title: ATR-FTIR study of lipopolysaccharides at mineral surfaces.
abstract: Lipopolysaccharides (LPS) are ubiquitous in natural aqueous systems because of bacterial cell turnover and lysis. LPS sorption and conformation at the mineral/water interface are strongly influenced by both solution and surface chemistry. In this study, the interaction of LPS with various surfaces (ZnSe, GeO(2), alpha-Fe(2)O(3), alpha-Al(2)O(3)) that vary in surface charge and hydrophobicity was investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The presence of Ca(2+) (versus Na(+)) in LPS solutions resulted in aggregate reorientation and increased sorptive retention. ATR-FTIR spectra of Na-LPS systems are consistent with reduced surface affinity and are similar to those of solution phase LPS. Ca-LPS spectra reveal hydrophobic interactions of the lipid A region at the ZnSe internal reflection element (IRE). However, pH-dependent charge controls Ca-LPS sorption to hydrophilic surfaces (GeO(2), alpha-Fe(2)O(3), and alpha-Al(2)O(3)), where bonding occurs principally via O-antigen functional groups. As a result of accumulation at the solid-liquid interface, spectra of Ca-LPS represent primarily surface-bound LPS. Variable-angle ATR-FTIR spectra of Ca-LPS systems show depth-dependent trends that occur at the spatial scale of LPS aggregates, consistent with the formation of vesicular structures.
authors.affiliation: Department of Plant and Soil Sciences, University of Delaware, Newark, DE 19716, United States.
authors.forename: Sanjai J
authors.initials: SJ
authors.lastname: Parikh
authors.forename: Jon
authors.initials: J
authors.lastname: Chorover
mesh_terms: D000327:Adsorption; D000465:Algorithms; D002118:Calcium / Q000737:chemistry; D004731:Endotoxins / Q000737:chemistry; D005857:Germanium / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D008070:Lipopolysaccharides / Q000737:chemistry*; D008903:Minerals / Q000737:chemistry; D008968:Molecular Conformation; D019081:O Antigens / Q000737:chemistry; D010087:Oxides / Q000737:chemistry; D012643:Selenium / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013499:Surface Properties; D015032:Zinc / Q000737:chemistry
chemical_list: D004731:Endotoxins; D008070:Lipopolysaccharides; D008903:Minerals; D019081:O Antigens; D010087:Oxides; D005857:Germanium; D012643:Selenium; D015032:Zinc; D002118:Calcium