Stimuli-responsive materials typically contain responsive molecular units that couple an external trigger to a defined macroscale response. Ongoing efforts to boost the versatility and complexity of these responses increasingly focus on multi-stimuli-responsive molecular units and crosslinkers, as these bear the potential to impart self-regulatory behaviors building on cooperative effects and feedback mechanisms. Herein, we study a stimuli-responsive platform consisting of polyacrylamide-based hydrogels with well-known multi-responsive spiropyrans covalently bound as pendant groups or ´non-innocent´ crosslinkers. Surprisingly, as compared to their appended counterparts, spiropyran crosslinkers cause up to two-fold larger hydrogel swelling in methylenebisacrylamide-crosslinked poly(acrylamide-co-acrylic acid) hydrogels, despite their increased relative crosslinking density. We seek the origin of this unexpected behavior by employing nanoindentation, swelling studies, and UV-vis spectroscopy to study changes in mechanical properties and in spiropyran isomer distribution as a function of solution pH, co-monomer chemistry, and swelling-induced polymer strain. We then estimate the osmotic counterion pressures as a function of spiropyran isomer distribution but find that such pressures alone are insufficient to explain the observed behavior. Charge complexation, cooperative effects between the hydrogel´s mechanics and chemistry, and aggregate formation may all be invoked to explain features of the observed ´non-innocence´ of spiropyran crosslinkers. Taken together, these insights will aid rational implementation of such responsive crosslinkers in materials design and extend the functionality of existing polymeric materials towards more complex and better tunable behaviors.
Supporting Information includes experimental procedures, characterization, and synthetic procedures of the spiropyran-precursors and spiropyran-modified hydrogels, study of hydrogel swelling behavior, nanoindentation measurements, UV-vis absorption and (ATR)-FTIR spectra, and theoretical modelling.