Chirality dependent inverse-melting and re-entrant gelation in α-cyclodextrin/1-phenylethylamine mixtures.

Solutions of cyclohexakis-(1→4)-α-d-glucopyranosyl, α-cyclodextrin, αCD, in R -(+)-1-phenylethylamine, αCD/R-PEA, and S -(-)-1-phenylethylamine, αCD/S-PEA, display abnormal phase transitions that strongly depend on supramolecular diastereomeric interactions. While αCD/R-PEA mixtures show one sol-gel inverse-melting phase transition, αCD/S-PEA mixtures show temperature dependent gel-sol-gel re-entrant behavior. NMR, Raman spectroscopy, microscopy and X-ray scattering measurements reveal that hydrogen bond weakening in solution, as well as changes in crystal composition are responsible for entropy increase and gel formation upon heating.