氮氧化物TEMPO清除过氧自由基的机理研究

doi:10.7503/cjcu20180244

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 1961.doi: 10.7503/cjcu20180244

氮氧化物TEMPO清除过氧自由基的机理研究

陈军超¹, 姚远¹(), 张辉²

1. 哈尔滨工业大学化工与化学学院, 新能源转换与储存关键材料技术工业和信息化部重点实验室, 哈尔滨 150080
2. 哈尔滨理工大学化学与环境工程学院, 哈尔滨 150080

收稿日期:2018-03-29 出版日期:2018-07-30 发布日期:2018-07-30
作者简介:
联系人简介: 姚远, 男, 博士, 副教授, 主要从事生物和有机催化理论研究. E-mail: yyuan@hit.edu.cn
基金资助:
黑龙江省自然科学基金(批准号: B201301)资助.

Reaction Mechanism of the Elimination of Peroxyl Radical by TEMPO^†

CHEN Junchao¹, YAO Yuan^1,^*(), ZHANG Hui²

1. Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, Ministry of Industry and Information Technology, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150080, China
2. College of Chemical and Environmental Engineering, Harbin University of Science and Technology, Harbin 150080, China

Received:2018-03-29 Online:2018-07-30 Published:2018-07-30
Contact: YAO Yuan E-mail:yyuan@hit.edu.cn
Supported by:
† Supported by the Natural Science Foundation of the Heilongjiang Province, China(No.B201301)

摘要/Abstract

摘要：

采用密度泛函理论、微扰理论和前线分子轨道分析, 对酸环境和无酸环境下的2,2,6,6-四甲基哌啶氮氧化物(TEMPO)捕获过氧自由基的机理进行了理论研究. 研究结果表明, 与B3LYP泛函相比, M06-2x泛函的计算结果更接近实验值, 更适合于所研究的体系; 在酸环境下, 质子化的TEMPO 经过质子耦合电子转移和电子转移两个反应过程清除过氧自由基, 并获得再生; 与之相比, 在无酸条件下TEMPO清除过氧自由基的反应过程则较为复杂, 包括了烷氧胺的生成、 β-氢原子转移、碳中心自由基的解离和TEMPO的再生4个反应步骤. 通过能量计算, 酸性条件下反应活化能为35.6 kJ/mol, 明显低于无酸环境下的96.8 kJ/mol, 说明酸性条件更有利于TEMPO清除过氧自由基, 并对这一现象的化学本质给予了理论解释.

关键词: 2,2,6,6-四甲基哌啶氮氧化物, 过氧自由基, 抗氧化

Abstract:

Density functional theory(DFT), Møller-Plesset(MP) and frontier molecular orbital methods were employed to investigate the fundamental reaction mechanism of the elimination of peroxyl radical by 2,2,6,6-tetramethylpiperidin-1-oxyl(TEMPO) with and without weak acid environment. The results showed that the calculated result from M06-2x method is in more agreement with the relative experimental results than that from B3LYP method, suggesting that the former is more suitable for the present system. With weak acid environment, the protonated TEMPO undergoes proton coupled electron transfer and electron transfer to eliminate peroxyl radical and get the regeneration. Without acid environment, the elimination of peroxyl radical by TEMPO consists of four steps, the formation of alkoxyamine, β-hydrogen atom transfer, the decomposition of carbon radical, and the regeneration of TEMPO. After the energy calculations, the activation free energy of the elimination of peroxyl radical by TEMPO with weak acid environment is calculated to be 35.6 kJ/mol, much lower than 96.8 kJ/mol without weak acid environment, showing that weak acid environment is more favorable for the reaction and this phenomenon has also been reasonably explained.

Key words: 2,2,6,6-Tetramethylpiperidin-1-oxyl(TEMPO), Peroxyl radical, Antioxidation

中图分类号:

TrendMD:

陈军超, 姚远, 张辉. 氮氧化物TEMPO清除过氧自由基的机理研究. 高等学校化学学报, 2018, 39(9): 1961.

CHEN Junchao,YAO Yuan,ZHANG Hui. Reaction Mechanism of the Elimination of Peroxyl Radical by TEMPO^†. Chem. J. Chinese Universities, 2018, 39(9): 1961.

图/表 7

Fig.1 Simplified Denisov cycle(X is H or alkyl chain)

Fig.2 Mechanisms for TEMPO regeneration with (A) and without(B) acid

Fig.3 Optimized geometries of the stationary points involved in acid-catalyzed TEMPO regeneration a. B3LYP; b. M06-2x. Bond lengths are in nm.

