Regioselective oxidation of heterocyclic aromatic hydrocarbons catalyzed by cytochrome P450: A case study of carbazole.

Recently there are increasing interests in accurately evaluating the health effects of heterocyclic PAHs. However, the activation mechanism and possible metabolites of heterocyclic PAHs catalyzed by human CYP1A1 is still elusive to a great extent. Here, leveraged to high level QM/MM calculations, the corresponding activation pathways of a representative heterocyclic PAHs, carbazole, were systematically explored. The first stage is electrophilic addition or hydrogen abstraction from N-H group. Electrophilic addition was evidenced to be more feasible and regioselectivity at C3 and C4 sites were identified. Correlations between energy barriers and key structural/electrostatic parameters reveal that O-Cα distance and Fe-O-Cα angle are the main origin for the catalytic regioselectivity. Electrophilic addition was determined as the rate-determining step and the subsequent possible reactions include epoxidation, NIH shift (the hydrogen migration from the site of hydroxylation to the adjacent carbon) and proton shuttle. The corresponding products are epoxides, ketones and hydroxylated carbazoles, respectively. The main metabolites (hydroxylated carbazoles) are estimated to be more toxic than carbazole. The regioselectivity of carbazole activated by CYP1A1 is different from the environmental processes (gas and aqueous phase). Collectively, these results will inform the in-depth understanding the metabolic processes of heterocyclic PAHs and aid the accurate evaluation of their health effects.

Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co-N4-C Intensified Radical and Nonradical Pathways.

Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co-N4-C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO4•- and HO•) and nonradical electron-transfer pathway (ETP) co-existed in the Co-N4-C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co-N4-C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the oxidation potential of Co-N4-C-PMS* complexes in ETP. Findings from this work will unravel the mysterious selective behavior of the SACs/PMS systems in the oxidation of different micropollutants.

Repeated fluctuation of Cu2+ concentration during photocatalytic purification of SMZ-Cu2+ combined pollution: Behavior, mechanism and application.

Although the effect of Cu2+ on antibiotic removal during photocatalytic reaction has been studied in depth, there is less known about the effect of antibiotics on Cu2+ removal. In this study, we report for the first time that, during the photocatalytic purification of sulfamerazine (SMZ) and Cu2+ combined pollution, Cu2+ concentration showed an obvious five-stage fluctuation, which was completely different from the simple promotion or inhibition reported in previous studies. By employing HPLC-MS analysis and density functional theory (DFT) calculation, the repeated fluctuation of Cu2+ concentration was found to be closely related to the SMZ degradation process, mainly resulting from solution pH drop and formation of Cu-containing intermediates which acted as sacrificial agents for Cu2+ reduction. In addition, compared with the SMZ-free system, the presence of SMZ can greatly enhance the deep removal of Cu2+ (minimum Cu2+ concentration was only 0.17 mg/L vs. 1.28 mg/L without SMZ), and there was a wide time interval to ensure the efficient recovery of Cu metal. More interestingly, the in-situ obtained Cu-decorated TiO2 photocatalyst performed well in water splitting, nitrogen fixation and bacterial sterilization. Results of this study confirmed the great potential of photocatalytic technology in purifying antibiotic-heavy metal combined pollution.