title: Structure of collagen adsorbed on a model implant surface resolved by polarization modulation infrared reflection-absorption spectroscopy.
abstract: The polarization modulation infrared reflection-absorption spectra of collagen adsorbed on a titania surface and quantum chemical calculations are used to describe components of the amide I mode to the protein structure at a sub-molecular level. In this study, imino acid rich and poor fragments, representing the entire collagen molecule, are taken into account. The amide I mode of the collagen triple helix is composed of three absorption bands which involve: (i) (∼1690cm(-1)) the CO stretching modes at unhydrated groups, (ii) (1655-1673cm(-1)) the CO stretching at carbonyl groups at imino acids and glycine forming intramolecular hydrogen bonds with H atoms at both NH2 and, unusual for proteins, CH2 groups at glycine at a neighbouring chain and (iii) (∼1640cm(-1)) the CO stretching at carbonyl groups forming hydrogen bonds between two, often charged, amino acids as well as hydrogen bonds to water along the entire helix. The IR spectrum of films prepared from diluted solutions (c<50μgml(-1)) corresponds to solution spectra indicating that native collagen molecules interact with water adsorbed on the titania surface. In films prepared from solutions (c⩾50μgml(-1)) collagen multilayers are formed. The amide I mode is blue-shifted by 18cm(-1), indicating that intramolecular hydrogen bonds at imino acid rich fragments are weakened. Simultaneous red-shift of the amide A mode implies that the strength of hydrogen bonds at the imino acid poor fragments increases. Theoretically predicted distortion of the collagen structure upon adsorption on the titania surface is experimentally confirmed.
authors.affiliation: Carl von Ossietzky University of Oldenburg, School of Mathematics and Science, Department of Chemistry, CIS - Center of Interface Science, D-26111 Oldenburg, Germany. Electronic address: izabella.brand@uni-oldenburg.de.
authors.forename: Izabella
authors.initials: I
authors.lastname: Brand
authors.affiliation: Carl von Ossietzky University of Oldenburg, School of Mathematics and Science, Department of Chemistry, CIS - Center of Interface Science, D-26111 Oldenburg, Germany.
authors.forename: Florian
authors.initials: F
authors.lastname: Habecker
authors.affiliation: Carl von Ossietzky University of Oldenburg, School of Mathematics and Science, Department of Chemistry, CIS - Center of Interface Science, D-26111 Oldenburg, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Ahlers
authors.affiliation: Carl von Ossietzky University of Oldenburg, School of Mathematics and Science, Department of Chemistry, CIS - Center of Interface Science, D-26111 Oldenburg, Germany.
authors.forename: Thorsten
authors.initials: T
authors.lastname: Klüner
mesh_terms: D000327:Adsorption; D000577:Amides / Q000737:chemistry*; D000818:Animals; D024042:Collagen Type I / Q000737:chemistry*; D006046:Gold / Q000737:chemistry; D006860:Hydrogen Bonding; D007098:Imino Acids / Q000737:chemistry; D019736:Prostheses and Implants; D011506:Proteins / Q000737:chemistry; D051381:Rats; D012996:Solutions; D013055:Spectrophotometry, Infrared; D017550:Spectroscopy, Fourier Transform Infrared; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D000577:Amides; D024042:Collagen Type I; D007098:Imino Acids; D011506:Proteins; D012996:Solutions; D014867:Water; D006046:Gold; D014025:Titanium
keywords: Amide I mode; Collagen type I; Density functional theory calculation; IR spectrum; Titanium implant