Macromolecular Rapid Communications, Vol.34, No.5, 417-422, 2013
Hofmeister Effect of Sodium Halides on the Switching Energetics of Thermoresponsive Polymer Brushes
A laser temperature-jump technique is used to probe the impact of sodium halides on the temperature-dependent switching kinetics and thermodynamics of poly(N-isopropylacrylamide) brushes. An analysis on the basis of a two-state model reveals van't Hoff enthalpy and entropy changes. Sodium halides increase the endothermicity and the entropic gain of the switching process below and above Tc following the Hofmeister series: NaCl > NaBr > NaI. In contrast, enthalpic and entropic changes at Tc remain virtually unaffected. This provides an unprecedented insight into the underlying switching energetics of this classic stimuli-responsive polymer. Because of its model character, these results represent an essential reference on the way to unpuzzle the molecular driving forces of the Hofmeister effect.
Keywords:cooperative effects;laser temperature-jump techniques;specific ion effects;stimuli-sensitive polymers;van't Hoff enthalpies