Fig.4 Highest occupied molecular orbitals for TS1a optimized at B3LYP(A) and M06-2x(B) methods and the singly occupied molecular orbital of TS1b at M06-2x(C) method

Fig.5 Free energy profile for acid-catalyzed TEMPO regeneration a. B3LYP; b. M06-2x.

Fig.6 Optimized geometries of the stationary points for TEMPO regeneration involved in Denisov cycle

Fig.7 Free energy profile for TEMPO regeneration involved in Denisov cycle

参考文献 31

[1]	Ingold K. U., Pratt D. A., Chem. Rev., 2014, 114(18), 9022—9046
[2]	Burton G. W., Ingold K. U., Acc. Chem. Res., 1986, 19(7), 194—201
[3]	Foti M. C., J. Pharm. Pharmacol., 2007, 59(12), 1673—1685
[4]	Brownlie I. T., Ingold K. U., Can. J. Chem., 1967, 45(20), 2427—2432
[5]	Bolsman T. A. B. M., Blok A. P., Frijns J. H. G., Recueil des Travaux Chimiques des Pays-Bas, 1978, 97(12), 310—312
[6]	Gijsman P., Photostabilisation of Polymer Materials, In Photochemistry and Photophysics of Polymer Materials, John Wiley & Sons, Inc., Hoboken, 2010, 627—679
[7]	Allen N. S., Chem. Soc. Rev., 1986, 15(3), 373—404
[8]	Brede O., Beckert D., Windolph C., Gottinger H. A., J. Phys. Chem. A, 1998, 102(9), 1457—1464
[9]	Pospíšil J., Aromatic and Heterocyclic Amines in Polymer Stabilization, In Adv. Polym. Sci., Springer, Berlin, 1995, 87—189
[10]	Geuskens G., Nedelkos G., Polym. Degrad. Stabil., 1987, 19(4), 365—378
[11]	Sedláar J., Petru̇j J., Pác J., Navrátil M., Polymer, 1980, 21(1), 5—7
[12]	Wiles D. M., Tovborg Jensen J. P., Carlsson D. J., Pure and App. Chem., 1983, 55(10), 1651—1659
[13]	Gugumus F., Polym. Degrad. Stabil., 1991, 34(1—3), 205—241
[14]	Gryn'ova G., Ingold K. U., Coote M. L., J. Am. Chem. Soc., 2012, 134(31), 12979—12988
[15]	Rossi I., Venturini A., Zedda A., J. Am. Chem. Soc., 1999, 121(34), 7914—7917
[16]	Stipa P., J. Chem. Soc., Perkin Trans., 2001, 2(9), 1793—1797
[17]	Goldstein S., Samuni A., J. Phys. Chem. A, 2007, 111(6), 1066—1072
[18]	Klemchuk P. P., Gande M. E., Cordola E., Polym. Degrad. Stabil., 1990, 27(1), 65—74
[19]	Barton D. H. R., Le Gloahec V. N., Smit. J., Tetrahedron Lett., 1998, 39(41), 7483—7486
[20]	Hodgson J. L., Coote M. L., Macromol., 2010, 43(10), 4573—4583
[21]	Haidasz E. A., Meng D., Amorati R., Baschieri A., Ingold K. U., Valgimigli L., Pratt D. A., J. Am. Chem. Soc., 2016, 138(16), 5290—5298
[22]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. J. A., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision C.01, Gaussian Inc., Wallingford CT, 2009
[23]	Mayer J. M., Hrovat D. A., Thomas J. L., Borden W. T., J. Am. Chem. Soc., 2002, 124(37), 11142—11147
[24]	Migliore A., Polizzi N. F., Therien M. J., Beratan D. N., Chem. Rev., 2014, 114, 3381—3465
[25]	Li J., Zhou S., Zhang J., Schlangen M., Usharani D., Shaik S., Schwarz H., J. Am. Chem. Soc., 2016, 138, (35) 11368—11377
[26]	Guo X. K., Zhang L. B., Wei D., Niu J. L., Chem. Sci., 2015, 6(12), 7059—7071
[27]	Qiao Y., Chen X., Wei D., Chang J., Scientific Rep., 2016, 6, 38200
[28]	Wang Y., Wu B., Zhang H., Wei D., Tang M., Phys. Chem. Chem.Phys., 2016, 18(29), 19933—19943
[29]	Cheng X. L., Li Y. J., Zhao Y. Y., Liu Y. J., Chem. J. Chinese Universities, 2018, 39(3), 521—529
	(程学礼, 李衍军, 赵燕云, 刘永军. 高等学校化学学报, 2018, 39(3), 521—529)
[30]	Valgimigli L., Amorati R., Petrucci S., Pedulli G. F., Hu D., Hanthorn J. J., Pratt D. A., Angew. Chem. Int. Ed., 2009, 48(44), 8348—8351
[31]	Sobek J., Martschke R., Fischer H., J. Am. Chem. Soc., 2001, 123(12), 2849—2857

