Base-catalyzed hydrolysis mechanism of polychlorinated dibenzo-p-dioxins based on quantitative structure-activity relationship

Polychlorinated dibenzo-p-dioxins (PCDDs) are persistent organic pollutants that pose considerable threats to ecological and human health owing to their high toxicity potential. Understanding the mechanisms for underlying the base-catalyzed hydrolysis of PCDDs in aquatic environments is essential for assessing their environmental behaviour and ecological risks. Herein, we combined quantitative structure-activity relationship (QSAR) models with density functional theory calculations to analyse the base-catalyzed hydrolysis mechanisms of PCDDs. Among the four developed QSAR models, the single-parameter QSAR model based on the lowest unoccupied molecular orbital energy (E_LUMO) demonstrated the best performance, achieving a coefficient of determination of 0.89 and a root mean square error of 0.49, indicating superior overall performance. Results indicate that the second-order rate constants for base-catalyzed hydrolysis (k_OH) of PCDDs are primarily influenced by E_LUMO, molecular polarizability (α), molecular volume (V_m), degree of chlorination (N_Cl), and chlorine position. Specifically, increases in the α and V_m values of PCDDs lead to higher logk_OH values, while an increase in the E_LUMO value results in a lower logk_OH value. This study elucidates the relationship between the molecular structure and the rate of base-catalyzed hydrolysis of PCDDs for the first time, providing valuable insight into their environmental fate. Furthermore, this research offers a novel theoretical perspective on the base-catalyzed hydrolysis of PCDDs, which will aid in regulatory assessments and risk management.