Thermodynamic and Kinetic Study of Ibuprofen with Hydroxyl Radical: A Density Functional Theory Approach

被引:102
作者
Xiao, Ruiyang [1 ]
Noerpel, Matthew [1 ]
Luk, Hoi Ling [2 ]
Wei, Zongsu [1 ]
Spinney, Richard [2 ]
机构
[1] Ohio State Univ, Dept Civil Environm & Geodet Engn, Columbus, OH 43210 USA
[2] Ohio State Univ, Dept Chem & Biochem, Columbus, OH 43210 USA
关键词
ibuprofen; ibuprofen anion; hydroxyl radical; density functional theory; H-atom abstraction; thermodynamic and kinetic study; PERSONAL CARE PRODUCTS; ADVANCED OXIDATION PROCESSES; LASER FLASH-PHOTOLYSIS; RATE CONSTANTS; AB-INITIO; QUANTUM-CHEMISTRY; PHARMACEUTICALS; DEGRADATION; ENVIRONMENT; OZONATION;
D O I
10.1002/qua.24518
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ibuprofen, a frequently detected pharmaceutical in natural and engineered waters, was studied in both neutral and anionic forms using density functional theory at the B3LYP/6-311++G**//B3LYP/6-31G* level of theory in its reaction with hydroxyl radical (center dot OH). The reaction pathways included center dot OH addition to aromatic ring, abstraction of a H-atom, and nucleophilic attack on the carbonyl group. The results showed that H-atom abstraction pathways are the most favorable. The free energy change for H-atom abstraction reaction ranges from -37.8 to -15.9 kcal/mol; for center dot OH addition ranges from -3.85 to -1.23 kcal/mol; and for nucleophilic attack on the carbonyl group is 13.9 kcal/mol. The calculated rate constant between neutral ibuprofen and center dot OH, 6.72 x 10(9) M(-1)s(-1), is consistent with the experimental value, 6.5 +/- 0.2 x 10(9) M(-1)s(-1). Our results provide direct evidence for byproduct formation and identification on the molecular level. (c) 2013 Wiley Periodicals, Inc.
引用
收藏
页码:74 / 83
页数:10
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