Distinct Cation–Anion Interactions in the UCST and LCST Behavior of Polyelectrolyte Complex Aqueous Solutions
Zhangxin Ye, Shengtong Sun*, and Peiyi Wu*. Distinct Cation–Anion Interactions in the UCST and LCST Behavior of Polyelectrolyte Complex Aqueous Solutions. ACS Macro Lett. 2020, 9, 974-979.
Polyelectrolyte complexes (PECs) are recently observed to possess diversified thermoresponsive phase transition behaviors in aqueous solutions. Herein, by adjusting the initial polymer concentrations (Cpi) of poly(styrenesulfonate) (PSS)/poly(diallyldimethylammonium) (PDADMA) PEC in the same saline solution, in addition to previously reported lower critical solution temperature (LCST), we experimentally observed the upper critical solution temperature (UCST)-type phase transition behavior of PSS/PDADMA PECs at a lower polymer concentration. As elucidated by temperature-dependent Raman spectroscopy and two-dimensional correlation analysis, at temperatures lower than UCST, more hydrophobic polyelectrolyte chains lead to a high proportion of contact ion pairs (CIPs), contributing to UCST-type solid–liquid phase transition; however, at higher concentrations of PEC, the less hydrophobic polyelectrolyte chains correspond to a higher proportion of solvent-separated ion pairs (SIPs), which enables the occurrence of LCST-type liquid–liquid phase transition. With the spectroscopic indicator of CIPs/SIPs peak ratio and monitoring the hydration state of polymer chains, the complex interplays of PSS/PDADMA PECs are hereby interpreted at the molecular level, which lays the mechanistic foundation for designing other thermoresponsive PEC assemblies.