Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

Adrian Sanchez-fernandez; Andrew J. Jackson; Sylvain F. Prévost; James J. Doutch; Karen J. Edler

doi:10.1021/jacs.1c04781

Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

Adrian Sanchez-fernandez, Andrew J. Jackson, Sylvain F. Prévost, James J. Doutch, Karen J. Edler

Research output: Contribution to journal › Article › peer-review

44 Citations (SciVal)

Abstract

While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion–ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.

Original language	English
Pages (from-to)	14158-14168
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	143
Issue number	35
Early online date	30 Aug 2021
DOIs	https://doi.org/10.1021/jacs.1c04781
Publication status	Published - 8 Sept 2021

Funding

The authors would like to thank the European Spallation Source and the University of Bath Alumni Fund for funding A.S.-F. The research activities were also supported by Vinnova – Swedish Governmental Agency for Innovation Systems within the NextBioForm Competence Centre, and the Crafoord Foundation (Grant 20190750). The authors thank ISIS Pulsed Neutron and Muon Source (RB1620126) and Institute Laue-Langevin (9-13-820) for the awarded beamtime. We would like to thank Dr. Wojciech Potrzebowski (European Spallation Source) for the fruitful discussions on the implementation of structure factor models in SasView. This work benefited from the use of the SasView application, originally developed under NSF award DMR-0520547. SasView contains code developed with funding from the European Union’s Horizon 2020 research and innovation programme under the SINE2020 project, Grant Agreement No. 654000.

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Cite this

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abstract = "While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion–ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.",

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AU - Sanchez-fernandez, Adrian

AU - Jackson, Andrew J.

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AU - Edler, Karen J.

PY - 2021/9/8

Y1 - 2021/9/8

N2 - While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion–ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.

AB - While the traditional consensus dictates that high ion concentrations lead to negligible long-range electrostatic interactions, we demonstrate that electrostatic correlations prevail in deep eutectic solvents where intrinsic ion concentrations often surpass 2.5 M. Here we present an investigation of intermicellar interactions in 1:2 choline chloride:glycerol and 1:2 choline bromide:glycerol using small-angle neutron scattering. Our results show that long-range electrostatic repulsions between charged colloidal particles occur in these solvents. Interestingly, micelle morphology and electrostatic interactions are modulated by specific counterion condensation at the micelle interface despite the exceedingly high concentration of the native halide from the solvent. This modulation follows the trends described by the Hofmeister series for specific ion effects. The results are rationalized in terms of predominant ion–ion correlations, which explain the reduction in the effective ionic strength of the continuum and the observed specific ion effects.

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Long-Range Electrostatic Colloidal Interactions and Specific Ion Effects in Deep Eutectic Solvents

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