Nucleotide Adsorption on Iron(III) Oxide Nanoparticle Surfaces: Insights into Nano-Geo-Bio Interactions Through Vibrational Spectroscopy.

Molecular processes at geochemical interfaces impact many environmental processes that are critical to the fate and transport of contaminants in water systems. Often these interfaces are coated with natural organic matter, oxyanions, or biological components, yet little is understood about these coatings. Herein, we are interested in better understanding the interaction of biological components with nanoscale iron oxide minerals. In particular, we use attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to investigate the adsorption behavior of deoxyadenosine monophosphate (dAMP) on hematite nanoparticle surfaces as a function of pH and in the presence and absence of adsorbed phosphate. These results show that fewer nucleotides adsorb at higher pH. Additionally, when phosphate anions are preadsorbed, nucleotide adsorption is significantly limited due to site-blocking by adsorbed inorganic phosphate. The pH dependence provides insights into the adsorption process and the importance of electrostatic interactions. Preadsorbed phosphate affects the binding mode of dAMP, suggesting synergistic interactions between the coadsorbates. Two-dimensional correlation spectroscopy was used to further analyze the infrared spectra. Based on this analysis, a dAMP adsorption pathway onto a preadsorbed phosphate-hematite surface was proposed, suggesting the displacement of adsorbed phosphate by dAMP. Overall, this study provides some insights into geochemical-biological interactions on nanoscale iron oxide surfaces using vibrational spectroscopy.