氮氧化物TEMPO清除过氧自由基的机理研究

Reaction Mechanism of the Elimination of Peroxyl Radical by TEMPO^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

[1]	黄罗仪, 翁约约, 黄旭慧, 王朝杰. 车前草中黄酮类成分结构和性质的理论研究[J]. 高等学校化学学报, 2021, 42(9): 2752.
[2]	胡皓程, 李文利, 张嘉宁, 刘宇博. 黑木耳寡糖的提取、结构表征及生物活性[J]. 高等学校化学学报, 2021, 42(8): 2465.
[3]	杨依然, 姚华, 闫江红, 孙志恒, 张余, 房雪晴, 李绪文, 金永日. 薤中新的甾体皂苷类化学成分[J]. 高等学校化学学报, 2021, 42(6): 1742.
[4]	帅蝶, 赵美娟, 陈丙年, 王力. 4种Keggin型磷钼酸盐对蘑菇酪氨酸酶活性和黑色素生成的抑制及抗氧化作用[J]. 高等学校化学学报, 2021, 42(12): 3579.
[5]	韩方杰, 代梦娇, 梁芷珊, 宋忠乾, 韩冬雪, 牛利. 光电化学技术应用于抗氧化分析的研究进展[J]. 高等学校化学学报, 2020, 41(4): 591.
[6]	袁中文, 贺利贞, 陈填烽. 单原子催化剂的生物医学应用[J]. 高等学校化学学报, 2020, 41(12): 2690.
[7]	李翠勤, 翟雪, 孙鹏, 高宇新, 张志秋, 王俊, 李锋. 树状桥联半受阻酚类抗氧剂的合成与抗氧化性能[J]. 高等学校化学学报, 2019, 40(7): 1535.
[8]	梁芷珊, 倪爽, 代梦娇, 韩方杰, 韩立鹏, 牛利, 韩冬雪. 基于g-C₃N₄/P25复合光电敏感体系的中草药抗氧化容量测定[J]. 高等学校化学学报, 2019, 40(10): 2081.
[9]	蒋静, 黄亚励, 张奇龙, 徐红, 孙晓红. 八元瓜环对氯化矢车菊素溶解性、稳定性及抗氧化性的影响[J]. 高等学校化学学报, 2019, 40(1): 76.
[10]	王雁冰, 张辉, 杨峻山, 陈炳鹏, 孙佳明. 破骨风中木脂素类化合物的分离鉴定及抗氧化活性[J]. 高等学校化学学报, 2018, 39(9): 1942.
[11]	张岩, 张盛明, 方桂珍. Ce掺杂固体酸活化的碱木质素的抗氧化性能[J]. 高等学校化学学报, 2018, 39(6): 1255.
[12]	练小卫, 黄净净, 陶朱, 周清娣, 张前军, 卫钢. 八元瓜环与乔松素的主客体作用及对乔松素性质的影响[J]. 高等学校化学学报, 2018, 39(2): 226.
[13]	黄净净, 许志玲, 练小卫, 张晓东, 陶朱, 周清娣, 张前军, 卫钢. 八元瓜环与黄岑苷的主客体相互作用及对黄岑苷性质的影响[J]. 高等学校化学学报, 2018, 39(11): 2425.
[14]	张露云, 徐倩, 夏广清, 丛丽, 王雨, 张辉, 朱俊义, 臧皓. 硫辛酸酯类衍生物的合成及生物活性[J]. 高等学校化学学报, 2018, 39(10): 2198.
[15]	臧皓, 沈鹏, 王恩鹏, 徐倩, 张露云, 夏广清, 朱俊义, 张辉, 杨晓虹. 酪醇酯类衍生物的合成及生物活性[J]. 高等学校化学学报, 2018, 39(1): 64.

氮氧化物TEMPO清除过氧自由基的机理研究

Reaction Mechanism of the Elimination of Peroxyl Radical by TEMPO†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

Reaction Mechanism of the Elimination of Peroxyl Radical by TEMPO^†