CONSTRUCTION OF INFRARED-ACTIVATED SCANNING AFM SURFACE ANALYZER AND ITS APPLICATION TO THE CHARACTERIZATION OF POLYMER THIN FILM-WATERINTERFACES.

构建了一种新型的红外激活扫描原子力显微镜表面分析仪，并利用该仪器对聚合物薄膜-水界面进行了表征。此外，用偏振拉曼光谱的O-H伸展轮廓分析了磺基甜菜碱聚合物水溶液中水的结构和氢键。聚合物的一个单体残基(N值)导致氢键断裂的数目是一个很小的正值，与中性聚合物的氢键数目相当。这与前体聚合物和普通聚电解质的大体上正的N值形成了很好的对比。结果表明，Zwitter型离子聚合物对水的氢键网络结构没有明显的干扰作用，这可能是由于阴阳离子基团之间的邻近性抵消了电致伸缩效应。此外，用衰减全反射红外光谱(ATR-IR)研究了甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸-2-甲氧乙酯(MEA)共聚物吸附水的结构。通过比较吸附到聚合物中的水与液态水和水蒸气的消光系数EOH，估算了聚合物链周围的有效水化区域。结果似乎表明，一次水化水与其周围的水分子之间的相互作用很弱。也就是说，聚合物链周围的有效水化区域非常小。这种具有较大EOH值的水似乎对应于一种“冷结晶”水，DSC观察到这是一种异常水，而不是中间水和不可冻结水。

A novel infrared-activated scanning AFM surface analyzer was constructed and characterization of polymer thin film-water interfaces using the apparatus was examined. Furthermore, the structure and hydrogen bonding of water in aqueous solution of sulfobetaine polymers were analyzed with contours of O-H stretching of polarized Raman spectra. The number of hydrogen bonding collapsed by the presence of one monomer residue (N value) for the polymers was a small positive value, and comparable to those for neutral polymers. This is in good contrast to the largely positive N values for the precursor polymer, and ordinary polyelectrolytes. The present results clearly indicate that the zwitter ionic polymers do not disturb the hydrogen-bonded network structure of water significantly, probably due to the counteraction of electrostriction effect by the proximity between the anionic and cationic groups. Moreover, the structure of water sorbed into copolymer of (2-methoxyethylacrylate) (MEA) and 2-hydroxyethylmethacrylate (HEMA) was investigated by an attenuated total reflection infrared (ATR-IR) spectroscopy. The effective hydration region around the polymer chain was estimated by the comparison of the extinction coefficient, eOH, for the water sorbed into the polymers contacting with liquid water and water vapor. The result seemed to indicate that the interaction between the primary hydration water and water molecules surrounding them around the MEA-containing polymer chain is very weak. Namely, the effective hydration region around the polymer chain is very small. Such water with the large eOH value seemed to correspond to a "cold-crystallizable" water, which has been observed by DSC as anomalous water other than intermediate and non-freezable waters.