Chemical specificity in polyzwitterion-polyelectrolyte coacervates: polycations vs polyanions

Keum, Jong K.; Christakopoulos, Panagiotis; Liu, Zening; Li, Tianyu; Chen, Jihua; Williams, Alexis; Hensley, Dale K.; Hong, Kunlun; Wang, Yangyang; Advincula, Rigoberto; Kumar, Rajeev

doi:10.1016/j.eurpolymj.2024.113177

Chemical specificity in polyzwitterion-polyelectrolyte coacervates: polycations vs polyanions

Journal Article · Thu Jun 06 00:00:00 EDT 2024 · European Polymer Journal

DOI:https://doi.org/10.1016/j.eurpolymj.2024.113177· OSTI ID:2376380

^[1]; ^[1]; Liu, Zening ^[1]; Li, Tianyu ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; Advincula, Rigoberto ^[1]; ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Aqueous solutions containing polyzwitterions and polyelectrolytes were studied to probe the effects of chemical specificity on the complexation among different types of chains and resulting liquid–liquid phase separation (coacervation). Two kinds of blends were studied. A polyzwitterion, poly(sulfobetaine methacrylate) (PSBMA), was blended with either (1) a polycation, poly(diallydimethylammonium chloride) (PDADMAC), or (2) a polyanion, sodium poly(styrene sulphonate) (NaPSS). Coacervation was observed in both blends after equilibration, while the freshly prepared blend solutions exhibited distinct behavior dependent on the mixing protocols. Mixing solutions of the polyzwitterions and the polycations led to coacervation almost instantaneously. In contrast, the blends containing the same polyzwitterions and the polyanions exhibited no such coacervation by following the same mixing protocol. However, blends prepared after dissolving a solid mixture containing the same polyzwitterions and the polyanions in water exhibited coacervation. Based on the small-angle X-ray scattering (SAXS), cryo-electron microscopy, and rheology measurements, complexation and coacervation in the polyzwitterion-polyelectrolyte blends is rationalized in terms of the entropy change associated with reorganization of solvent (water), which appears to be larger in the polyzwitterion-polycation case in comparison with the polyzwitterion-polyanion blends. These results highlight the importance of chemical specificity and mixing protocols leading to metastable structures in designing a new class of materials based on macromolecular complexation of polyzwitterions.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2376380

Journal Information:: European Polymer Journal, Journal Name: European Polymer Journal Vol. 215; ISSN 0014-3057

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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