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Relationship between Elastic Properties and Gel-to-Sol Transition in Cyclodextrin-Based Hydrogel

Majolino D, Venuti V, Crupi V, Rossi B, Fontana A, Mele A, Melone L, Punta C, Trotta F, Giarola M and Mariotto G

In order to elucidate the effects of the nature of the cross-linker, of the hydration level and of the hydrophobic/ hydrophilic balance on the macro- and microscopic properties of a paradigmatic model of polysaccharide hydrogel, an integrated approach based on the combined use of low-frequency Raman scattering and FTIR-ATR absorption has been developed. The proposed methodology aims to explore the stability range of the liquid and gel phase diagram of the system. This approach was applied to cyclodextrin based nanosponges (CDNS), prepared by polymerization of α-, β-, and γ-cylcodextrins (CDNS) with an activated derivative of ethylenediamine tetra acetic acid. It revealed successful, on one side, for a comparative analysis of the elasticity, as mesoscopic parameter, of the dry polymeric network, measured by Raman spectroscopy in the low frequency (0 ÷ 150 cm–1) range, and, on the other side, for the investigation of the water holding capacity, as macroscopic parameter, through the analysis of the vibrational dynamics of water molecules in the swollen polymers, monitored by FTIR-ATR spectroscopy in two selected wavenumber regions, i.e. 2800 ÷ 3800 cm–1 and 1500 ÷ 1800 cm–1, where the O-H stretching and H-O-H bending vibrations respectively occur. As main result, the same evolution as a function of the molar ratio n, has been observed for the elasticity on mesoscopic scale, as described by the Boson Peak (ωBP) and the swelling ability on macroscopic scale, expressed by the mass ratio m describing the gel-to-sol transition in these systems. From the results, the way for a rational development of stimuli-responsive systems with specific performances, by modulating the stability range of the liquid suspension and gel phases properly changing the molar ratio n during the synthesis, is opened.

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