ATR-FTIR studies of phospholipid vesicle interactions with α-FeOOH and α-Fe₂O₃ surfaces

Prior infrared spectroscopic studies of extracellular polymeric substances (EPS) and live bacterial cells have indicated that organic phosphate groups mediate cell adhesion to iron oxides via inner-sphere P-OFe surface complexation. Since cell membrane phospholipids are a potential source of organic phosphate groups, we investigated the adhesion of phospholipidic vesicles to the surfaces of the iron (oxyhydr)oxides goethite (α-FeOOH) and hematite (α-Fe₂O₃) using attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. l-α-Phosphatidylcholine (PC), phosphatidylethanolamine (PE) and phosphatidic acid (PA) were used because they are vesicle forming phospholipids representative of prokaryotic and eukaryotic cell surface membranes. Phospholipid vesicles, formed in aqueous suspension, were characterized by transmission electron microscopy (TEM), multi-angle laser light scattering (MALS) and quasi-elastic light scattering (QELS). Their adhesion to goethite and hematite surfaces was studied with ATR-FTIR at pH 5. Results indicate that PC and PE adsorption is affected by electrostatic interaction and H-bonding (PE). Conversely, adsorption of PA involves phosphate inner-sphere complexes, for both goethite and hematite, via P-OFe bond formation. Biomolecule adsorption at the interface was observed to occur on the scale of minutes to hours. Exponential and linear increases in peak intensity were observed for goethite and hematite, respectively. Our ATR-FTIR results on the PA terminal phosphate are in good agreement with those on EPS reacted with goethite and on bacterial cell adhesion to hematite. These findings suggest that the plasma membrane, and the PA terminal phosphate in particular, may play a role in mediating the interaction between bacteria and iron oxide surfaces during initial stages of biofilm formation.