Structure of Water in the Vicinity of Amphoteric Polymers as Revealed by Vibrational Spectroscopy

Abstract

The water incorporated in a thin film of amphoteric terpolymers composed of various ratios of methacrylic acid (MA), N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) and n-butyl methacrylate was analyzed using the band shapes of the O–H stretching in the infrared spectra. At an early stage of sorption of water into the polymer film, the O–H stretching band for the water incorporated in the film with comparative contents of MA and DMAPMA residues was similar to that for bulk water. These results clearly indicate that the amphoteric polymers with comparative contents of cationic and anionic groups do not significantly disturb the hydrogen-bonded network structure of water, probably due to the counteraction of the electrostatic hydration effect by the proximity between the anionic and cationic side groups. The number of platelets adhered to the film with comparative contents of MA and DMAPMA residues was relatively the smallest among the examined terpolymer films, which suggested a correlation between the mildness of the charge-balanced polymeric materials to the structure of incorporated water and their blood-compatibilities. In addition, the structure and hydrogen bonding of water in an aqueous solution of co-polymers composed of various ratios of MA and DMAPMA or [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) were also analyzed using the contours of the O–H stretching in the polarized Raman spectra. The number of hydrogen bonds disrupted due to the presence of one monomer residue (N corr value) for PolyMA was largely positive, and with an increase in the content of the DMAPMA or MAPTAC residues, the N corr value became smaller, and after passing a minimum (which was still slightly positive) at a roughly equivalent molar ratio, the N corr value increased again. This is in a significant contrast with the largely positive N corr values for the homo-polymers (PolyMA, PolyDMAPMA and PolyMAPTAC), and other ordinary polyelectrolytes. The effect of the charge-balanced co-polymer on the hydrogen-bonded network structure of vicinal water observed by Raman spectroscopy was in accordance with that of the charge-balanced terpolymer film observed by infrared spectroscopy.