Fig. 2: Small molecule CRN model for signal-induced and fuel-driven autonomous cycle.

a CRN of fuel with t-Am-1 (DABCO) or t-Am-2 (pyridine) and SH-3 in signal-induced mode or fuel with t-Am-2 and excess NH₂-4 in fuel-driven autonomous mode. Conversion of the reactants was monitored by ¹H NMR over time in D₂O/phosphate buffer 1:9 (pH = 7.4, 0.1 M (signal-induced cycle) or 0.5 M (autonomous cycle)) at room temperature. b Signal-induced cycle (Supplementary Fig. 6) with t-Am-1: DVP (42 mM, 1.0 eq.), t-Am-1 (0.2 eq.) and four times addition of SH-3 (0.2 eq.). c Signal induced cycle (Supplementary Fig. 7) with t-Am-2: DVP (42 mM, 1.0 eq.), t-Am-2 (0.2 eq.) and four times addition of SH-3 (0.2 eq.). Autonomous cycle (Supplementary Figs. 8–10) with fuel/nucleophile variations at constant t-Am-2 (8.5 mM, 1.0 eq.) concentration (d): DVP (2.0 eq.) and NH₂-4 (4.0 eq.), e DVP (4.0 eq.) and NH₂-4 (8.0 eq.), f DVP (1.0 eq.) and NH₂-4 (2.0 eq.). d–f At observed equilibrium an additional 4.0, 8.0, and 2.0 equivalents of NH₂-4 were added to one of the duplicate reaction mixtures, respectively. The error bars represent the standard deviation of duplicate measurements. For (d, e) the product percentages were normalized to 100. Activated intermediates were isolated by exchanging their counterion from acetate to chloride (for full characterisation see Supplementary Figs. 34–43, 54 and 55).