水液相下缬氨酸钠螯合物清除羟基自由基的反应机制

Reaction Mechanism of Hydroxyl Radical Scavenging by Sodium Valine Chelate in Aqueous Liquid Phase

摘要

采用密度泛函理论(DFT)研究钠离子的缬氨酸螯合物(Val→Na⁺)在310.15 K的水液相环境下与羟基自由基(·OH)的反应机理,考察Val→Na⁺与·OH的提H和加成反应势能面以及它们之间单电子转移反应的自由能垒和自由能变.计算结果表明:热力学均允许其提H反应,隐性水溶剂效应下其反应能垒为23.3~75.6 kJ/mol,显性水溶剂效应下其反应能垒为33.8~81.2 kJ/mol,大多数提H能垒小幅度升高;在隐性和显性水溶剂效应下,热力学均不允许其加成反应;在隐性和显性水溶剂效应下,热力学和动力学均不允许其电子转移.可见,水液相下Val→Na⁺可通过提H反应快速消除·OH,缬氨酸钠螯合物可作为·OH清除剂.

Abstract

We used density functional theory (DFT) to investigate the reaction mechanisms of the sodium ion valine chelates (Val→Na⁺) with hydroxyl radicals (·OH) in aqueous liquid environment at 310.15 K. We explored the potential energy surfaces of the hydrogen abstraction and addition reactions of Val→Na⁺ and ·OH, and the free energy barriers and free energy changes of the single-electron transfer reactions between them. The calculation results show that thermodynamics allows for the hydrogen abstraction reactions with a reaction energy barrier of 23.3—75.6 kJ/mol for implicit water solvent effects, and 33.8—81.2 kJ/mol for explicit water solvent effects. Most hydrogen abstraction energy barriers increase slightly. Thermodynamics and kinetics do not allow for electron transfer under both implicit and explicit solvent effects. It can be seen that Val→Na⁺ can rapidly scavenge ·OH through hydrogen abstraction reaction in aqueous liquid phase, and sodium valine chelate can be used as ·OH scavenger.

关键词

缬氨酸钠 / 羟基自由基 / 密度泛函理论 / 溶剂效应 / 氢键 / 自由能垒

Key words

sodium valine / hydroxyl radical / density functional theory / solvent effect / hydrogen bond / free energy barrier

参考文献

[1] Perez-González A, Rebollar-Ze-Peda A M, León-Carmona J R, et al. Reactivity Indexes and O-H Bond Dissociation Energiles of Alarge Series of Polyphenols: Implications for Their Free Radical Scavenging Activity[J]. Journal of the Mexican Chemical Society, 2012, 56(3): 241-249.

[2] De Zwart L L, Meerman J H, Commandeur J N, et al. Biomarkers of Free Radical Damage Applications in Experimental Animals and in Humans[J]. Free Radic Biol Med, 1999, 26(1/2): 202-226.

[3] 王颢霖, 杨应, 张雪娇, 等. 生理环境下羟基脯氨酸清除羟基自由基的反应机制[J]. 武汉大学学报(理学版), 2024, 70(5):603-612.

[4] (Wang H L, Yang Y, Zhang X J, et al. Mechanism of Hydroxproline Eliminating Hydroxyl Radical in Physiological Environment[J]. Journal of Wuhan University (Natural Science Edition), 2024, 70(5): 603-612.)

[5] 王佐成, 张雪娇, 孙鸣, 等. 生理环境下α-丙氨酸消除羟自由基反应的理论研究[J]. 江西师范大学学报(自然科学版), 2026, 50(1):92-101.

[6] (Wang Z C, Zhang X J, Sun M, et al. The Theoretical Study of Hydroxyl Radical Scavenging by α-Alanine under Physiological Conditions[J]. Journal of Jiangxi Normal University (Natural Science Edition), 2026, 50(1): 92-101.)

