Light-Fueled Primitive Replication and Selection in Biomimetic Chemical Systems

Abstract

The concept of chemically evolvable replicators is central to abiogenesis. Chemical evolvability requires three essential components: energy-harvesting mechanisms for nonequilibrium dissipation, kinetically asymmetric replication and decomposition pathways, and structure-dependent selective templating in the autocatalytic cycles. We observed a UVA light-fueled chemical system displaying sequence-dependent replication and replicator decomposition. The system was constructed with primitive peptidic foldamer components. The photocatalytic formation−recombination cycle of thiyl radicals was coupled with the molecular recognition steps in the replication cycles. Thiyl radical-mediated chain reaction was responsible for the replicator death mechanism. The competing and kinetically asymmetric replication and decomposition processes led to light intensity-dependent selection far from equilibrium. Here, we show that this system can dynamically adapt to energy influx and seeding. The results highlight that mimicking chemical evolution is feasible with primitive building blocks and simple chemical reactions.

The Role of Hydrogen Bonds in Thermally Responsive Crystallization‐Driven Template Autocatalysis

“…Given that product inhibition is a result of the irreversible bonding formation, autocatalytic reactions commonly occur far from thermodynamic equilibrium [6b,10] . Along this line, dissipative out‐of‐equilibrium systems driven by chemical fuels, [11] chemical oscillations, [12] transient assembly, [13] reactive diffusion, [14] and energy consumption [15] have recently been investigated. Of significant advance are the representative works reported by Otto and co‐workers, [16] in which upon continuously shaking or stirring the reaction mixture, nanofibers assembled from the size‐selective macrocycles can be sheared into numerous short segments with active ends for templating reversible cyclization of dithiol precursors.…”

New Insights on the Chemical Origin of Life: The Role of Aqueous Polymerization of N‐carboxyanhydrides (NCA)

“…[65b,66] Moreover, self-selection can be pushed out-of equilibrium through macromolecular replication, as shown with RNA [5] or with primitive peptidic foldamer components. [67] Indeed, the secondary structure of polypeptides (α-helix, β-sheet, figure 4) has also yielded already surprising results. [36a] Secondary structures of polypeptides can self-organize according to thermodynamic processes very similar to crystallization phenomena.…”

Photochromic clock reaction of anthraquinone in supramolecular gel and its application to spatiotemporal patterning

“…20,21 In photochemical reactions, if clock behaviors that the desired reaction proceeds with a well-defined induction period after starting photoirradiation are achieved, it leads to the prevention of accidental reaction progress by ambient light and the development of temporally-controlled photofunctional materials and light-fueled dissipative chemical systems. 22–27…”