Nature uses catalysis as an indispensable tool to control assembly and reaction cycles in vital non-equilibrium supramolecular processes. For instance, enzymatic methionine oxidation regulates actin (dis)assembly, and catalytic guanosine triphosphate hydrolysis is found in tubulin (dis)assembly. Here we present a completely artificial reaction cycle which is driven by a chemical fuel that is catalytically obtained from a 'pre-fuel'. The reaction cycle controls the disassembly and re-assembly of a hydrogel, where the rate of pre-fuel turnover dictates the morphology as well as the mechanical properties. By adding additional fresh aliquots of fuel and removing waste, the hydrogels can be reprogrammed time after time. Overall, we show how catalysis can control fuel generation to control reaction / assembly kinetics and materials properties in lifelike non-equilibrium systems. File list (4) download file view on ChemRxiv REV_SachCHO_20191221_Chemrxiv.pdf (1.38 MiB) download file view on ChemRxiv REV_SI_SachCHO_20191221_GF_v2.pdf (1.37 MiB) download file view on ChemRxiv Video1_gel-sol-gel_vial.mp4 (109.69 MiB) download file view on ChemRxiv Video2_microscopy.mp4 (62.71 MiB)

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.

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