Unveiling chlorine's role: How it shapes the formation and light-activated oxygen dynamics of chlorophenol-derived environmental persistent free radicals

Xingzhi Jin; Di Gao; Chunyan Zhang; Chen Chen; Yuyue Li; Hao Chen; Peng Cai; Jianwei Li; Xing Ding

doi:10.1016/j.jhazmat.2024.135870

Unveiling chlorine's role: How it shapes the formation and light-activated oxygen dynamics of chlorophenol-derived environmental persistent free radicals

J Hazard Mater. 2024 Sep 16:480:135870. doi: 10.1016/j.jhazmat.2024.135870. Online ahead of print.

Authors

Xingzhi Jin¹, Di Gao¹, Chunyan Zhang¹, Chen Chen¹, Yuyue Li¹, Hao Chen¹, Peng Cai², Jianwei Li³, Xing Ding⁴

Affiliations

¹ College of Chemistry, Huazhong Agricultural University, Wuhan 430070, China.
² National Key Laboratory of Agricultural Microbiology, Huazhong Agricultural University, Wuhan 430070, China; Hubei Key Laboratory of Soil Environment and Pollution Remediation, Huazhong Agricultural University, Wuhan 430070, China.
³ MediCity Research Laboratory, University of Turku, Tykistökatu 6, Turku 20520, Finland.
⁴ College of Chemistry, Huazhong Agricultural University, Wuhan 430070, China. Electronic address: dingx@mail.hzau.edu.cn.

PMID: 39298961
DOI: 10.1016/j.jhazmat.2024.135870

Abstract

Environmental persistent free radicals (EPFRs) derived from chlorophenols, triggered by light or heat exposure, pose significant ecological concerns, yet the impact of chlorine substituents on EPFRs formation and reactivity remains inadequately understood. Through an intentional synthesis of chlorophenol-derived EPFRs with varying chlorine contents and positioning, we elucidated the role of chlorine in the photoactivation of molecular oxygen. Our combined experimental and theoretical analysis reveals that these EPFRs are primarily oxygen-centered phenoxy radicals, establishing a direct link between chlorine substitution patterns and their ability to activate molecular oxygen under visible light. Increased chlorine content enhances EPFRs formation by elevating the positive charge on the phenolic hydroxyl group's hydrogen atom, facilitating its removal. Moreover, the capability of EPFRs to activate molecular oxygen was directly correlated with chlorine content, with 2,3,5,6-tetrachlorophenol-derived EPFRs showcasing the highest activity. This activity is attributed to their structural propensity for TCSQ^·- species generation. Furthermore, our study established a significant correlation between the toxicity and activity of EPFRs, emphasizing the critical role of halogen substituents in determining the reactivity of EPFRs. These insights contribute to our understanding of their environmental and toxicological ramifications, underscoring the imperative for continued research aimed at mitigating their detrimental impacts.

Keywords: Environmental persistent free radicals; Molecular oxygen activation; Polychlorophenol; Reactive oxygen species; Visible light.