Theoretical Soft Matter and Biophysics, Institute for Complex Systems, Forschungszentrum Jülich, 52425 Jülich, Germany.
Langmuir. 2011 Apr 5;27(7):3416-23. doi: 10.1021/la200138b. Epub 2011 Mar 7.
Binary mixtures of amphiphiles in solution can self-assemble into a wide range of structures when the two species individually form aggregates of different curvatures. A specific example of this is seen in solutions of lipid mixtures where the two species form lamellar structures and spherical micelles, respectively. Here, vesicles connected by threadlike micelles can form in a narrow concentration range of the sphere-forming lipid. We present a study of these structures based on self-consistent field theory (SCFT), a coarse-grained model of amphiphiles. First, we show that the addition of sphere-forming lipid to a solution of lamella-former can lower the free energy of cylindrical, threadlike micelles and hence encourage their formation. Next, we demonstrate the coupling between composition and curvature; specifically, that increasing the concentration of sphere-former in a system of two bilayers connected by a thread leads to a transfer of amphiphile to the thread. We further show that the two species are segregated within the structure, with the concentration of sphere-former being significantly higher in the thread. Finally, the addition of larger amounts of sphere-former is found to destabilize the junctions linking the bilayers to the cylindrical micelle, leading to a breakdown of the connected structures. The degree of segregation of the amphiphiles and the amount of sphere-former required to destabilize the junctions is shown to be sensitive to the length of the hydrophilic block of the sphere-forming amphiphiles.
在两种物质分别形成不同曲率的聚集物时,溶液中的两亲混合物可以自组装成广泛的结构。脂质混合物溶液就是一个具体的例子,其中两种物质分别形成层状结构和球形胶束。在形成球形胶束的脂质的狭窄浓度范围内,可以形成由线状胶束连接的囊泡。我们基于自洽场理论(SCFT)对这些结构进行了研究,SCFT 是一种粗粒化的两亲物模型。首先,我们表明,向形成层状结构的溶液中添加形成球形结构的脂质可以降低圆柱形线状胶束的自由能,从而促进其形成。接下来,我们证明了组成和曲率之间的耦合关系;具体来说,在由两个双层通过线状结构连接的体系中,增加球形形成物的浓度会导致两亲物转移到线状结构中。我们进一步表明,两种物质在结构内被分离,线状结构中的球形形成物浓度明显更高。最后,发现添加更多量的球形形成物会使连接双层和圆柱形胶束的连接点失稳,导致连接结构的破裂。两亲物的分离程度和使连接点失稳所需的球形形成物的量对球形形成物的亲水性链段的长度敏感。