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. 2023 Nov;42(11):2317-2328.
doi: 10.1002/etc.5716. Epub 2023 Aug 17.

Modeling the Partitioning of Anionic Carboxylic and Perfluoroalkyl Carboxylic and Sulfonic Acids to Octanol and Membrane Lipid

Tifany L Torralba-Sanchez  1 , Dominic M Di Toro  2 , Olga Dmitrenko  2 , Jimmy Murillo-Gelvez  2 , Paul G Tratnyek  3
Affiliations

Modeling the Partitioning of Anionic Carboxylic and Perfluoroalkyl Carboxylic and Sulfonic Acids to Octanol and Membrane Lipid

Tifany L Torralba-Sanchez et al. Environ Toxicol Chem. 2023 Nov.

Abstract

Perfluoroalkyl carboxylic and sulfonic acids (PFCAs and PFSAs, respectively) have low acid dissociation constant values and are, therefore, deprotonated under most experimental and environmental conditions. Hence, the anionic species dominate their partitioning between water and organic phases, including octanol and phospholipid bilayers which are often used as model systems for environmental and biological matrices. However, data for solvent-water (SW) and membrane-water partition coefficients of the anion species are only available for a few per- and polyfluoroalkyl substances (PFAS). In the present study, an equation is derived using a Born-Haber cycle that relates the partition coefficients of the anions to those of the corresponding neutral species. It is shown via a thermodynamic analysis that for carboxylic acids (CAs), PFCAs, and PFSAs, the log of the solvent-water partition coefficient of the anion, log KSW (A- ), is linearly related to the log of the solvent-water partition coefficient of the neutral acid, log KSW (HA), with a unity slope and a solvent-dependent but solute-independent intercept within a PFAS (or CA) family. This finding provides a method for estimating the partition coefficients of PFCAs and PFSAs anions using the partition coefficients of the neutral species, which can be reliably predicted using quantum chemical methods. In addition, we have found that the neutral octanol-water partition coefficient, log KOW , is linearly correlated to the neutral membrane-water partition coefficient, log KMW ; therefore, log KOW , being a much easier property to estimate and/or measure, can be used to predict the neutral log KMW . Application of this approach to KOW and KMW for PFCAs and PFSAs demonstrates the utility of this methodology for evaluating reported experimental data and extending anion property data for chain lengths that are unavailable. Environ Toxicol Chem 2023;42:2317-2328. © 2023 SETAC.

Keywords: Abraham pp-LFER; Environmental partitioning; In silico calibration; Poly- and perfluoroalkyl substances; QSAR; Speciation; log KOW; pKa.

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