Thermal Transitions in Polyelectrolyte Assemblies Occur via a Dehydration Mechanism

Yildirim E., Zhang Y., Lutkenhaus J. L., Sammalkorpi M.

ACS MACRO LETTERS, vol.4, no.9, pp.1017-1021, 2015 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 4 Issue: 9
  • Publication Date: 2015
  • Doi Number: 10.1021/acsmacrolett.5b00351
  • Journal Name: ACS MACRO LETTERS
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1017-1021
  • Middle East Technical University Affiliated: No


Hydrated polyelectrolyte (PE) complexes and multilayers undergo a well-defined thermal transition that bears resemblance to a glass transition. By combining molecular simulations and differential scanning calorimetry (DSC) of poly(diallyldimethylammonium) (PDAC) and poly(styrenesulfonate) (PSS) multilayers, we establish for the first time that dehydration drives the thermally induced change in plasticization of the complex and in the diffusion behavior of its components. DSC experiments show that the thermal transition appears when the assemblies are hydrated in water but not in the presence of alcohols, which supports that water is required for this transition. These findings connect PE complexes more generally to thermoresponsive polymers and liquid crystal phases, which bear phase transitions driven by the (de)hydration of functional groups, thus forming a fundamental link toward an integrated understanding of the thermal response of molecular materials in aqueous environments.