[7] 王佐成, 闫红彦, 赵红迪, 等. 生理环境下缬氨酸消除羟自由基反应的密度泛函理论研究[J]. 江西师范大学学报(自然科学版), 2026, 50(2):147-156.

[8] (Wang Z C, Yan H Y, Zhao H D, et al. The Density Functional Theory Study on the Elimination of Hydroxyl Radical Catalyzed by Val under Physiological Conditions[J]. Journal of Jiangxi Normal University (Natural Science Edition), 2026, 50(2): 147-156.)

[9] 杨静, 张雪娇, 孙冠军, 等. 生理环境下双α-丙氨酸螯合钾清除羟自由基的反应机理[J]. 中山大学学报(自然科学版中英文), 2025, 64(6):53-61.

[10] (Yang J, Zhang X J, Sun G J, et al. Reaction Mechanism of Potassium Chelated by Two α-Alanine Molecules for Scavenging Hydroxyl Radicals under Physiological Conditions[J]. Acta Scientiarum Naturalium Universitatis Sunyatseni, 2025, 64(6): 53-61.)

[11] 姜春旭, 吕东月, 杨静, 等. 生理环境下双丙氨酸二价铜消除羟自由基的反应机制[J]. 复旦学报(自然科学版), 2025, 64(4):437-447.

[12] (Jiang C X, Lü D Y, Yang J, et al. Reaction Mechanism of Hydroxyl Radical Elimination by Bis-alanine Divalent Copper in Physiological Environment[J]. Fudan Journal (Natural Science), 2025, 64(4): 437-447.)

[13] 王月囡, 张雪娇, 杨应, 等. 生理环境下双α-丙氨酸螯合钙消除羟自由基的反应机制[J]. 南开大学学报(自然科学版), 2025, 58(4):108-119.

[14] (Wang Y N, Zhang X J, Yang Y, et al. Reaction Mechanism of Hydroxyl Radical Elimination by Bis-α-alanine Chelated Calcium under Physiological Conditions[J]. Journal of Nankai University (Natural Science Edition), 2025, 58(4): 108-119.)

[15] 姜春旭, 王佐成, 赵红迪, 等. 水液相下2α-A→Mg²⁺清除·OH反应的密度泛函理论研究[J]. 吉林大学学报(理学版), 2025, 63(6):1784-1794.

[16] (Jiang C X, Wang Z C, Zhao H D, et al. Density Functional Theory by 2α-Ala→Mg²⁺ Scavenging ·OH Reaction in Aqueous Phase[J]. Journal of Jilin University (Science Edition), 2025, 63(6): 1784-1794.)

[17] 王佐成, 杨静, 吴静, 等. 生理环境下2α-Ala→Na⁺消除·OH反应的密度泛函理论研究[J]. 江西师范大学学报(自然科学版), 2025, 49(4):401-409.

[18] (Wang Z C, Yang J, Wu J, et al. The Density Functional Theory Study of the OH Elimination Reaction of 2α-Ala→Na⁺ in a Physiological Setting[J]. Journal of Jiangxi Normal University (Normal Science Edition), 2025, 49(4): 401-409.)

[19] Gorb L, Leszczynski J. Intramolecular Proton Transfer in Mono- and Dihydrated Tautomers of Guanine: An ab initio Post Hartree-Fock Study[J]. Journal of the American Chemical Society, 1998, 120(20): 5024-5032.

[20] 苏旭发, 杨应, 杨清荟, 等. 水溶液环境下维生素C与羟基自由基反应的DFT研究[J]. 江西师范大学学报(自然科学版), 2024, 48(2):147-157.

[21] (Su X F, Yang Y, Yang Q H, et al. DFT Study of the Reaction between Vitamin C and Hydroxyl Radicals in Aqueous Solution[J]. Journal of Jiangxi Normal University (Normal Science Edition), 2024, 48(2): 147-157.)

