Nakahara Hiromichi, Shibata Osamu
Department of Biophysical Chemistry, Faculty of Pharmaceutical Sciences, Nagasaki International University, Sasebo, Nagasaki 859-3298, Japan.
J Oleo Sci. 2013;62(7):471-80. doi: 10.5650/jos.62.471.
The miscibility of Langmuir monolayers of egg yolk lecithin (eggPC) with n-hexadecanoic acid (PA), 1-hexadecanol (HD), and their equimolar mixture (PA/HD) was investigated thermodynamically and morphologically. Surface pressure (π)-molecular area (A) and surface potential (ΔV)-A isotherms for the binary and ternary systems were measured, employing the Wilhelmy method and the ionizing (241)Am electrode method, respectively. From the thermodynamic perspective, eggPC was partially miscible with PA, HD, and PA/HD within the monolayer state, in terms of an excess Gibbs free energy of mixing calculated from the π-A isotherms and a two-dimensional phase diagram based on a monolayer collapse pressure. This was also directly supported by phase behavior observations using fluorescence microscopy (FM). EggPC formed a typical liquid-expanded (LE) monolayer, and the others formed liquid-condensed (LC) monolayers. The FM images exhibited miscible modes at middle molar fractions of PA, HD, and PA/HD, and immiscible patterns at large molar fractions for all the systems examined. A new finding in the present study was that the eggPC/PA, eggPC/HD, and eggPC/(PA/HD) systems exhibited partial miscibility, although the systems were made of both LE (eggPC) and LC monolayers (the others). This miscibility is considered to be attributable to the molecular species comprising eggPC.
从热力学和形态学角度研究了蛋黄卵磷脂(eggPC)与正十六烷酸(PA)、1-十六醇(HD)及其等摩尔混合物(PA/HD)的Langmuir单分子层的混溶性。分别采用Wilhelmy法和电离(241)Am电极法测量了二元和三元体系的表面压力(π)-分子面积(A)和表面电位(ΔV)-A等温线。从热力学角度来看,根据从π-A等温线计算出的混合过量吉布斯自由能和基于单分子层崩塌压力的二维相图,eggPC在单分子层状态下与PA、HD和PA/HD部分混溶。使用荧光显微镜(FM)进行的相行为观察也直接支持了这一点。eggPC形成典型的液体扩张(LE)单分子层,其他物质形成液体凝聚(LC)单分子层。对于所有研究的体系,FM图像在PA、HD和PA/HD的中等摩尔分数下呈现混溶模式,在大摩尔分数下呈现不混溶模式。本研究的一个新发现是,eggPC/PA、eggPC/HD和eggPC/(PA/HD)体系表现出部分混溶性,尽管这些体系由LE(eggPC)和LC单分子层(其他物质)组成。这种混溶性被认为归因于构成eggPC的分子种类。