Hydrogen-bond dynamics of water confined in cyclodextrin nanosponges hydrogel

Cyclodextrin nanosponges (CDNS) are a very promising class of cross-linked polymers, made up of cyclodextrins. CDNS swollen in aqueous solution give rise to cyclodextrin-based hydrogel in different states-gel or liquid suspension-depending on the hydration level of the system. Here we present a thorough inspection of the vibrational dynamics of these hydrogel by Raman scattering experiments, with the aim of clarifying the role played by the hydrogen-bond dynamics of water molecules confined into the nano-sized pores of nanosponges in determining the rigidity of the hydrogel network and their maximum water-holding capacity. Changes occurring in the spectral shape of the OH stretching band of water were interpreted by accounting the connectivity pattern of water molecules concurring to the gelation process. Spectral deconvolution analysis gives evidence of the existence of a characteristic cross-over hydration level associated to the rearrangement of water molecules in more cooperative, bulk-like networks as a consequence of saturation sites of water confinement of nanosponges. This interpretation is further confirmed by the inspection of the estimated collective intensities. These findings also support the existence of a specific phase diagram of the cyclodextrin nanosponges hydrogel, where the molecular structure of the cross-linking agent used during the synthesis of nanosponge plays a fundamental role in defining the nano- and microscopic properties of the system.