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Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent

Manasi, Iva ; Andalibi, Mohammad R. ; Atri, Ria S. ; Hooton, Jake ; King, Stephen M. and Edler, Karen J. LU orcid (2021) In Journal of Chemical Physics 155(8).
Abstract

Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C12TANO3/C12TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene... (More)

Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C12TANO3/C12TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C12EO6) and octaethylene glycol monohexadecyl ether (C16EO8) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C12TANO3, C12TAB, C12EO6, and C16EO8 form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO3)3 in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.

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author
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publishing date
type
Contribution to journal
publication status
published
in
Journal of Chemical Physics
volume
155
issue
8
article number
084902
pages
14 pages
publisher
American Institute of Physics (AIP)
external identifiers
  • pmid:34470344
  • scopus:85113681231
ISSN
0021-9606
DOI
10.1063/5.0059238
language
English
LU publication?
no
additional info
Publisher Copyright: © 2021 Author(s).
id
28cb65cb-12e2-4420-83b2-5978f9c509d7
date added to LUP
2022-07-12 15:36:52
date last changed
2024-04-16 08:07:51
@article{28cb65cb-12e2-4420-83b2-5978f9c509d7,
  abstract     = {{<p>Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle formation has only been reported in type III DESs, consisting solely of organic species. In this work, we have explored the self-assembly of cationic surfactant dodecyl trimethylammonium nitrate/bromide (C<sub>12</sub>TANO<sub>3</sub>/C<sub>12</sub>TAB), anionic surfactant sodium dodecyl sulfate (SDS), and non-ionic surfactants hexaethylene glycol monododecyl ether (C<sub>12</sub>EO<sub>6</sub>) and octaethylene glycol monohexadecyl ether (C<sub>16</sub>EO<sub>8</sub>) in a type IV DES comprising metal salt, cerium (III) nitrate hexahydrate, and a hydrogen bond donor, urea, in the molar ratio 1:3.5. C<sub>12</sub>TANO<sub>3</sub>, C<sub>12</sub>TAB, C<sub>12</sub>EO<sub>6</sub>, and C<sub>16</sub>EO<sub>8</sub> form spherical micelles in the DES with the micelle size dependent on both the surfactant alkyl chain length and the head group, whereas SDS forms cylindrical micelles. We hypothesize that the difference in the micelle shape can be explained by counterion stabilization of the SDS headgroup by polycations in the DES compared to the nitrate/bromide anion interaction in the case of cationic surfactants or molecular interaction of the urea and the salting out effect of (CeNO<sub>3</sub>)<sub>3</sub> in the DES on the alkyl chains/polyethoxy headgroup for non-ionic surfactants. These studies deepen our understanding of amphiphile self-assembly in this novel, ionic, and hydrogen-bonding solvent, raising the opportunity to use these structures as liquid crystalline templates to generate porosity in metal oxides (ceria) that can be synthesized using these DESs.</p>}},
  author       = {{Manasi, Iva and Andalibi, Mohammad R. and Atri, Ria S. and Hooton, Jake and King, Stephen M. and Edler, Karen J.}},
  issn         = {{0021-9606}},
  language     = {{eng}},
  month        = {{08}},
  number       = {{8}},
  publisher    = {{American Institute of Physics (AIP)}},
  series       = {{Journal of Chemical Physics}},
  title        = {{Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent}},
  url          = {{http://dx.doi.org/10.1063/5.0059238}},
  doi          = {{10.1063/5.0059238}},
  volume       = {{155}},
  year         = {{2021}},
}