Interplay of network architectures and ionic environments in dictating pNIPAM microgel thermoresponsiveness

The utility of non-functionalized poly(N-isopropylacrylamide) (pNIPAM) microgels in physiological and environmental applications is strictly dependent on their reversible thermoresponsiveness and stability in saline media. Despite their importance, a unified understanding of how network topology, specifically crosslinker concentration and crosslinking distribution regulates ionic sensitivity remains fragmented in the literature. This work systematically investigates the interplay between network topology and ionic strength (0-100 mM NaCl) across eight distinct microgel architectures, ranging from ultra-low crosslinked (ULC) to core-corona and homogeneously crosslinked (HC) variants. Utilizing dynamic light scattering across 22 batches, we analyzed critical thermoresponsive properties, including volume phase transition temperature (VPTT) shifts, salt tolerance thresholds, hysteresis indices, and flocculation kinetics (only at extreme salinity, 1000 mM NaCl and at 25 °C). This comprehensive investigation enables a multi-dimensional analysis of how ionic strength, the presence or absence of crosslinkers (MBA), spatial crosslinking distribution, and thermodynamic states dictate microgel behavior across varying temperatures. Finally, we evaluate the applicability of this experimental dataset to established theoretical frameworks, specifically the Flory-Rehner and Flory-Rehner-Donnan models, making an attempt to address the ongoing debate regarding their validity in describing complex microgels.