ABSTRACT
Quenching method is widely used to assess the contribution of specified reactive species through the probe inhibition efficiency (IE) caused by adding excessive quencher. However, for reactive species with weak ability such as singlet oxygen (1O2), the quenching results are prone to ambiguity. In this study, an 1O2 system using furfuryl alcohol (FFA) as a probe was successfully constructed by methylene-blue-N vis-photosensitization, to discuss the quenching, interference elimination and pollutant degradation ability of 1O2. Inhibition of FFA transformation caused by both quenching and interrupting of 1O2 production was found. The quenching is affected by quencher dosage and ability, which depends on the second-order-rate constant (k). A high k means a strong ability, and less dosage is required to achieve the same IE. Comparison between the calculated ratio of reactive species consumed by quencher and experimental IE helps to judge the interruption of 1O2 production. None of the organic-solvents (methanol, ethanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, tetrahydrofuran, acetonitrile, acetone and chloroform) scavenged 1O2, which would be used as screening-agent for other reactive species (e.g., hydroxyl radicals) that would interrupt 1O2 contribution assessment. Besides, 1O2 was powerless to degrade most selected pollutants. These results encourage proper use of quenchers and better experimental design.
ABSTRACT
Polybrominated dibenzofurans (PBDFs) are characteristic dioxin-like products of polybrominated diphenyl ether (PBDE) photolysis. In this study, competition mechanisms of radical-based cyclization and hydrogen abstraction reactions are proposed in PBDF formation. Commonly, the ortho C-Br bond dissociation during photolysis generates aryl radicals, which undergo intramolecular cyclization to form PBDFs or hydrogen abstraction with hydrogen donors (such as organic solvents and water) to form lower brominated PBDEs. By using 2,4,4'-tribromodiphenyl ether (BDE-28) as the model reactant, the experimental PBDF formation ratios in various solutions are explained quantitatively by the calculated rate constants of cyclization and hydrogen abstraction reactions using the density functional theory (DFT) method. The solvent effect of pure and mixed solvents on PBDF formation is illustrated successfully. The structure-related hydrogen donation ability for hydrogen abstraction controls the bias of competition reactions and influences PBDF formation. Water resulted to be the most significant generation of PBDFs. Fulvic and humic acid display higher hydrogen donation ability than small-molecule organics due to the partitioning effect in aqueous solution. Quantitative structure-activity relationship (QSAR) models of the calculated rate constants for 512 cyclization and 319 hydrogen abstraction reactions using 189 PBDEs as the initial reactants in water are established, revealing the high risk of PBDF formation in aqueous solution.
