Vonk Kasper M, Meijer E W, Vantomme Ghislaine
Institute for Complex Molecular Systems, Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology P.O. Box 513 5600 MB Eindhoven The Netherlands
Chem Sci. 2021 Sep 29;12(40):13572-13579. doi: 10.1039/d1sc04545h. eCollection 2021 Oct 20.
Controlling the reciprocity between chemical reactivity and supramolecular structure is a topic of great interest in the emergence of molecular complexity. In this work, we investigate the effect of a covalent reaction as a trigger to depolymerize a supramolecular assembly. We focus on the impact of an thiol-ene reaction on the (co)polymerization of three derivatives of benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with cysteine, hexylcysteine, and alkyl side chains: , , and . Long supramolecular polymers of can be depolymerized into short dimeric aggregates of the thiol-ene reaction. Analysis of the system by time-resolved spectroscopy and light scattering unravels the fast dynamicity of the structures and the mechanism of depolymerization. Moreover, by intercalating the reactive monomer into an unreactive inert polymer, the thiol-ene reaction transforms the intercalator into a sequestrator and induces the depolymerization of the unreactive polymer. This work shows that the implementation of reactivity into supramolecular assemblies enables temporal control of depolymerization processes, which can bring us one step closer to understanding the interplay between non-covalent and covalent chemistry.
控制化学反应性与超分子结构之间的相互作用是分子复杂性出现过程中一个备受关注的课题。在这项工作中，我们研究了共价反应作为触发超分子组装解聚的效应。我们重点关注硫醇-烯反应对三种用半胱氨酸、己基半胱氨酸和烷基侧链功能化的苯-1,3,5-三甲酰胺（BTA）单体衍生物的（共）聚合反应的影响： 、 和 。 的长超分子聚合物可通过硫醇-烯反应解聚为 的短二聚体聚集体。通过时间分辨光谱和光散射对该体系进行分析，揭示了结构的快速动力学以及解聚机制。此外，通过将反应性 单体插入无反应性的惰性聚合物中，硫醇-烯反应将嵌入剂转化为螯合剂，并诱导无反应性聚合物解聚。这项工作表明，将反应性引入超分子组装体能够实现对解聚过程的时间控制，这能使我们在理解非共价化学和共价化学之间的相互作用方面更进一步。
