Molecular Physics Laboratory, Ruder Bošković Institute, P.O. Box 180, Zagreb HR-10002, Croatia.
J Chem Phys. 2011 Jan 14;134(2):024701. doi: 10.1063/1.3522646.
The aim of this study was to investigate the connection between the lipid/amphiphile monolayer structure at the interface and its macroscopic/rheological properties, in particular, to establish the link between the fractality of the monolayer structure and its compressibility modulus. To that purpose we have used fractal analysis of images obtained by Brewster angle microscopy to infer the fractal dimension of the monolayer structure and relate its change to the corresponding changes in compressibility derived from a simultaneously measured π-A isotherm. The results of the study confirmed the starting assumption based on theoretical considerations that the fractal dimension of an amphiphilic monolayer and its compressibility should be correlated. We have shown that there exists a strong correlation between the fractal dimension and the corresponding compressibility modulus of different amphiphilic materials. Thus, confirming the link between the short ordered structure on the molecular level and the macroscopic property-compressibility of the monolayer. The established correlation between the fractal dynamics and compressibility modulus of the monolayer enabled identification of onset of percolation-a second-order phase transition that is otherwise not easy and unambiguously detectable. We have found that the signature of percolation in a monolayer, regardless of its composition, is the occurrence of a sharp increase (a jump) of compressibility modulus (at macroscopic level) at the characteristic value of the corresponding fractal dimension D = 1.89. This is the result of the abrupt establishment of a connected structure on the molecular level, consequently involving a change in the elastic properties of the monolayer on a macroscopic scale. The results of this investigation provide means for unambiguous identification of the onset of percolation in the Langmuir layer and should facilitate a more efficient application of the percolation theory in further study of processes and structures at the interface during the monolayer compression.
本研究旨在探讨界面处的脂质/两亲单分子层结构与其宏观/流变性质之间的联系,特别是建立单分子层结构的分形与压缩模量之间的联系。为此,我们使用布儒斯特角显微镜获得的图像的分形分析来推断单分子层结构的分形维数,并将其变化与从同时测量的 π-A 等温线得出的相应压缩性变化相关联。研究结果证实了基于理论考虑的初始假设,即两亲单分子层的分形维数与其压缩性应该相关。我们表明,不同两亲材料的分形维数与其相应的压缩模量之间存在很强的相关性。因此,证实了分子水平上的短有序结构与单层的宏观性质-压缩性之间的联系。建立的单分子层分形动力学与压缩模量之间的相关性使得能够识别渗流的发生-这是一种二阶相变,否则不容易且不易明确检测。我们发现,无论组成如何,单分子层中渗流的特征是在相应分形维数 D=1.89 的特征值处,压缩模量(在宏观水平上)发生急剧增加(跳跃)。这是由于在分子水平上突然建立了一个连接结构,从而导致单分子层的弹性性质在宏观尺度上发生变化。这项研究的结果为在 Langmuir 层中明确识别渗流的发生提供了手段,应该有助于更有效地将渗流理论应用于单分子层压缩过程中界面处的过程和结构的进一步研究。