TY - JOUR A1 - Kreuzer, Lucas A1 - Lindenmeir, Christoph A1 - Geiger, Christina A1 - Widmann, Tobias A1 - Hildebrand, Viet A1 - Laschewsky, André A1 - Papadakis, Christine M. A1 - Müller-Buschbaum, Peter T1 - Poly(sulfobetaine) versus poly(N-isopropylmethacrylamide) BT - co-nonsolvency-type behavior of thin films in a water/methanol atmosphere JF - Macromolecules : a publication of the American Chemical Society N2 - The swelling and co-nonsolvency behaviors in pure H2O and in a mixed H2O/CH3OH vapor atmosphere of two different polar, water-soluble polymers in thin film geometry are studied in situ. Films of a zwitterionic poly(sulfobetaine), namely, poly[3-((2-(methacryloyloxy)ethyl)dimethylammonio) propane-1-sulfonate] (PSPE), and a polar nonionic polymer, namely, poly(N-isopropylmethacrylamide) (PNIPMAM), are investigated in real time by spectral reflectance (SR) measurements and Fourier transform infrared (FTIR) spectroscopy. Whereas PSPE is insoluble in methanol, PNIPMAM is soluble but exhibits cononsolvency behavior in water/methanol mixtures. First, the swelling of PSPE and PNIPMAM thin films in H2O vapor is followed. Subsequently, CH3OH is added to the vapor atmosphere, and its contracting effect on the water-swollen films is monitored, revealing a co-nonsolvency-type behavior for PNIPMAM and PSPE. SR measurements indicate that PSPE and PNIPMAM behave significantly different during the H2O swelling and subsequent exposure to CH3OH, not only with respect to the amounts of absorbed water and CH3OH, but also to the cosolvent-induced contraction mechanisms. While PSPE thin films exhibit an abrupt one-step contraction, the contraction of PNIPMAM thin films occurs in two steps. FTIR studies corroborate these findings on a molecular scale and reveal the role of the specific functional groups, both during the swelling and the cosolvent-induced switching of the solvation state. Y1 - 2021 U6 - https://doi.org/10.1021/acs.macromol.0c02281 SN - 0024-9297 SN - 1520-5835 VL - 54 IS - 3 SP - 1548 EP - 1556 PB - American Chemical Society CY - Washington ER -