Department of Chemical and Biological Engineering, University of Wisconsin-Madison, 1415 Engineering Drive, Madison, Wisconsin 53705, United States.
Langmuir. 2011 May 17;27(10):5719-38. doi: 10.1021/la103301d. Epub 2010 Nov 19.
This feature article describes recent advances in several areas of research involving the interfacial ordering of liquid crystals (LCs). The first advance revolves around the ordering of LCs at bio/chemically functionalized surfaces. Whereas the majority of past studies of surface-induced ordering of LCs have involved surfaces of solids that present a limited diversity of chemical functional groups (surfaces at which van der Waals forces dominate surface-induced ordering), recent studies have moved to investigate the ordering of LCs on chemically complex surfaces. For example, surfaces decorated with biomolecules (e.g., oligopeptides and proteins) and transition-metal ions have been investigated, leading to an understanding of the roles that metal-ligand coordination interactions, electrical double layers, acid-base interactions, and hydrogen bonding can play in the interfacial ordering of LCs. The opportunity to create chemically responsive LCs capable of undergoing ordering transitions in the presence of targeted molecular events (e.g., ligand exchange around a metal center) has emerged from these fundamental studies. A second advance has focused on investigations of the ordering of LCs at interfaces with immiscible isotropic fluids, particularly water. In contrast to prior studies of surface-induced ordering of LCs on solid surfaces, LC-aqueous interfaces are deformable and molecules at these interfaces exhibit high levels of mobility and thus can reorganize in response to changes in the interfacial environment. A range of fundamental investigations involving these LC-aqueous interfaces have revealed that (i) the spatial and temporal characteristics of assemblies formed from biomolecular interactions can be reported by surface-driven ordering transitions in the LCs, (ii) the interfacial phase behavior of molecules and colloids can be coupled to (and manipulated via) the ordering (and nematic elasticity) of LCs, and (iii) the confinement of LCs leads to unanticipated size-dependent ordering (particularly in the context of LC emulsion droplets). The third and final advance addressed in this article involves interactions between colloids mediated by LCs. Recent experiments involving microparticles deposited at the LC-aqueous interface have revealed that LC-mediated interactions can drive interfacial assemblies of particles through reversible ordering transitions (e.g., from 1D chains to 2D arrays with local hexagonal symmetry). In addition, recent single-nanoparticle measurements suggest that the ordering of LCs about nanoparticles differs substantially from micrometer-sized particles and that the interactions between nanoparticles mediated by the LCs are far weaker than predicted by theory (sufficiently weak that the interactions are reversible and thus enable self-assembly). Finally, LC-mediated interactions between colloidal particles have also been shown to lead to the formation of colloid-in-LC gels that possess mechanical properties relevant to the design of materials that interface with living biological systems. Overall, these three topics serve to illustrate the broad opportunities that exist to do fundamental interfacial science and discovery-oriented research involving LCs.
本文主要介绍了液晶(LC)界面有序化研究领域的一些最新进展。首先,研究集中在生物/化学功能化表面上 LC 的有序化。虽然过去大多数关于 LC 表面诱导有序化的研究都涉及到固体表面,这些表面具有有限的化学官能团多样性(范德华力主导表面诱导有序化的表面),但最近的研究已经转向研究化学复杂表面上 LC 的有序化。例如,研究了用生物分子(例如寡肽和蛋白质)和过渡金属离子修饰的表面,从而了解了金属配体配位相互作用、双电层、酸碱相互作用和氢键在 LC 界面有序化中的作用。这些基础研究为创造能够在靶向分子事件(例如金属中心周围的配体交换)存在下进行有序化转变的化学响应型 LC 提供了机会。第二个进展集中在研究与不混溶各向同性流体(特别是水)的 LC 界面有序化。与之前关于固体表面上 LC 表面诱导有序化的研究相比,LC-水界面是可变形的,界面处的分子具有较高的流动性,因此可以响应界面环境的变化进行重新排列。涉及这些 LC-水界面的一系列基础研究表明:(i)通过 LC 中的表面驱动有序化转变,可以报告生物分子相互作用形成的组装体的空间和时间特征,(ii)分子和胶体的界面相行为可以通过 LC 的有序化(和向列弹性)进行耦合和操纵,以及(iii)LC 的限制导致出乎意料的尺寸依赖性有序化(特别是在 LC 乳液液滴的情况下)。本文讨论的第三个也是最后一个进展涉及 LC 介导的胶体相互作用。最近涉及在 LC-水界面上沉积的微粒子的实验表明,LC 介导的相互作用可以通过可逆的有序化转变(例如,从 1D 链到具有局部六方对称性的 2D 阵列)驱动粒子的界面组装。此外,最近的单纳米粒子测量表明,纳米粒子周围 LC 的有序化与微米级粒子有很大不同,并且由 LC 介导的纳米粒子之间的相互作用远弱于理论预测(弱到足以使相互作用可逆,从而实现自组装)。最后,还表明 LC 介导的胶体粒子之间的相互作用导致胶体在 LC 凝胶中的形成,该凝胶具有与与活生物系统相互作用的材料设计相关的机械性能。总体而言,这三个主题说明了在涉及 LC 的基础界面科学和面向发现的研究中存在广泛的机会。