Long Tairen, Wan Haiyan, Zhang Jianqiang, Wu Jie, Liang Jin-Xia, Zhu Chun
School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, China.
Guizhou Fukangren Pharmaceutical Co., Ltd, Guiyang, China.
Front Chem. 2022 Jun 2;10:884105. doi: 10.3389/fchem.2022.884105. eCollection 2022.
The degradation of BaP into hydroxybenzo[a]pyrene by Mn-corrolazine and its regulation by an oriented external electronic field (OEEF) were systematically studied using first-principle calculations. Extensive density function calculations showed that the degradation of BaP into hydroxybenzo[a]pyrene by Mn-corrolazine occurs a three-step process in the absence of OEEF, in which a more toxic and stable epoxide intermediate is generated. However, upon application of OEEF along the intrinsic Mn-O reaction axis, the degradation of BaP into hydroxybenzo[a]pyrene is greatly simplified. The negative charge on the terminal O atom of Mn-OO corrolazine increases with an increase in the OEEF intensity. As the intensity of the OEEF increases over 0.004 a.u., the negatively charged terminal O atom has the ability to directly abstract the positively charged H atom of BaP and the degradation of BaP into hydroxybenzo[a]pyrene can be completed a one-step process, avoiding the production of more toxic epoxide intermediates.
利用第一性原理计算系统地研究了锰-咕啉将苯并[a]芘降解为羟基苯并[a]芘及其受定向外部电场（OEEF）调控的情况。大量密度泛函计算表明，在不存在OEEF的情况下，锰-咕啉将苯并[a]芘降解为羟基苯并[a]芘是一个三步过程，在此过程中会生成毒性更强且更稳定的环氧化合物中间体。然而，当沿固有的锰-氧反应轴施加OEEF时，苯并[a]芘向羟基苯并[a]芘的降解过程大大简化。随着OEEF强度的增加，锰-氧咕啉末端氧原子上的负电荷增加。当OEEF强度增加超过0.004原子单位时，带负电荷的末端氧原子能够直接夺取苯并[a]芘带正电荷的氢原子，苯并[a]芘向羟基苯并[a]芘的降解可以一步完成，避免了生成毒性更强的环氧化合物中间体。
