Sharko Anastasiia, Livitz Dimitri, De Piccoli Serena, Bishop Kyle J M, Hermans Thomas M
University of Strasbourg & CNRS, UMR7140, Strasbourg 67000, France.
Department of Chemical Engineering, Columbia University, New York, New York 10027, United States.
Chem Rev. 2022 Jul 13;122(13):11759-11777. doi: 10.1021/acs.chemrev.1c00958. Epub 2022 Jun 8.
Supramolecular polymerization can be controlled in space and time by chemical fuels. A nonassembled monomer is activated by the fuel and subsequently self-assembles into a polymer. Deactivation of the molecule either in solution or inside the polymer leads to disassembly. Whereas biology has already mastered this approach, fully artificial examples have only appeared in the past decade. Here, we map the available literature examples into four distinct regimes depending on their activation/deactivation rates and the equivalents of deactivating fuel. We present increasingly complex mathematical models, first considering only the chemical activation/deactivation rates (i.e., transient activation) and later including the full details of the isodesmic or cooperative supramolecular processes (i.e., transient self-assembly). We finish by showing that sustained oscillations are possible in chemically fueled cooperative supramolecular polymerization and provide mechanistic insights. We hope our models encourage the quantification of activation, deactivation, assembly, and disassembly kinetics in future studies.
超分子聚合可以通过化学燃料在空间和时间上进行控制。一种未组装的单体被燃料激活，随后自组装成聚合物。分子在溶液中或聚合物内部失活会导致解聚。虽然生物学已经掌握了这种方法，但完全人工的例子直到过去十年才出现。在这里，我们根据可用文献中的例子的激活/失活速率以及失活燃料的当量，将它们划分为四个不同的区域。我们提出了越来越复杂的数学模型，首先只考虑化学激活/失活速率（即瞬态激活），后来纳入了等键或协同超分子过程的全部细节（即瞬态自组装）。我们通过表明在化学驱动的协同超分子聚合中可能存在持续振荡来结束本文，并提供了机理见解。我们希望我们的模型能鼓励在未来的研究中对激活、失活、组装和解聚动力学进行量化。
