Insights into Chemically Fueled Supramolecular Polymers

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.

Automated summary

Supramolecular polymerization can be controlled in space and time by chemical fuels. The activation and deactivation of a nonassembled monomer leads to self-assembly into a polymer and subsequent disassembly. This approach, which has been mastered by biology, has recently been achieved in fully artificial systems. Mathematical models have been developed to describe the activation, deactivation, assembly, and disassembly kinetics in different regimes of chemically fueled cooperative supramolecular polymerization, with the possibility of sustained oscillations. These models encourage further quantification in future studies.