Light-Mediated Interconversion\nbetween a Foldamer\nand a Self-Replicator

Self-replicating molecules and well-defined folded macromolecules\nare of great significance in the emergence and evolution of life.\nHow they may interconnect and affect each other remains largely elusive.\nHere, we demonstrate an abiotic system where a single building block\ncan oligomerize to yield either a self-replicating molecule or a foldamer.\nSpecifically,\nagitation of a disulfide-based dynamic combinatorial library at moderately\nelevated pH channels it selectively into a self-replicating hexamer\nassembled into fibers, after passing through a period where a 15-subunit\nmacrocyclic foldamer existed transiently. Without mechanoagitation\nor at lower pH, the formation of hexamer fiber is suppressed, resulting\nin the accumulation of the 15mer foldamer. Foldamer and self-replicator\ncan be interconverted in response to external stimuli, including agitation\nand a change in pH. Furthermore, upon the addition of a photoacid,\nthe pH of the medium can be controlled by irradiation, driving the\nswitching between replicator and foldamer and allowing a dissipative\nout-of-equilibrium state to be accessed, using light as a source of\nenergy.