Singlet oxygen production abilities of oxidated aromatic compounds in natural water

Singlet oxygen (¹O₂) is well known to be formed through energy transfer from excited state organic matters to O₂, playing an important role in the transformations of contaminants. However, the contribution of small oxidated aromatic compounds (OACs) to the production of ¹O₂ in surface water is unclear. In this study, 28 OACs were selected to investigate the correlations between their photochemical production abilities of ¹O₂ and molecular structures. Our results showed that the steady-state concentrations and quantum yields of ¹O₂ (Φ_1O2) generated by OACs were in the range of 7.0 × 10^-14-1.4 × 10^-12 M and 2.2 × 10^-4-4.7 × 10^-2, respectively, indicating that the photochemical production abilities of ¹O₂ by OACs varied greatly with types and positions of functional groups on the molecule. More importantly, the observed photochemical production of ¹O₂ was most notable in cases of molecules containing -OCH₃ group and benzoquinone. A good quantitative structure-property relationship model was established between ¹O₂ producing ability, energy of the lowest unoccupied molecular orbitals (E_LUMO) and the most positive net charge of hydrogen atoms (qH⁺) of OACs. In addition, the role of ¹O₂ produced by 2, 6-dimethoxy-1, 4-benzoquinone, the OAC with the highest Φ_1O2, in the photodegradation of organic contaminants was validated by the enhanced degradation of atorvastatin under simulated sunlight, suggesting that OACs ubiquitously existed in surface water may greatly affect the fate and ecological risks of organic contaminants.