Tunable swelling kinetics in core--shell hydrogel nanoparticles.

Thermoresponsive, core--shell poly-N-isopropylacrylamide (p-NIPAm) nanoparticles (microgels) have been synthesized by seed and feed precipitation polymerization, and the influence of chemical differentiation between the core and shell polymers on the phase transition kinetics and thermodynamics has been examined. The results suggest that the core--shell architecture is a powerful one for the design of colloidal "smart gels" with tunable properties. To examine these materials, differential scanning calorimetry (DSC), (1)H NMR, and temperature-programmed photon correlation spectroscopy (TP-PCS) have been employed. These measurements show that the addition of small concentrations of a hydrophobic monomer (butyl methacrylate, BMA) into the particle shell produces large decreases in the rate of thermo-induced particle collapse. Conversely, these low levels of hydrophobic modification do not perturb the thermodynamics of the particle phase transition. When these results are examined in light of previous studies of macroscopic hydrogels, they suggest that the formation of a thin, stable skin layer at the particle exterior during the early stages of particle collapse is the rate limiting factor in particle deswelling. Finally, the hydrophobicity (BMA content) of the shell determines the magnitude of the hydrogel collapse rate, while the thickness of the BMA containing region does not impact the observed kinetics. Together, these results suggest that control over the kinetics of microgel deswelling events can be accomplished simply by modification of the particle periphery, and therefore do not require homogeneous modification of the entire polymer structure.