Nature uses complex self-assembly pathways to access distinct functional non-equilibrium self-assemblies. This remarkable ability to steer same set of biomolecules into different self-assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over ‘Pathway Complexity’ to access self-assemblies different from equilibrium structures remains challenging. Here we show versatile non-equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non-classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)-crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft-materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self-assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

中文翻译：

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复杂的途径驱动多能 Fmoc-亮氨酸自组装


大自然使用复杂的自组装途径来获得不同的功能性非平衡自组装。这种将同一组生物分子引导到不同自组装状态的非凡能力是通过避免热力学坑来实现的。在合成系统中，按需控制“路径复杂性”以访问不同于平衡结构的自组装仍然具有挑战性。在这里，我们展示了同一单体通过替代组装途径的多功能非平衡组装。该组件使用非经典或经典成核途径成核成不同的亚稳态（瞬态水凝胶）、动力学（稳定水凝胶）和热力学结构[（多）晶体和二维片]。初始的化学和热输入迫使单体遵循不同的组装路径，并形成具有与平衡状态不同的分子排列的软材料。在许多情况下，平衡结构充当热力学汇，消耗亚稳态结构中的单体，从而产生瞬时形成的材料。这种动力学可以通过化学或热调节来减缓瞬时水凝胶的溶解，或者完全跳过中间水凝胶以达到最终的平衡组装。如果需要，可以在动力学上捕获这种亚稳态，以提供数天内稳定的强水凝胶。这种控制不同自组装状态的方法可以在类似的仿生系统中找到潜在用途，以获取适合各种应用的新材料。