Ou-Yang Wei, Weis Martin, Yamamoto Tetsuya, Manaka Takaaki, Iwamoto Mitsumasa
Department of Physical Electronics, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
J Chem Phys. 2009 Mar 14;130(10):104706. doi: 10.1063/1.3086730.
The effect of external electrostatic charge on the shapes of liquid condensed (LC) phase domains in monolayer at the air/water interface was investigated. For this reason the thermodynamic properties, domain size, and spontaneous polarization were analyzed by surface pressure-area isotherms, Brewster angle microscopy (BAM), and Maxwell displacement current technique. The analysis indicated magnesium ions preferred to bond with dipalmitoyl phosphatidylcholine negative head group in liquid expanded phase and/or at domain boundary at low ion concentration and got an access to binding with molecules inside of the LC domains for higher ion concentration. Domain size increase characterized by BAM was discussed in respect to the shape equation on the basis of electrostatic energy contribution. Although molecular repulsive force increased by adding of ions into subphase, the growth of domain size exceeded this tendency. Following shape equation analysis it was suggested that this effect corresponded to change in dipole moment orientation represented by increase in spontaneous polarization in normal projection. This demonstrated impact of local electrostatic field on molecular dipoles and free energy of LC domains.
研究了外部静电荷对空气/水界面单分子层中液体凝聚(LC)相域形状的影响。为此,通过表面压力-面积等温线、布鲁斯特角显微镜(BAM)和麦克斯韦位移电流技术分析了热力学性质、域尺寸和自发极化。分析表明,在低离子浓度下,镁离子更倾向于与液体扩张相和/或域边界处的二棕榈酰磷脂酰胆碱负头基结合,而在较高离子浓度下,镁离子可以与LC域内的分子结合。基于静电能贡献,根据形状方程讨论了以BAM表征的域尺寸增加。尽管通过向亚相中添加离子增加了分子排斥力,但域尺寸的增长超过了这种趋势。通过形状方程分析表明,这种效应对应于法向投影中自发极化增加所代表的偶极矩取向变化。这证明了局部静电场对分子偶极子和LC域自由能的影响。