Elucidating the state of interfacial water, especially the hydrogen-bond configurations, is considered to be key for a better understanding of the functions of polymers that are exhibited in the presence of water. Here, an analysis in this direction is conducted for two water-insoluble biocompatible polymers, poly(2-methoxyethyl acrylate) and cyclic(poly(2-methoxyethyl acrylate)), and a non-biocompatible polymer, poly(n-butyl acrylate), by measuring their IR spectra under humidified conditions and by carrying out theoretical calculations on model complex systems. It is found that the OH stretching bands of water are decomposed into four components, and while the higher-frequency components (with peaks at ∼3610 and ∼3540 cm^-1) behave in parallel with the C═O and C-O-C stretching and CH deformation bands of the polymers, the lower-frequency components (with peaks at ∼3430 and ∼3260 cm^-1) become pronounced to a greater extent with increasing humidity. From the theoretical calculations, it is shown that the OH stretching frequency that is distributed from ∼3650 to ∼3200 cm^-1 is correlated to the hydrogen-bond configurations and is mainly controlled by the electric field that is sensed by the vibrating H atom. By combining these observed and calculated results, the configurations of water at the interface of the polymers are discussed.

The correlation between the interfacial structure and protein adsorption at a polymer/water interface was investigated. Poly(2-methoxyethyl acrylate)(PMEA), which is one of the best blood compatible polymers available, was employed. Nanometer-scale structures generated through the phase separation of polymer and water were observed at the PMEA/phosphate buffered saline interface. The interaction between the interfacial structures and fibrinogen (FNG) was measured using atomic force microscopy. Attraction was observed in the polymer-rich domains as well as in the non-blood compatible polymer. In contrast, no attractive interactions were observed, and only a repulsion occurred in the water-rich domains. The non-adsorption of FNG into the water rich domains was also clarified through topographic and phase image analyses. Furthermore, the FNG molecules adsorbed on the surface of PMEA were easily desorbed, even in the polymer-rich domains. Water molecules in the water-rich domains are anticipated to be the dominant factor in preventing FNG adsorption and thrombogenesis on a PMEA interface.