Noguchi Hidenori, Hiroshi Minowa, Tominaga Taiki, Gong Jian Ping, Osada Yoshihito, Uosaki Kohei
Physical Chemistry Laboratory, Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
Phys Chem Chem Phys. 2008 Aug 28;10(32):4987-93. doi: 10.1039/b807297n. Epub 2008 Jul 17.
Interfacial structures of water at polyvinyl alcohol (PVA) and poly(2-acrylamido-2-methypropane) sulfonic acid sodium salt (PNaAMPS)/quartz interfaces were investigated by sum frequency generation (SFG) spectroscopy. Two broad peaks were observed in OH stretching region at 3200 and 3400 cm(-1), corresponding to the symmetric OH stretching of tetrahedrally coordinated, i.e., strongly hydrogen bonded "ice-like" water, and the asymmetric OH stretching of water in a more random arrangement, i.e., weakly hydrogen bonded "liquid-like" water, respectively, in both cases. The "liquid-like" water became dominant when the PVA gel was pressed against the quartz surface. The relative intensity of the SFG signal due to the "liquid-like" water to that due to the "ice-like water" at the quartz surface modified with a self-assembled monolayer of aminopropyltrimethoxysilane (APS) became higher when the negatively charged PNaMPS gel was contacted to the APS modified quartz surface in a solution of pH = 12, where the surface was negatively charged and electrostatic repulsive interaction and low friction were present between the PNaMPS gel and the APS modified surface. It, however, did not change in a solution of pH = 2, where the surface was positively charged and electrostatic attractive interaction and very high friction were present between the PNaMPS gel and the APS modified surface. These results suggest the important role of water structure for small friction at the polymer gel/solid interface.
采用和频振动光谱(SFG)研究了聚乙烯醇(PVA)以及聚(2-丙烯酰胺-2-甲基丙烷)磺酸钠盐(PNaAMPS)/石英界面处水的界面结构。在3200和3400 cm⁻¹的OH伸缩振动区域观察到两个宽峰,分别对应四面体配位的对称OH伸缩振动,即强氢键结合的“类冰”水,以及更无序排列的水的不对称OH伸缩振动,即弱氢键结合的“类液体”水。当PVA凝胶压在石英表面时,“类液体”水占主导。当在pH = 12的溶液中,带负电的PNaMPS凝胶与氨基丙基三甲氧基硅烷(APS)修饰的石英表面接触时,石英表面上由于“类液体”水产生的SFG信号与由于“类冰”水产生的SFG信号的相对强度会升高,此时表面带负电,PNaMPS凝胶与APS修饰表面之间存在静电排斥相互作用和低摩擦。然而,在pH = 2的溶液中该相对强度不变,此时表面带正电,PNaMPS凝胶与APS修饰表面之间存在静电吸引相互作用和非常高的摩擦。这些结果表明水结构在聚合物凝胶/固体界面处的小摩擦中起重要作用。