Structure of water at zwitterionic copolymer film-liquid water interfaces as examined by the sum frequency generation method

A copolymer film composed of zwitterionic carboxymethylbetaine (CMB) and n-butyl methacrylate (BMA), Poly(CMB r-BMA), was cast on a flat plane of an octadecyltrichlorosilane (ODS)-modified fused quartz prism with a semi-cylindrical shape. C. H stretching of the polymer film and O. H stretching of water at the surface of the film were examined using the sum frequency generation (SFG) technique. The C. H stretching band of the cast film, indicating a gauche defect of the film, was affected by the contact medium including dry nitrogen, water vapor-saturated nitrogen and liquid water. In contrast, the C. H stretching of an octadecyl group introduced onto the quartz prism for stable attachment of the cast film was not significantly changed by the contact medium. The O. H stretching band indicated that water molecules at the surface of the Poly(CMB r-BMA) film in contact with liquid water were not greatly oriented in comparison with those at the surfaces of a bare prism, an ODS SAM-modified prism, and a prism covered with a PolyBMA film or a copolymer film of BMA and methacrylic acid or 2-(dimethylamino)ethyl methacrylate. A similar small perturbation of the structure of water was previously observed in the vicinity of water-soluble zwitterionic polymers and zwitterionic copolymer films using Raman and attenuated total reflection infrared spectroscopies, respectively. A distinct effect of charge neutralization to diminish the perturbation of the structure of interfacial water around polymer materials was suggested.