Predicting Partition Coefficients of Polyfluorinated and Organosilicon Compounds using Polyparameter Linear Free Energy Relationships (PP-LFERs)

Abstract

The environmental behavior, fate, and effects of polyfluorinated compounds (PFCs) and organosilicon compounds (OSCs) have received increasing attention in recent years. In this study, polyparameter linear free energy relationships (PP-LFERs) were evaluated for predicting partition coefficients of neutral PFCs and OSCs, using experimental data for fluorotelomer alcohols (FTOHs) and cyclic volatile methylsiloxanes (cVMS) reported in the literature and measured newly for this work. It was found that the recently proposed PP-LFER model that uses the McGowan characteristic volume (V), the logarithmic hexadecane-air partition coefficient (L), and three polar interaction descriptors can accurately describe partition coefficients of PFCs and OSCs. The prediction errors were <1 log unit when literature descriptors were used, and the errors were reduced to <0.2 log units on average by further optimization of the descriptors. Surprisingly, the conventional forms of PP-LFERs that include the excess molar refraction (E) sometimes led to substantial errors (>1 log unit) even with optimized parameters. The system parameters for octanol-water, air-water, octanol-air, oil-water, liposome-water, and organic carbon-water partition coefficients as well as the solute descriptors for FTOHs and cVMS were recalibrated in this work, which should provide even more reliable predictions of partition coefficients. The results also confirm the consistency of the published experimental partition coefficients for FTOHs and cVMS.