ABSTRACT
A photoresponsive 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. Photoresponsive units within the amphiphilic pre-catalysts allow for switching between assembled and disassembled states, thereby modulating the catalytic activity. The ability to reversibly form cooperative catalysts within a dynamic self-assembled system represents a conceptually new tool for the design of complex artificial systems in water.
ABSTRACT
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.
Subject(s)
Biomimetic Materials/chemistry , Coordination Complexes/chemistry , Surface-Active Agents/chemistry , Zinc/chemistry , 2,4-Dinitrophenol/analogs & derivatives , 2,4-Dinitrophenol/chemistry , Adenosine Triphosphate/chemistry , Aza Compounds/chemistry , Catalysis , Organophosphates/chemistry , Piperidines/chemistry , ThermodynamicsABSTRACT
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.
