Citation:
Luo, Z. ; Zhu, N. ; Zhao, D. *. Helical Folding Competing with Unfolded Aggregation in Phenylene Ethynylene Foldamers. Chem. Eur. J. 2016, 22, 11028-11034.
摘要:
The folding and aggregation behavior of a pair of oligo(phenylene ethynylene) (OPE) foldamers are investigated by means of UV/Vis absorption and circular dichroism spectroscopy. With identical OPE backbones, two foldamers, 1 with alkyl side groups and 2 with triethylene glycol side chains, manifest similar helical conformations in solutions in n-hexane and methanol, respectively. However, disparate and competing folding and aggregation processes are observed in alternative solvents. In cyclohexane, oligomer 1 initially adopts the helical conformation, but the self-aggregation of unfolded chains, as a minor component, gradually drives the folding-unfolding transition eventually to the unfolded aggregate state completely. In contrast, in aqueous solution (CH3OH/H2O) both folded and unfolded oligomer 2 appear to undergo self-association; aggregates of the folded chains are thermodynamically more stable. In solutions with a high H2O content, self-aggregation among unfolded oligomers is kinetically favored; these oligomers very slowly transform into aggregates of helical structures with greater thermodynamic stability. The folded-unfolded conformational switch thus takes place with the free (nonaggregated) molecules, and the very slow folding transition is due to the low concentration of molecularly dispersed oligomers.See also: 2016