Effect of Ethanol and Urea as Solvent Additives on PSS-PDADMA Polyelectrolyte Complexation

Mohammad Khavani, Piotr Batys, Suvesh M. Lalwani, Chikaodinaka I. Eneh, Anna Leino, Jodie L. Lutkenhaus*, Maria Sammalkorpi*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

12 Citations (Scopus)
125 Downloads (Pure)

Abstract

The effect of urea and ethanol additives on aqueous solutions of poly(styrenesulfonate) (PSS), poly(diallyldimethylammonium) (PDADMA), and their complexation interactions are examined here via molecular dynamics simulations, interconnected laser Doppler velocimetry, and quartz crystal microbalance with dissipation. It is found that urea and ethanol have significant, yet opposite influences on PSS and PDADMA solvation and interactions. Notably, ethanol is systematically depleted from solvating the charge groups but condenses at the hydrophobic backbone of PSS. As a consequence of the poorer solvation environment for the ionic groups, ethanol significantly increases the extent of counterion condensation. On the other hand, urea readily solvates both polyelectrolytes and replaces water in solvation. For PSS, urea causes disruption of the hydrogen bonding of the PSS headgroup with water. In PSS-PDADMA complexation, these differences influence changes in the binding configurations relative to the case of pure water. Specifically, added ethanol leads to loosening of the complex caused by the enhancement of counterion condensation; added urea pushes polyelectrolyte chains further apart because of the formation of a persistent solvation shell. In total, we find that the effects of urea and ethanol rise from changes in the microscopic-level solvation environment and conformation resulting from solvating water being replaced by the additive. The differences cannot be explained purely via considering relative permittivity and continuum level electrostatic screening. Taken together, the findings could bear significance in tuning polyelectrolyte materials' mechanical and swelling characteristics via solution additives.

Original languageEnglish
Pages (from-to)3140–3150
Number of pages11
JournalMacromolecules
Volume55
Issue number8
Early online date15 Apr 2022
DOIs
Publication statusPublished - 26 Apr 2022
MoE publication typeA1 Journal article-refereed

Fingerprint

Dive into the research topics of 'Effect of Ethanol and Urea as Solvent Additives on PSS-PDADMA Polyelectrolyte Complexation'. Together they form a unique fingerprint.

Cite this