Fig. 3. Redox mediated generation of transient-dormant monomer states.

a Schematic representation of unfolding of PNF CT foldamer upon reduction with SDT to its PNF-NDI^•− and PNF-NDI²⁻ reduced states. b Absorption spectral changes on addition of varying eq. of SDT to PNF, generating PNF-NDI^•− and PNF-NDI²⁻ and c corresponding absorbance plot monitoring at the maxima of both reduced states. Photographs of all NDI states are shown in the inset of c. d DLS spectra indicates the formation of smaller size aggregates of PNF-NDI^•− assembly with hydrodynamic diameter (d_H) = 100 ± 25 nm (PDI obtained from DLS (PDI_DLS) = 0.45) compared to PNF tape structures with d_H = 554 ± 150 nm (PDI_DLS = 0.59), on addition of SDT. e AFM image of the unfolded PNF-NDI^•− assemblies exhibiting the spherical aggregate morphology. f, g corresponds to the snapshots, before addition of SDT and after addition of 40 eq. SDT at different time intervals respectively, taken from the Supplementary movie 1. Dotted circle points the surface bound micrometer long tape structures which undergoes disassembly and forms aligned spherical aggregates of PNF-NDI^•−. The difference in kinetics compared to solution state kinetics is due to different experimental conditions, as for microscopy the solution is more exposed to air and the supramolecular polymers captured are sticking on the surface thus SDT needs to diffuse to the fibers to induce disassembly. [PNF] = 5 × 10⁻⁵ M, CH₃CN/H₂O (1:1 v/v). pH = 8, buffer.