pKa prediction of per- and polyfluoroalkyl acids in water using in silico gas phase stretching vibrational frequencies and infrared intensities
| Author(s) | Murillo-Gelvez, Jimmy | |
| Author(s) | Dmitrenko, Olga | |
| Author(s) | Torralba-Sanchez, Tifany L. | |
| Author(s) | Tratnyek, Paul G. | |
| Author(s) | Di Toro, Dominic M. | |
| Date Accessioned | 2024-01-11T14:30:08Z | |
| Date Available | 2024-01-11T14:30:08Z | |
| Publication Date | 2023-09-01 | |
| Description | This article was originally published in Physical Chemistry Chemical Physics. The version of record is available at: https://doi.org/10.1039/D3CP01390A. This article will be embargoed until 09/01/2024. | |
| Abstract | To successfully understand and model the environmental fate of per- and polyfluoroalkyl substances (PFAS), it is necessary to know key physicochemical properties (PChPs) such as pKa; however, measured PChPs of PFAS are scarce and of uncertain reliability. In this study, quantitative structure–activity relationships (QSARs) were developed by correlating calculated (M062-X/aug-cc-pVDZ) vibrational frequencies (VF) and corresponding infrared intensities (IRInt) to the pKa of carboxylic acids, sulfonic acids, phosphonic acids, sulfonamides, betaines, and alcohols. Antisymmetric stretching VF of the anionic species were used for all subclasses except for alcohols where the OH stretching VF performed better. The individual QSARs predicted the pKa for each subclass mostly within 0.5 pKa units from the experimental values. The inclusion of IRInt as a pKa predictor for carboxylic acids improved the results by decreasing the root-mean-square error from 0.35 to 0.25 (n > 100). Application of the developed QSARs to estimate the pKa of PFAS within each subclass revealed that the length of the perfluoroalkyl chain has minimal effect on the pKa, consistent with other models but in stark contrast with the limited experimental data available. | |
| Sponsor | This research was supported by the Strategic Environmental Research and Development Program (SERDP) under project ER20-1481. The computations were supported in part through the use of Information Technologies (IT) resources at the University of Delaware, specifically the high-performance computing resources. | |
| Citation | J. Murillo-Gelvez, O. Dmitrenko, T. Lorena Torralba Sánchez, P. G. Tratnyek and D. Di Toro, Phys. Chem. Chem. Phys., 2023, DOI: 10.1039/D3CP01390A. | |
| ISSN | 1463-9084 | |
| URL | https://udspace.udel.edu/handle/19716/33789 | |
| Language | en_US | |
| Publisher | Physical Chemistry Chemical Physics | |
| Title | pKa prediction of per- and polyfluoroalkyl acids in water using in silico gas phase stretching vibrational frequencies and infrared intensities | |
| Type | Article |
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