TY - JOUR
T1 - Relating side chain organization of PNIPAm with its conformation in aqueous methanol
AU - Mukherji, Debashish
AU - Wagner, Manfred
AU - Watson, Mark D.
AU - Winzen, Svenja
AU - De Oliveira, Tiago E.
AU - Marques, Carlos M.
AU - Kremer, Kurt
N1 - Publisher Copyright:
© 2016 The Royal Society of Chemistry.
PY - 2016
Y1 - 2016
N2 - Combining nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and μs long all-atom simulations with two million particles, we establish a delicate correlation between increased side chain organization of PNIPAm and its collapse in aqueous methanol mixtures. We find that the preferential binding of methanol with PNIPAm side chains, bridging distal monomers along the polymer backbone, results in increased organization. Furthermore, methanol-PNIPAm preferential binding is dominated by hydrogen bonding. Our findings reveal that the collapse of PNIPAm is dominated by enthalpic interactions and that the standard poor solvent (entropic) effects play no major role.
AB - Combining nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and μs long all-atom simulations with two million particles, we establish a delicate correlation between increased side chain organization of PNIPAm and its collapse in aqueous methanol mixtures. We find that the preferential binding of methanol with PNIPAm side chains, bridging distal monomers along the polymer backbone, results in increased organization. Furthermore, methanol-PNIPAm preferential binding is dominated by hydrogen bonding. Our findings reveal that the collapse of PNIPAm is dominated by enthalpic interactions and that the standard poor solvent (entropic) effects play no major role.
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U2 - 10.1039/c6sm01789d
DO - 10.1039/c6sm01789d
M3 - Article
AN - SCOPUS:84989327951
VL - 12
SP - 7995
EP - 8003
IS - 38
ER -