Projects per year
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 language | English |
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Pages (from-to) | 3140–3150 |
Number of pages | 11 |
Journal | Macromolecules |
Volume | 55 |
Issue number | 8 |
Early online date | 15 Apr 2022 |
DOIs | |
Publication status | Published - 26 Apr 2022 |
MoE publication type | A1 Journal article-refereed |
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LIBER Sammalkorpi: Life-like hybrid materials Sammalkorpi
Sammalkorpi, M. (Principal investigator), Hasheminejad, K. (Project Member), Holl, M. (Project Member), Harmat, A. (Project Member), Kastinen, T. (Project Member), Morais Jaques, Y. (Project Member) & Scacchi, A. (Project Member)
01/01/2022 → 31/12/2024
Project: Academy of Finland: Other research funding
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MM-IRD-POLYMER
Sammalkorpi, M. (Principal investigator), Hasheminejad, K. (Project Member) & Scacchi, A. (Project Member)
01/01/2020 → 30/04/2022
Project: Business Finland: Strategic research openings
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Molecular Modelling in Industrial Research and Development
Karttunen, A. (Principal investigator), Conley, K. (Project Member), Mattila, N. (Project Member), Miikkulainen, V. (Project Member), Haimi, E. (Project Member), Möttönen, N. (Project Member) & Eklund, K. (Project Member)
01/01/2020 → 30/04/2022
Project: Business Finland: Strategic research openings
Equipment
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Bioeconomy Research Infrastructure
Seppälä, J. (Manager)
School of Chemical EngineeringFacility/equipment: Facility
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Raw Materials Research Infrastructure
Karppinen, M. (Manager)
School of Chemical EngineeringFacility/equipment: Facility