Kinzel Stefka, Gradzielski Michael
Stranski-Laboratorium für Physikalische und Theoretische Chemie, Institut für Chemie, Technische Universität Berlin, Berlin, Germany.
Langmuir. 2008 Sep 16;24(18):10123-32. doi: 10.1021/la801452z. Epub 2008 Aug 2.
The effect of the addition of two cationic surfactants of different chain length (decyl and dodecyl trimethylammonium bromide, DeTMABr and DTMABr, respectively) and one anionic surfactant of identical chain length (sodium dodecyl sulfate, SDS) on phase behavior, structure, and macroscopic properties of a bilayer forming nonionic surfactant (Brij 30) has been investigated by means of phase studies, rheology, turbidity measurements, dynamic light scattering, and freeze-fracture transmission electron microscopy. We concentrated on DTMABr because of the generically similar behavior for the other ionic surfactants. It is found that already very small amounts of added ionic surfactant have a very pronounced effect on the phase behavior of these systems. The pure nonionic surfactant forms bilayers and has a tendency for the formation of vesicles which becomes enhanced by charging the bilayer through the incorporation of the ionic surfactant. The presence of the ionic surfactant leads to much more viscous systems, which already at a total surfactant concentration of 150 mM become gel-like. For a given surfactant concentration, the elastic properties of the gels increase largely upon the addition of ionic surfactant. This effect is strongly synergistic, requiring only very small amounts of added ionic surfactant, and the elastic properties pass through a maximum for a content of ionic surfactant of about 3-5 mol %. This behavior can be explained in a self-consistent way by a simple rheological model and by combining it with light scattering data. For the addition of larger amounts, the elastic properties decrease again and the formed vesicles become structurally less defined as one is leaving the range of conditions for forming well-defined vesicles, which are required for forming elastic vesicle gels.
通过相研究、流变学、浊度测量、动态光散射和冷冻断裂透射电子显微镜,研究了添加两种不同链长的阳离子表面活性剂(分别为癸基三甲基溴化铵和十二烷基三甲基溴化铵,DeTMABr和DTMABr)以及一种相同链长的阴离子表面活性剂(十二烷基硫酸钠,SDS)对形成双层的非离子表面活性剂(Brij 30)的相行为、结构和宏观性质的影响。由于其他离子表面活性剂的行为普遍相似,我们重点研究了DTMABr。发现添加极少量的离子表面活性剂就会对这些体系的相行为产生非常显著的影响。纯非离子表面活性剂形成双层,并且有形成囊泡的趋势,通过掺入离子表面活性剂使双层带电会增强这种趋势。离子表面活性剂的存在导致体系的粘性大大增加,在总表面活性剂浓度仅为150 mM时就变成凝胶状。对于给定的表面活性剂浓度,凝胶的弹性性质在添加离子表面活性剂后大幅增加。这种效应具有很强的协同性,只需要添加极少量的离子表面活性剂,并且弹性性质在离子表面活性剂含量约为3 - 5 mol%时达到最大值。这种行为可以通过一个简单的流变模型并结合光散射数据以自洽的方式来解释。对于添加量较大的情况,弹性性质又会下降,并且随着体系偏离形成结构明确的囊泡所需的条件范围,形成的囊泡在结构上变得不那么明确,而弹性囊泡凝胶的形成需要结构明确囊泡。