10.1021/acsmacrolett.7b00557.s001 Sebastian Backes Sebastian Backes Patrick Krause Patrick Krause Weronika Tabaka Weronika Tabaka Marcus U. Witt Marcus U. Witt Debashish Mukherji Debashish Mukherji Kurt Kremer Kurt Kremer Regine von Klitzing Regine von Klitzing Poly(<i>N</i>‑isopropylacrylamide) Microgels under Alcoholic Intoxication: When a LCST Polymer Shows Swelling with Increasing Temperature American Chemical Society 2017 bulk solution properties VPTT volume phase transition temperature LCST Polymer Shows isopropylacrylamide PNIPAM microgels reswelling 2017-09-12 12:50:48 Journal contribution https://acs.figshare.com/articles/journal_contribution/Poly_i_N_i_isopropylacrylamide_Microgels_under_Alcoholic_Intoxication_When_a_LCST_Polymer_Shows_Swelling_with_Increasing_Temperature/5398423 Poly­(<i>N</i>-isopropylacrylamide) (PNIPAM) microgel is a smart polymer that shows a volume phase transition temperature (VPTT) at around 32 °C in aqueous solutions, above which it collapses. In this work, combining experiments and molecular simulations, it is shown that PNIPAM microgels do not always exhibit a collapsed structure above the VPTT. Instead, PNIPAM in aqueous alcohol mixtures shows a two-step conformational transition, i.e., a collapse at low temperatures (<i>T</i> < 32 °C) and a reswelling when <i>T</i> > 50 °C. The present analysis indicates that delicate microscopic interaction details, together with the bulk solution properties, play a key role in dictating the reswelling behavior. Even when PNIPAM microgels swell with increasing <i>T</i>, this is not a standard upper critical solution behavior.