Dissipative self-assembly processes in Nature rely on chemical fuels that activate proteins for assembly through the formation of a noncovalent complex. The catalytic activity of the assemblies causes fuel degradation, resulting in the formation of an assembly in a high-energy, out-of-equilibrium state. Herein, we apply this concept to a synthetic system and demonstrate that a substrate can induce the formation of vesicular assemblies, which act as cooperative catalysts for cleavage of the same substrate.
Aphotoresponsive system where structure formation is coupled to catalytic activity is presented. The observed catalytic activity is reliant on intermolecular cooperative effects that are present when amphiphiles assemble into vesicular structures.P hotoresponsive units within the amphiphilic precatalysts allowfor switching between assembled and disassembled states,therebymodulating the catalytic activity.The ability to reversibly form cooperative catalysts within adynamic selfassembled system represents ac onceptually new tool for the design of complex artificial systems in water.
Enzymes accelerate chemical reactions by forming cooperative interactions using precisely positioned functional groups. This has inspired the construction of artificial catalysts by the attachment of functional groups onto molecular scaffolds or solid supports to induce synergistic interactions. Herein, the transphosphorylation reaction is used as a model to demonstrate that cooperativity can also occur intermolecularly between multiple functional groups within self-assembled vesicular structures. We demonstrate that the modular and dynamic nature of such systems allow for triggered reorganization and the up-or downregulation of catalytic activity. Such concepts have the potential to be used in the design of synergistic catalysts and their incorporation into responsive catalytic systems in water.
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