Thermally reversible pattern formation in arrays of molecular rotors
Thermally reversible pattern formation in arrays of molecular rotors
复制标题
分子转子阵列中热可逆图案的形成
DOI：
10.1039/d2nr05813h
复制
发表时间：
2023
期刊：
影响因子：
6.7
通讯作者：
Arya, Gaurav
中科院分区：
文献类型：
--
作者：
DeLuca, Marcello;Pfeifer, Wolfgang G.;Randoing, Benjamin;Huang, Chao-Min;Poirier, Michael G.;Castro, Carlos E.;Arya, Gaurav
控制材料的介观尺度到微观尺度的图案化是软物质界非常感兴趣的问题。受DNA折纸转子的启发，我们引入了一种旋转转子的2D最近邻晶格，它展示了离散的取向状态和与邻居的相互作用。对转子晶格的蒙特卡罗模拟表明，它们表现出各种有趣的有序化行为和形态，可以通过转子设计参数来调节。转子阵列在其有序状态下表现出包括闭合回路、辐射回路和砖瓦结构在内的各种图案。对于较小的系统尺寸，它们在很低的温度下表现出特定的热峰，并且一些系统根据转子间相互作用的设计而表现出多个有序-无序转变。我们设计了一个基于能量的有序参数，并通过伞形抽样和直方图加权表明，该有序参数很好地捕捉到了这些系统中发生的有序-无序转变。我们制造了真实的DNA折纸转子，这些转子本身可以通过可编程的DNA碱基配对相互作用进行排序，并展示了有序和无序相，说明了转子晶格如何在实验上实现并用于响应组织。这项工作确立了实现具有局部介导性微尺度图案的结构纳米材料的可行性，这可能在传感和精密表面图案化方面有应用。
Control over the mesoscale to microscale patterning of materials is of great interest to the soft matter community. Inspired by DNA origami rotors, we introduce a 2D nearest-neighbor lattice of spinning rotors that exhibit discrete orientational states and interactions with their neighbors. Monte Carlo simulations of rotor lattices reveal that they exhibit a variety of interesting ordering behaviors and morphologies that can be modulated through rotor design parameters. The rotor arrays exhibit diverse patterns including closed loops, radiating loops, and bricklayer structures in their ordered states. They exhibit specific heat peaks at very low temperatures for small system sizes, and some systems exhibit multiple order–disorder transitions depending on inter-rotor interaction design. We devise an energy-based order parameter and show via umbrella sampling and histogram reweighting that this order parameter captures well the order–disorder transitions occurring in these systems. We fabricate real DNA origami rotors which themselves can order via programmable DNA base-pairing interactions and demonstrate both ordered and disordered phases, illustrating how rotor lattices may be realized experimentally and used for responsive organization. This work establishes the feasibility of realizing structural nanomaterials that exhibit locally mediated microscale patterns which could have applications in sensing and precision surface patterning.