M.; Luo, Y.; Xu, X. J. Comput. Chem. 2011,32, 1824. doi: 10.1002/jcc.v32.9
(62) Wu, J. M.; Zhang, I. Y.; Xu, X. ChemPhysChem 2010, 11, 2561.doi: 10.1002/cphc.201000273
(63) Alecu, I. M.; Truhlar, D. G. J. Phys. Chem. A 2011, 115, 2811.doi: 10.1021/jp110024e
(64) Dhaouadi, Z.; Nsangou, M.; Garrab, N.; Anouar, E. H.;Marakchi, K.; Lahmar, S. J. Mol. Struct. -Theochem 2009, 904,35. doi: 10.1016/j.theochem.2009.02.034
(65) Mikulski, D.; Gorniak, R.; Molski, M. Eur. J. Med. Chem. 2010,45, 1015. doi: 10.1016/j.ejmech.2009.11.044
(66) Trouillas, P.; Marsal, P.; Siri, D.; Lazzaroni, R.; Duroux, J. L.Food Chem. 2006, 97, 679. doi: 10.1016/j.foodchem.2005.05.042
(67) Leopoldini, M.; Pitarch, I. P.; Russo, N.; Toscano, M. J. Phys. Chem. A 2004, 108, 92. doi: 10.1021/jp035901j
(68) Bowater, L.; Fairhurst, S. A.; Just, V. J.; Bornemann, S. FEBS Lett. 2004, 557, 45. doi: 10.1016/S0014-5793(03)01439-X
(69) Lien, E. J.; Ren, S.; Bui, H. H.;Wang, R. Free Radic. Biol. Med. 1999, 26, 285. doi: 10.1016/S0891-5849(98)00190-7
(70) Tejero, I.; Gonzalez-Garcia, N.; Gonzalez-Lafont, A.; Lluch, J.M. J. Am. Chem. Soc. 2007, 129, 5846. doi: 10.1021/ja063766t

[1]	徐涵煜, 宋雪旦, 张青, 于畅, 邱介山. 理论研究Cu@C₂N催化剂表面上水分子对电催化CO₂还原反应机理的影响[J]. 物理化学学报, 2024, 40(1): 2303040 - .
[2]	高凤雨, 刘恒恒, 姚小龙, Sani Zaharaddeen, 唐晓龙, 罗宁, 易红宏, 赵顺征, 于庆君, 周远松. 球形表面富锰Mn_xCo_3−xO_4−ƞ尖晶石型催化剂选择性催化还原NO_x研究[J]. 物理化学学报, 2023, 39(9): 2212003 -0 .
[3]	李莹, 来雪琦, 曲津朋, 赖勤志, 伊廷锋. 钠离子电池用高性能锑基负极材料的调控策略研究进展[J]. 物理化学学报, 2022, 38(11): 2204049 - .
[4]	陈鹏, 周莹, 董帆. 二维光催化材料电子结构和性能调控策略研究进展[J]. 物理化学学报, 2021, 37(8): 2010010 - .
[5]	刘东, 陈圣韬, 李仁杰, 彭天右. 用于光催化能量转换的Z-型异质结的研究进展[J]. 物理化学学报, 2021, 37(6): 2010017 - .
[6]	胡媛媛,王从洋. 双金属促进的均相碳氢键活化反应[J]. 物理化学学报, 2019, 35(9): 913 -922 .
[7]	单春晖,白若鹏,蓝宇. 过渡金属参与C―H键切断模式的理论研究进展[J]. 物理化学学报, 2019, 35(9): 940 -953 .
[8]	赵越,崔佳桐,胡继闯,马嘉璧. VO_1-4⁺阳离子与n-C_mH_2m+2 (m = 3, 5, 7)烷烃的反应性研究：氧含量和碳链长度的影响[J]. 物理化学学报, 2019, 35(5): 531 -538 .
[9]	郑东,熊鹏飞,钟北京. NOFBX新型绿色推进剂燃烧化学反应动力学模型[J]. 物理化学学报, 2019, 35(11): 1241 -1247 .
[10]	陈必华,ELAGEED Elnazeer H. M.,张永亚,高国华. 离子液体BmmimOAc催化2-芳氨基乙醇与二硫化碳一步缩合合成3-芳基-2-噻唑硫酮[J]. 物理化学学报, 2018, 34(8): 952 -958 .
[11]	任春醒,李晓霞,郭力. CL-20热分解反应机理的ReaxFF分子动力学模拟[J]. 物理化学学报, 2018, 34(10): 1151 -1162 .
[12]	王子民,郑默,谢勇冰,李晓霞,曾鸣,曹宏斌,郭力. 基于ReaxFF力场的对硝基苯酚臭氧氧化分子动力学模拟[J]. 物理化学学报, 2017, 33(7): 1399 -1410 .
[13]	张英杰,朱子翼,董鹏,邱振平,梁慧新,李雪. LiFePO₄电化学反应机理、制备及改性研究新进展[J]. 物理化学学报, 2017, 33(6): 1085 -1107 .
[14]	李申慧,李静,郑安民,邓风. 固体酸催化剂结构与催化反应机理的核磁共振研究[J]. 物理化学学报, 2017, 33(2): 270 -282 .
[15]	郑东,钟北京,姚通. 航空煤油替代燃料模型构建方法及HEF航空煤油替代燃料模型[J]. 物理化学学报, 2017, 33(12): 2438 -2445 .