Fig. 3: Studies on monomer folding.
From: Living supramolecular polymerization of fluorinated cyclohexanes
a CD monitoring (260 nm) of M3 (1.2 mM) in cyclohexane/chloroform (84:16 v/v) at 293 K, indicating remarkable kinetic stability. b Temperature-dependent CD spectra of M3 (1.2 mM) in cyclohexane/chloroform (84:16 v/v) upon cooling from 293 K to 275 K (0.5 K min−1). c CD monitoring (260 nm) of cooling (blue) and heating (red) of a 1.2 mM solution of M3 in cyclohexane/chloroform (84:16 v/v) at a rate of 0.5 K min−1. Once nucleation starts in a concentrated solution at temperatures for which ΔG is already negative, polymerization proceeds very rapidly since the concentration of free monomer in solution is high, leading to a very sharp transition during cooling (blue line). d Free energy surface (FES) estimated from WT-MetaD simulations, showing monomer conformations and their relative free energies as a function of collective variables CV1 (x-axis: difference between the distance between pentafluorocyclohexyl-Hs and the amide oxygen and the distance between the pentafluorocyclohexyl-Fs and the amide nitrogen) and CV2 (y-axis: radius of gyration of M3 monomer core). Blue colored areas represent the low free energy domains while the gray colored background is high in free energy or not accessible. Four representative monomer conformations (I, II, III, IV) taken from the FES are reported (alkyl chains are shown in transparency for clarity). Color code: green: F; red: O; blue: N; gray: C.
