Devising Synthetic Reaction Cycles for Dissipative Nonequilibrium Self-Assembly.

Fuel-driven reaction cycles are found in biological systems to control the assembly and disassembly of supramolecular materials such as the cytoskeleton. Fuel molecules can bind noncovalently to a self-assembling building block or they can react with it, resulting in covalent modifications. Overall the fuel can either switch the self-assembly process on or off. Here, a closer look is taken at artificial systems that mimic biological systems by making and breaking covalent bonds in a self-assembling motif. The different chemistries used so far are highlighted in chronological order and the pros and cons of each system are discussed. Moreover, the desired traits of future reaction cycles, their fuels, and waste management are outlined, and two chemistries that have not been explored up to now in chemically fueled dissipative self-assembly are suggested.