Das Soumik, Roh Sangchul, Atzin Noe, Mozaffari Ali, Tang Xingzhou, de Pablo Juan J, Abbott Nicholas L
Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, United States.
Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States.
Langmuir. 2022 Mar 22;38(11):3575-3584. doi: 10.1021/acs.langmuir.2c00231. Epub 2022 Mar 9.
AC electric fields cause three-dimensional orientational fluctuations (solitons) to form and rapidly propagate in confined films of liquid crystals (LCs), offering the basis of a new class of active soft matter (e.g., for accelerating mixing and transport processes in microscale chemical systems). How surface chemistry impacts the formation and trajectories of solitons, however, is not understood. Here, we show that self-assembled monolayers (SAMs) formed from alkanethiols on gold, which permit precise control over surface chemistry, are electrochemically stable over voltage and frequency windows (<100 V; 1 kHz) that lead to soliton formation in achiral nematic films of 4'-butyl-4-heptyl-bicyclohexyl-4-carbonitrile (CCN-47). By comparing soliton formation in LC films confined by SAMs formed from hexadecanethiol (CSH) or pentadecanethiol (CSH), we reveal that the electric field required for soliton formation increases with the LC anchoring energy: surfaces patterned with regions of CSH and CSH SAMs thus permit spatially controlled creation and annihilation of solitons necessary to generate a net flux of solitons. We also show that solitons propagate in orthogonal directions when confined by obliquely deposited gold films decorated with SAMs formed from CSH or CSH and that the azimuthal direction of propagation of solitons within achiral LC films possessing surface-induced twists is not unique but reflects variation in the spatial location of the solitons across the thickness of the twisted LC film. Finally, discontinuous changes in LC orientation induced by patterned surface anchoring lead to a range of new soliton behaviors including refraction, reflection, and splitting of solitons at the domain boundaries. Overall, our results provide new approaches for the controlled generation and programming of solitons with complex and precise trajectories, principles that inform new designs of chemical soft matter.
交流电场会使三维取向涨落(孤子)形成并在液晶(LC)受限薄膜中快速传播,这为一类新型活性软物质(例如用于加速微尺度化学系统中的混合和传输过程)奠定了基础。然而,表面化学如何影响孤子的形成和轨迹尚不清楚。在此,我们表明,由金表面的烷硫醇形成的自组装单分子层(SAMs),能够精确控制表面化学性质,在导致4'-丁基-4-庚基-双环己基-4-腈(CCN-47)非手性向列相薄膜中形成孤子的电压和频率窗口(<100 V;1 kHz)内具有电化学稳定性。通过比较由十六烷硫醇(CSH)或十五烷硫醇(CSH)形成的SAMs限制的LC薄膜中的孤子形成情况,我们发现孤子形成所需的电场随LC锚定能增加:用CSH和CSH SAMs区域图案化的表面因此允许在空间上控制孤子的产生和湮灭,这对于产生孤子的净通量是必要的。我们还表明,当由用CSH或CSH形成的SAMs装饰的倾斜沉积金薄膜限制时,孤子在正交方向传播,并且在具有表面诱导扭曲的非手性LC薄膜内孤子传播的方位角方向不是唯一的,而是反映了孤子在扭曲LC薄膜厚度上空间位置的变化。最后,由图案化表面锚定引起的LC取向的不连续变化导致了一系列新的孤子行为,包括孤子在畴边界处的折射、反射和分裂。总体而言,我们的结果为具有复杂和精确轨迹的孤子的可控产生和编程提供了新方法,这些原理为化学软物质的新设计提供了依据。