Binding interaction of environmental DNA with typical emerging perfluoroalkyl acids and its impact on bioavailability

As the replacement compounds of perfluoroalkyl acids (PFAAs), emerging PFAAs generally exhibit equal or more hazardous toxicity than legacy PFAAs. Numerous DNA as environmental organic matters coexists with emerging PFAAs, but their interactions and the resulting interaction impacts on the bioavailability of emerging PFAAs remain insufficiently understood. Here, we studied the binding strength and mechanism between DNA and emerging PFAAs (perfluorobutyric acid, perfluorobutylsulfonic acid, and hexafluoropropylene oxide dimer acid) using perfluorooctanoic acid as the control, and further investigated the impacts of DNA binding on the bioavailability of the emerging PFAAs. Isothermal titration calorimetry and quantum chemical calculation found that the emerging PFAAs could bind with DNA bases (main thymine) by van der Waals force and halogen-bond, showing the binding affinities in the range of 7.87 x 104 to L/mol to 6.54 x 106 L/mol. The PFAAs-DNA binding significantly decreased the bioavailability of the PFAAs in both seedlings and plants of pakchoi (Brassica chinensis L.), with little differences in bioavailability change extent among PFAAs. The findings highlight the universality and similarity of the DNA binding effects on PFAAs bioavailability, which can be the natural detoxification mechanism for response to the PFAAs pollution.