title: Spectroscopic ellipsometry of mucin layers on an amphiphilic diblock copolymer surface.
abstract: Both visible and infrared (IR) spectroscopic ellipsometry have been employed to study the structure of thin layers of bovine submaxillary mucin (BSM) adsorbed on poly(acrylic acid-block-methyl methacrylate) (PAA-b-PMMA) copolymer and poly(methyl methacrylate) (PMMA) surfaces at three pH values (3, 7, and 10). The adsorbed mucin layer on the copolymer surface had the greatest thickness (17 nm) when adsorbed from a mucin solution at a pH of 3. For the first time, IR ellipsometry was used to identify adhesive interactions and conformational changes in mucin/polymer double layers. After applying the regularized method of deconvolution in the analysis, the formation of hydrogen bonds between the carboxyl groups of the BSM and PAA-b-PMMA copolymer in double layers has been found. The IR ellipsometry data, in agreement with the visible ellipsometry analysis, indicate the pH dependence of adhesion of mucin to the copolymer surface. There is an increase in the amount of hydrogen-bonded carboxyl groups in mucin deposited at a pH of 3. There is no evidence that the amide groups of the mucin participate in this bonding. At the lower pH, the IR ellipsometry spectra after deconvolution reveal an increase in the proportion of beta-sheets in the BSM upon adsorption on the copolymer surface, indicating a more unfolded, aggregated structure. The IR ellipsometry data also indicated some changes in the conformational states of the side groups in the copolymer induced by entanglements and bonding interactions with the mucin macromolecules. Deconvolution provides an unprecedented level of information from the IR ellipsometry spectra and yields important insights.
authors.affiliation: B.I. Stepanov Institute of Physics, National Academy of Sciences of Belarus, Nezalezhnasti Ave. 68, 220072 Minsk, Belarus. na_nikonenko@yahoo.ca
authors.forename: Nataliya A
authors.initials: NA
authors.lastname: Nikonenko
authors.forename: Ibraheem A
authors.initials: IA
authors.lastname: Bushnak
authors.forename: Joseph L
authors.initials: JL
authors.lastname: Keddie
mesh_terms: D000327:Adsorption; D000818:Animals; D002417:Cattle; D006046:Gold / Q000737:chemistry; D006860:Hydrogen Bonding; D006863:Hydrogen-Ion Concentration; D015394:Molecular Structure; D009077:Mucins / Q000737:chemistry*; D011109:Polymethacrylic Acids / Q000737:chemistry*; D019904:Polymethyl Methacrylate / Q000737:chemistry; D013055:Spectrophotometry, Infrared / Q000379:methods*; D013499:Surface Properties
chemical_list: D009077:Mucins; D011109:Polymethacrylic Acids; C507106:poly(acrylic acid-co-methyl methacrylate); D006046:Gold; D019904:Polymethyl Methacrylate