A spectroscopic study of bacterial polymers mediating cell adhesion and mineral transformations

Current understanding of molecular-level interactions is inadequate to explain the initial moments of bacterial adhesion. Such information is required to develop appropriate models for bacteria-surface interactions and predictions of cell transport in subsurface environments. Bacterial adhesion is influenced by bacterial surfaces, substratum physical-chemical characteristics, and solution chemistry. Extracellular polymeric substances (EPS), surface proteins, and lipopolysaccharides (LPS) mediate cell adhesion and conditioning film formation via direct bonding to a substrate. The goal of this dissertation is to probe molecular-scale interactions of cell surface macromolecules at mineral surfaces under environmentally-relevant conditions.; Four primary investigations are presented in this dissertation. The first study uses in situ attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy to reveal that prior to Mn-oxidation via Pseudomonas putida GB-1, cell adhesion to ZnSe is favorable. Subsequent Mn-oxidation results in increased extracellular proteins expression. Conversely, planktonic cell adhesion is inhibited for Mn-oxide coated cells via blocking of surface proteins.; The second investigation reveals the formation of inner-sphere complexes between bacteria surface phosphoryl groups and nanohematite (alpha-Fe 2O3). Spectra of bacteria (P. aeruginosa PAO1, Shewanella oneidensis MR-1, and Bacillus subtilis ) on alpha-Fe2O3 contain peaks indicative of P-OFe inner-sphere bonding. Spectra collected for oxide-adsorbed model P-containing compounds give spectral signatures similar to those P-OFe bonding interactions observed for whole cell and EPS.; The behavior of P. aeruginosa serotype 10 LPS in aqueous solutions was investigated in the third study. Ionic strength, pH, and electrolyte composition were varied during collection of ATR-FTIR and dynamic light scattering (DLS) data. Results reveal stable aggregate Na-LPS aggregates, whereas binding of Ca2+ to phosphate groups in the lipid A region leads to aggregate reorientation and increased interaction with ZnSe (hydrophobic). DLS data demonstrate decreasing hydrodynamic radius of LPS aggregates with increasing I and decreasing pH.; In the fourth investigation, ATR-FTIR was used to probe the solid-solution interface of LPS on surfaces of ZnSe, Ge, alpha-Fe2O3, and alpha-Al2O3 in solutions of varying ionic composition and pH. Na-LPS aggregates remain stable and spectra are biased towards solution phase LPS. Ca-LPS aggregates are disrupted, leading to enhanced interaction with surfaces via hydrophobic (lipid A- ZnSe) and electrostatic (O-antigen-hydrophilic surfaces) interactions.