Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics
In this article, ion-specific effects in aqueous solutions of polyelectrolytes (PEs) are addressed. We focus on ionene cationic chains, featuring simple structure, absence of side groups, and very regular chain charge density. Ion-specific effects in ionene solutions are demonstrated using a series...
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Académie des sciences
2025-01-01
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| Series: | Comptes Rendus. Chimie |
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| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.326/ |
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| author | Hotton, Claire Sakhawoth, Yasine Rollet, Anne-Laure Sirieix-Plénet, Juliette Tea, Lingsam Combet, Sophie Sharp, Melissa Hoffmann, Ingo Nallet, Frédéric Malikova, Natalie |
| author_facet | Hotton, Claire Sakhawoth, Yasine Rollet, Anne-Laure Sirieix-Plénet, Juliette Tea, Lingsam Combet, Sophie Sharp, Melissa Hoffmann, Ingo Nallet, Frédéric Malikova, Natalie |
| author_sort | Hotton, Claire |
| collection | DOAJ |
| description | In this article, ion-specific effects in aqueous solutions of polyelectrolytes (PEs) are addressed. We focus on ionene cationic chains, featuring simple structure, absence of side groups, and very regular chain charge density. Ion-specific effects in ionene solutions are demonstrated using a series of monovalent (halide) counterions. The study combines both static and dynamic measurements by small angle neutron scattering, neutron spin echo (NSE), and pulsed field gradient NMR (PFG-NMR). Ion-specific effects are a phenomenon at high PE concentration, and the nature of the counterion is seen to influence drastically ionene chain–chain interactions via what we refer to as “ion-specific screening”. The origin lies in the closer approach of large, highly polarisable counterions to the chain backbone, leading to more constricted counterion clouds. Equally affected is the local chain rigidity as well as collective and self-diffusion coefficients at larger scales. Small, nonpolarisable, strongly hydrating counterions, here F- ions, lead to locally rigid chains. For such chains, the nm-scale collective dynamics as seen by NSE is the fastest while self-diffusion seen at the µm scale by PFG-NMR is the slowest. In other words, the loss of charge on the chain due to ion-specific screening has the opposite effect on collective diffusion and self-diffusion of the chains. |
| format | Article |
| id | doaj-art-87d086ee12de437cb219c019078510e9 |
| institution | Kabale University |
| issn | 1878-1543 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Académie des sciences |
| record_format | Article |
| series | Comptes Rendus. Chimie |
| spelling | doaj-art-87d086ee12de437cb219c019078510e92025-02-07T13:41:23ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432025-01-0111310.5802/crchim.32610.5802/crchim.326Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamicsHotton, Claire0https://orcid.org/0000-0002-8088-4170Sakhawoth, Yasine1Rollet, Anne-Laure2https://orcid.org/0000-0001-6150-768XSirieix-Plénet, Juliette3https://orcid.org/0000-0002-9873-8534Tea, Lingsam4https://orcid.org/0000-0003-2732-9028Combet, Sophie5https://orcid.org/0000-0002-8672-4514Sharp, Melissa6https://orcid.org/0000-0002-4629-2868Hoffmann, Ingo7https://orcid.org/0000-0001-7178-6467 Nallet, Frédéric8Malikova, Natalie9https://orcid.org/0000-0002-3692-1958Laboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceLaboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceLaboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceLaboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceLaboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceLaboratoire Léon-Brillouin (LLB), UMR12 CEA-CNRS, Université Paris-Saclay, F-91191 Gif-sur-Yvette CEDEX, FranceEuropean Spallation Source (ESS) AB, Box 176, S-22100 Lund, SwedenInstitut Laue Langevin (ILL), Grenoble F-38042, FranceCentre de Recherche Paul-Pascal, UMR Université de Bordeaux–CNRS 5031, 115 Avenue du Dr Albert Schweitzer, 33600 Pessac, FranceLaboratory of Physical Chemistry of Electrolytes and Interfacial Nanosystems (PHENIX), Sorbonne Université, CNRS, 75005 Paris, FranceIn this article, ion-specific effects in aqueous solutions of polyelectrolytes (PEs) are addressed. We focus on ionene cationic chains, featuring simple structure, absence of side groups, and very regular chain charge density. Ion-specific effects in ionene solutions are demonstrated using a series of monovalent (halide) counterions. The study combines both static and dynamic measurements by small angle neutron scattering, neutron spin echo (NSE), and pulsed field gradient NMR (PFG-NMR). Ion-specific effects are a phenomenon at high PE concentration, and the nature of the counterion is seen to influence drastically ionene chain–chain interactions via what we refer to as “ion-specific screening”. The origin lies in the closer approach of large, highly polarisable counterions to the chain backbone, leading to more constricted counterion clouds. Equally affected is the local chain rigidity as well as collective and self-diffusion coefficients at larger scales. Small, nonpolarisable, strongly hydrating counterions, here F- ions, lead to locally rigid chains. For such chains, the nm-scale collective dynamics as seen by NSE is the fastest while self-diffusion seen at the µm scale by PFG-NMR is the slowest. In other words, the loss of charge on the chain due to ion-specific screening has the opposite effect on collective diffusion and self-diffusion of the chains.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.326/PolyelectrolytesIon-specific effectsInter-chain interactionsSelf-diffusionCollective diffusionPFG-NMRNeutron spin echo |
| spellingShingle | Hotton, Claire Sakhawoth, Yasine Rollet, Anne-Laure Sirieix-Plénet, Juliette Tea, Lingsam Combet, Sophie Sharp, Melissa Hoffmann, Ingo Nallet, Frédéric Malikova, Natalie Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics Comptes Rendus. Chimie Polyelectrolytes Ion-specific effects Inter-chain interactions Self-diffusion Collective diffusion PFG-NMR Neutron spin echo |
| title | Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics |
| title_full | Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics |
| title_fullStr | Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics |
| title_full_unstemmed | Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics |
| title_short | Ion-specific effects in polyelectrolyte solutions: chain–chain interactions, chain rigidity and dynamics |
| title_sort | ion specific effects in polyelectrolyte solutions chain chain interactions chain rigidity and dynamics |
| topic | Polyelectrolytes Ion-specific effects Inter-chain interactions Self-diffusion Collective diffusion PFG-NMR Neutron spin echo |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.326/ |
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