Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53706, USA.
Langmuir. 2010 Jun 15;26(12):10234-42. doi: 10.1021/la100376u.
We demonstrate that the assembly of an amphiphilic polyamine on the interfaces of micrometer-sized droplets of a thermotropic liquid crystal (LC) dispersed in aqueous solutions can be used to facilitate the immobilization of LC droplets on chemically functionalized surfaces. Polymer 1 was designed to contain both hydrophobic (alkyl-functionalized) and hydrophilic (primary and tertiary amine-functionalized) side chain functionality. The assembly of this polymer at the interfaces of aqueous dispersions of LC droplets was achieved by the spontaneous adsorption of polymer from aqueous solution. Polymer adsorption triggered transitions in the orientational ordering of the LCs, as observed by polarized light and bright-field microscopy. We demonstrate that the presence of polymer 1 on the interfaces of these droplets can be exploited to immobilize LC droplets on planar solid surfaces through covalent bond formation (e.g., for surfaces coated with polymer multilayers containing reactive azlactone functionality) or through electrostatic interactions (e.g., for surfaces coated with multilayers containing hydrolyzed azlactone functionality). The characterization of immobilized LC droplets by polarized, fluorescence, and laser scanning confocal microscopy revealed the general spherical shape of the polymer-coated LC droplets to be maintained after immobilization, and that immobilization led to additional ordering transitions within the droplets that were dependent on the nature of the surfaces with which they were in contact. Polymer 1-functionalized LC droplets were not immobilized on polymer multilayers treated with poly(ethylene imine) (PEI). We demonstrate that the ability to design surfaces that promote or prevent the immobilization of polymer-functionalized LC droplets can be exploited to pattern the immobilization of LC droplets on surfaces. The results of this investigation provide the basis of an approach that could be used to tailor the properties of dispersed LC emulsions and to immobilize these droplets on functional surfaces of interest in a broad range of fundamental and applied contexts.
我们证明,在热致液晶(LC)微滴的水相分散体的界面上组装两亲性聚多胺可以促进 LC 微滴在化学功能化表面上的固定化。聚合物 1 被设计为含有疏水性(烷基功能化)和亲水性(伯胺和叔胺功能化)侧链官能团。通过聚合物从水溶液中的自发吸附,实现了该聚合物在 LC 微滴水相分散体界面上的组装。聚合物吸附触发了 LC 取向有序的转变,这可以通过偏振光和明场显微镜观察到。我们证明,这些液滴界面上的聚合物 1 的存在可以通过共价键形成(例如,对于涂有含有反应性氮丙啶官能团的聚合物多层的表面)或通过静电相互作用(例如,对于涂有含有水解氮丙啶官能团的多层的表面)来利用固定化 LC 液滴。通过偏振、荧光和激光扫描共聚焦显微镜对固定化 LC 液滴的表征表明,固定化后涂有聚合物的 LC 液滴保持大致球形,并且固定化导致液滴内的额外有序转变,这取决于它们与之接触的表面的性质。聚合物 1 功能化的 LC 液滴不能固定在用聚乙烯亚胺(PEI)处理的聚合物多层上。我们证明,设计能够促进或阻止聚合物功能化 LC 液滴固定化的表面的能力,可以用于在表面上对 LC 液滴的固定化进行图案化。这项研究的结果为一种方法提供了基础,该方法可以用于调整分散 LC 乳液的性质,并在广泛的基础和应用背景下将这些液滴固定在感兴趣的功能表面上。