Headgroup-Specific Interaction of Biological Lipid Monolayer/Water Interface with Perfluorinated Persistent Organic Pollutant (f-POP): As Observed with Interface-Selective Vibrational Spectroscopy

Perfluoro compounds are widely used in various manufacturing processes, which leads to their bioaccumulation and subsequent adverse effects on human health. Using interface-selective vibrational spectroscopy (heterodyne-detected vibrational sum frequency generation (HD-VSFG)), we have elucidated the molecular mechanism of the perturbation of lipid monolayers on the water surface using a prototype perfluorinated persistent organic pollutant, perfluoroheptanoic acid (PFHA). PFHA disrupts the well-ordered alltrans conformation of a cationic lipid (1,2-dipalmitoyl-3-trimethylammonium propane (DPTAP)) monolayer and reduces the interfacial electric field at the lipid/water interface. In contrast, the hydrophobic packing of an anionic lipid (1,2-dipalmitoyl-sn-glycero-3-phospoglycerol (DPPG)) monolayer remains largely unaffected in the presence of PFHA, though the interfacial electric field is reduced. For a zwitterionic lipid (1,2-dipalmitoyl-sn-glycero-3- phosphocholine (DPPC))/water interface, both alkyl chain ordering and interfacial electric field are fairly perturbed by PFHA. Lipid headgroup-specific interaction of PFHA and the repulsive interaction of oleophobic fluoroalkyl chain with the lipid alkyl chains govern these distinct perturbations of the lipid monolayers on the water surface.

Automated summary

Perfluoro compounds, commonly used in manufacturing processes, lead to bioaccumulation and negative effects on human health. This study investigated the perturbation of lipid monolayers on the water surface by a prototype perfluorinated persistent organic pollutant, highlighting the disruption of lipid arrangements and interfacial electric fields by PFHA, influenced by specific interactions with lipid headgroups and oleophobic fluoroalkyl chains.