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The vibrational dynamics of a new class of cross-linked polymers made up of cyclodextrins is here investigated in the microscopic range by the joint use of light and inelastic neutron scattering experiments. The effect of increasing the connectivity of the polymeric network on the vibrational dynamics of the system is studied by exploiting the complementarity of these two different probes. The derived densities of vibrational states of the polymers evidence the presence of the characteristic anomalous excess of vibrational modes with respect to the Debye level, already observed in the low-frequency Raman spectra and referred to as boson peak (BP). The overall analysis of the spectra suggests an emerging picture in which the motions of hydrogen atoms of the polymers are progressively hampered when the cross-linking degree of the covalent network increases. At the same time, the frequency and intensity of the BP are found to significantly change by increasing the cross-linking degree of the polymeric network, as clearly suggested by the existence of a scaling-law for the BP evolution. These findings support the conclusion that the growing of the covalent connectivity of the system induces a general modifications of the elastic properties of these cyclodextrin-based polymers, which are, once again, modulated by the cross-linking agent/cyclodextrin molar ratio.

The effect of the inclusion into cyclodextrins (CD) cavity on the low-frequency vibrational dynamics of the anti-inflammatory drug ibuprofen (IBP) is here investigated by using Raman and inelastic neutron scattering (INS) experiments. The differences observed in the frequency regime 0-100 cm(-1) between the vibrational modes of uncomplexed racemic and enantiomeric IBP are discussed on the basis of comparison with the quantum chemical computation results, taking into account the distinct symmetry properties of the molecules involved in the formation of the host-guest complex. Subsequently, the inspection of the same frequency range in the spectra of pure host methyl-β-CD and its IBP-inclusion complexes allows one to identify significant modifications in the vibrational dynamics of the guest molecule after their confinement into CD cavity. The experimental Raman and neutron spectra and the derived Raman coupling function C(R)(ω) show that the complexation process gives rise to a complete amorphization of the drug, as well as to a partial hindering, in the vibrational dynamics of complexes, of the modes between 50 and 150 cm(-1) attributed to CD molecule. The comparison between the Raman and neutron spectra of free and complexed IBP in the energy range of the Boson peak (BP) gives evidence that the dynamics related to this specific vibrational feature is sensitive to complexation phenomena.

An integrated experimental approach, based on inelastic light-scattering techniques, has been here employed for a multilength scale characterization of networking properties of cyclodextrin nanosponges, a new class of cross-linked polymeric materials built up from natural oligosaccharides cyclodextrins. By using Raman and Brillouin scattering experiments, we performed a detailed inspection of the vibrational dynamics of these polymers over a wide frequency window ranging from gigahertz to terahertz, with the aim of providing physical descriptors correlated to the cross-linking degree and elastic properties of the material. The results seem to suggest that the stiffness of cross-linked polymers can be successfully tuned by acting on the type and the relative amount of the cross-linker during the synthesis of a polymer matrix, predicting and controlling their swelling and entrapment properties. The proposed experimental approach is a useful tool for investigating the structural and physicochemical properties of polymeric network systems.