The
insertion of nanoparticles into smart hydrogels can diversify
their functionalities by a synergistic combination of the components
properties within the hydrogels. While these hybrid systems are attractive
to the biomaterials field, careful design and control of their properties
are required since the new interactions between the polymer and the
nanoparticles can result in changes or the loss of hydrogels stimuli
response. In order to understand the physicochemical aspects of the
thermoresponsive systems, nanocomposites of poly(N-vinylcaprolactam) (PNVCL) and silica nanoparticles with different
sizes and concentrations were synthesized. The UV–vis and DLS
techniques showed that the PNVCL has a sharp phase transition at 34
°C, while the nanocomposites have a diffuse transition. The nanocomposites
showed an initial coil–globule transition before the phase
transition takes place. This was identified by the evolution of the
hydrodynamic diameter of the nanocomposite globules before the cloud
point temperature (T
cp), which remained
constant for PNVCL. This new transition profile can be described by
two stages in which microscopic volume transitions occur first, followed
by the macroscopic transition that forms the hydrogel. These results
show that the proposed nanocomposites can be designed to have tunable
stimuli response to smaller temperature variations with the formation
of intermediate globule states.