Structural investigation of the complexation between vitamin B12 and per- and polyfluoroalkyl substances: Insights into degradation using density functional theory.

ABSTRACT

Environmental remediation of per- and polyfluoroalkyl substances (PFAS) has become a significant research topic in recent years due to the fact that these materials are omnipresent, resistant to degradation and thus environmentally persistent. Unfortunately, they have also been shown to cause health concerns. PFAS are widely used in industrial applications and consumer products. Vitamin B12 (B12) has been identified as being catalytically active towards a variety of halogenated compounds such as PFAS. It has also been shown to be effective when using sulfide as a reducing agent for B12. This is promising as sulfide is readily available in the environment. However, there are many unknowns with respect to PFAS interactions with B12. These include the reaction mechanism and B12's specificity for PFAS with certain functionalization(s). In order to understand the specificity of B12 towards branched PFAS, we examined the atomistic interactions between B12 and eight different PFAS molecules using Density Functional Theory (B3LYP/cc-pVDZ). The PFAS test set included linear PFAS and their branched analogs, carboxylic acid and sulfonic acid headgroups, and aromatic and non-aromatic cyclic structures. Conformational analyses were carried out to determine the lowest energy configurations. This analysis showed that small chain PFAS such as perfluorobutanoic acid interact with the cobalt center of B12. Bulkier PFAS prefer to interact with the amine and carbonyl groups on the sidechains of the B12 ring system. Furthermore, computed complexation energies determined that, in general, branched PFAS (e.g. perfluoro-5-methylheptane sulfonic acid) interact more strongly than linear molecules (e.g. perfluorooctanesulfonic acid). Our results indicate that it may be possible to alter the interactions between B12 and PFAS by synthetically modifying the sidechains of the ring structure.