EPR spectroscopy reveals nanoinhomogeneities in the structure and reactivity of thermoresponsive hydrogels.

The dynamic and chemical behavior of solute molecules inside new thermoresponsive hydrogels (photocrosslinked poly(N-isopropylacrylamide) (pNiPAAm) copolymers) is studied by continuous-wave electron paramagnetic resonance spectroscopy. Via addition of paramagnetic tracer molecules (so-called spin probes) a picture is obtained of the thermally induced collapse on the molecular scale, which proceeds over a substantially broader temperature range than indicated by the sharp macroscopic volume transition. The sampling of hydrophilic and hydrophobic environments suggests a discontinuous collapse mechanism with a coexistence of collapsed and expanded network regions. These structural inhomogeneities on the nanoscale also lead to an inhomogeneity in chemical reactivity. The hydrophilic regions form nanoreactors, which strongly accelerate the reaction while the hydrophobic regions act as nanoshelters, in which enclosed spin probes are protected from the decay. The results show that the system consisting of a statistical binary or tertiary copolymer displays remarkably complex behavior that mimics spatial and chemical inhomogeneities observed in functional biopolymers such as enzymes.