Thermal Transitions in Polyelectrolyte Assemblies Occur via a Dehydration Mechanism

Date

2015-09-01

Author

Yıldırım, Erol
Lutkenhaus, Jodie L.
Sammalkorpi, Maria

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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.

Subject Keywords

By-layer assemblies, Multilayers, Temperature, Behavior

URI

https://hdl.handle.net/11511/35255

Journal

ACS MACRO LETTERS

DOI

https://doi.org/10.1021/acsmacrolett.5b00351

Collections

Department of Chemistry, Article

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Citation Formats

E. Yıldırım, J. L. Lutkenhaus, and M. Sammalkorpi, “Thermal Transitions in Polyelectrolyte Assemblies Occur via a Dehydration Mechanism,” ACS MACRO LETTERS, pp. 1017–1021, 2015, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/35255.