Dissipative Organization of DNA Oligomers for Transient Catalytic Function

The development of synthetic non‐equilibrium systems opens doors for man‐made life‐like materials. Yet, creating distinct transient functions from artificial fuel‐driven structures remains a challenge. Building on our ATP‐driven dynamic covalent DNA assembly in an enzymatic reaction network of concurrent ATP‐powered ligation and restriction, we introduce ATP‐fueled transient organization of functional subunits for various functions. The programmability of the ligation/restriction site allows to precisely organize multiple sticky‐end‐encoded oligo segments into double‐stranded (ds) DNA complexes. We demonstrate principles of ATP‐driven organization into sequence‐defined oligomers by sensing barcode‐embedded targets with different defects. Furthermore, ATP‐fueled DNAzymes for substrate cleavage are achieved by transiently ligating two DNAzyme subunits into a dsDNA complex, rendering ATP‐fueled transient catalytic function.