Lewis Reece W, Klemm Benjamin, Macchione Mariano, Eelkema Rienk
Department of Chemical Engineering, Delft University of Technology Van der Maasweg 9 2629 HZ Delft The Netherlands
Chem Sci. 2022 Mar 31;13(16):4533-4544. doi: 10.1039/d2sc00805j. eCollection 2022 Apr 20.
Fuel-driven macromolecular coacervation is an entry into the transient formation of highly charged, responsive material phases. In this work, we used a chemical reaction network (CRN) to drive the coacervation of macromolecular species readily produced using radical polymerisation methods. The CRN enables transient quaternization of tertiary amine substrates, driven by the conversion of electron deficient allyl acetates and thiol or amine nucleophiles. By incorporating tertiary amine functionality into block copolymers, we demonstrate chemical triggered complex coacervate core micelle (C3M) assembly and disassembly. In contrast to most dynamic coacervate systems, this CRN operates at constant physiological pH without the need for complex biomolecules. By varying the allyl acetate fuel, deactivating nucleophile and reagent ratios, we achieved both sequential signal-induced C3M (dis)assembly, as well as transient non-equilibrium (dis)assembly. We expect that timed and signal-responsive control over coacervate phase formation at physiological pH will find application in nucleic acid delivery, nano reactors and protocell research.
燃料驱动的大分子凝聚是进入高电荷、响应性材料相瞬态形成的一种方式。在这项工作中，我们使用化学反应网络（CRN）来驱动通过自由基聚合方法容易产生的大分子物种的凝聚。该CRN能够通过缺电子烯丙基乙酸酯与硫醇或胺亲核试剂的转化来驱动叔胺底物的瞬态季铵化。通过将叔胺官能团引入嵌段共聚物中，我们展示了化学触发的复合凝聚核胶束（C3M）组装和解组装。与大多数动态凝聚系统不同，该CRN在恒定的生理pH值下运行，无需复杂的生物分子。通过改变烯丙基乙酸酯燃料、失活亲核试剂和试剂比例，我们实现了顺序信号诱导的C3M（去）组装以及瞬态非平衡（去）组装。我们预计，在生理pH值下对凝聚相形成进行定时和信号响应控制将在核酸递送、纳米反应器和原细胞研究中得到应用。
