Probing the Structural Dynamics of the Coil-Globule Transition of Thermosensitive Nanocomposite Hydrogels

Nanocomposite hydrogels have emerged to exhibit multipurpose properties, boosting especially the biomaterial field. However, the development and characterization of these materials can be a challenge, especially stimuli-sensitive materials with dynamic properties in response to external stimuli. By employing UV-vis spectroscopy and NMR relaxation techniques, we could outline the formation and behavior of thermosensitive nanocomposites obtained by in situ polymerization of poly(N-vinylcaprolactam) (PNVCL) and mesoporous silica nanofibers under temperature stimuli. For instance, inorganic nanoparticles covalently linked to PNVCL changed the pattern of temperature-induced phase transition despite showing similar critical temperatures to neat PNVCL. Thermodynamic parameters indicated the formation of an interconnected system of silica and polymer chains with reduced enthalpic contribution and mobility. The investigation of water molecule and polymer segment motions also revealed that the absorption and release of water happened in a wider temperature range for the nanocomposites, and the polymer segments respond in different ways during the phase transition in the presence of silica. This set of techniques was essential to reveal the polymer motions and structural features in nanocomposite hydrogels under temperature stimuli, demonstrating its potential use as experimental guideline to study multicomponent nanocomposites with diverse functionalities and dynamic properties.