[22] 王佐成, 赵宇, 杨静, 等. 水液相下沙利度胺与羟基自由基反应的密度泛函理论研究[J]. 江西师范大学学报(自然科学版), 2025, 49(1):58-72.

[23] (Wang Z C, Zhao Y, Yang J, et al. The Density Functional Theory Study of Reaction between Thalidomide and Hydroxyl Radicals in Aqueous Liquid Phase[J]. Journal of Jiangxi Normal University (Natural Science Edition), 2025, 49(1): 58-72.)

[24] 王佐成, 赵宇, 闫红彦, 等. 生理环境下没食子酸甲酯消除羟基自由基的理论研究[J]. 武汉大学学报(理学版), 2025, 71(6):881-891.

[25] (Wang Z C, Zhao Y, Yan H Y, et al. Theoretical Study on the Scavenging of Hydroxyl Radical by Methyl Gallate under Physiological Conditions[J]. Journal of Wuhan University (Natural Science Edition), 2025, 71(6): 881-891.)

[26] 杨静, 闫红彦, 赵红迪, 等. 生理环境下没食子酸乙酯与羟基自由基反应的理论研究[J]. 浙江大学学报(理学版), 2026, 53(4):490-499.

[27] (Yang J, Yan H Y, Zhao H D, et al. Theoretical Study on the Reaction between Ethyl Gallate and Hydroxyl Radicals under Physiological Conditions[J]. Journal of Zhejiang University (Natural Science Edition), 2026, 53(4): 490-499.)

[28] 王月囡, 闫红彦, 吴琳, 等. 生理环境下苹果酸消除羟自由基反应的密度泛函理论研究[J]. 南开大学学报(自然科学版), 2025, 58(5):68-79.

[29] (Wang Y N, Yan H Y, Wu L, et al. Density Functional Theory Study on the Reaction Mechanism of MA Eliminating OH in Physiological Environment[J]. Journal of Nankai University (Natural Science), 2025, 58(5): 68-79.)

[30] 赵宇, 杨应, 刘芳, 等. 水液相下缬氨酸钠配合物对映异构的密度泛函理论研究[J]. 复旦学报(自然科学版), 2024, 63(6):784-794.

[31] (Zhao Y, Yang Y, Liu F, et al. Density Functional Theory Study on Enantiomeric of Sodium Valine Complex in Aqueous Liquid Phase[J]. Journal of Fudan University (Natural Science), 2024, 63(6): 784-794.)

[32] Wang Y, Verma P, Zhang L J, et al. M06-SX Screened-Exchange Density Functional for Chemistry and Solid-State Physics[J]. Proceedings of the National Academy of Sciences of the United States of America, 2020, 117(5): 2294-2301.

[33] Garrett B C, Truhlar D G. Criterion of Minimum State Density in the Transition State Theory of Bimolecular Reactions[J]. The Journal of Chemical Physics, 1979, 70(4): 1593-1598.

[34] Hratchian H P, Schlegel H B. Using Hessian Updating to Increase the Efficiency of a Hessian Based Predictor-Corrector Reaction Path Following Method[J]. Journal of Chemical Theory and Computation, 2005, 1(1): 61-69.

[35] Yu H S, He X, Li S L, et al. MN15: A Kohn-Sham Global-Hybrid Exchange-Correlation Density Functional with Broad Accuracy for Multi-reference and Single-Reference Systems and Noncovalent Interactions[J]. Chemical Science, 2016, 7(8): 5032-5051.

[36] Marenich A V, Cramer C J, Truhlar D G. Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions[J]. The Journal of Physical Chemistry B, 2009, 113(18): 6378-6396.

[37] Marcus R A. Electron Transfer Reactions in Chemistry. Theory and Experiment[J]. Journal of Electroanalytical Chemistry, 1997, 438: 215-259.

基金资助

吉林省教育厅科学研究项目(JJKH20261226KJ)

吉林省自然科学基金(YDZJ202401628ZYTS)