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Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant

Masanobu Sagisaka, Tatsuya Saito, Masashi Abe, Atsushi Yoshizawa, Marijana Blesic, Sarah E. Rogers, Shirin Alexander Orcid Logo, Frédéric Guittard, Christopher Hill, Julian Eastoe

Langmuir, Volume: 36, Issue: 26, Pages: 7418 - 7426

Swansea University Author: Shirin Alexander Orcid Logo

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DOI (Published version): 10.1021/acs.langmuir.0c00970

Abstract

To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 μEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water–CO2 interfaces, these surfactants must also be economical, preven...

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Published in: Langmuir
ISSN: 0743-7463 1520-5827
Published: American Chemical Society (ACS) 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa54870
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Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 &#x3BC;Es with high water-to-surfactant molar ratios (W0) up to &#x223C;50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445&#x2212;3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 &#x3BC;Es, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 &#x3BC;Es (maximum W0 = 60&#x2013;80). 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spelling 2020-09-17T14:57:05.9866189 v2 54870 2020-08-04 Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant 0773cc55f7caf77817be08806b8b7497 0000-0002-4404-0026 Shirin Alexander Shirin Alexander true false 2020-08-04 CHEG To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 μEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water–CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 μEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445−3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 μEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 μEs (maximum W0 = 60–80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 μEs with high stability and water solubilization. Journal Article Langmuir 36 26 7418 7426 American Chemical Society (ACS) 0743-7463 1520-5827 Supercritical CO2, Microemulsion, Catanionic Surfactant, Solubilizing Power, Small-Angle Neutron Scattering 7 7 2020 2020-07-07 10.1021/acs.langmuir.0c00970 COLLEGE NANME Chemical Engineering COLLEGE CODE CHEG Swansea University 2020-09-17T14:57:05.9866189 2020-08-04T16:16:05.5547644 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Masanobu Sagisaka 1 Tatsuya Saito 2 Masashi Abe 3 Atsushi Yoshizawa 4 Marijana Blesic 5 Sarah E. Rogers 6 Shirin Alexander 0000-0002-4404-0026 7 Frédéric Guittard 8 Christopher Hill 9 Julian Eastoe 10 54870__17878__2dc7ae3f9a5b4eaf80621d9e8fa85667.pdf 54870SI.pdf 2020-08-06T16:21:42.3323713 Output 776401 application/pdf Accepted Manuscript true 2021-06-12T00:00:00.0000000 true eng
title Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
spellingShingle Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
Shirin Alexander
title_short Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
title_full Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
title_fullStr Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
title_full_unstemmed Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
title_sort Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant
author_id_str_mv 0773cc55f7caf77817be08806b8b7497
author_id_fullname_str_mv 0773cc55f7caf77817be08806b8b7497_***_Shirin Alexander
author Shirin Alexander
author2 Masanobu Sagisaka
Tatsuya Saito
Masashi Abe
Atsushi Yoshizawa
Marijana Blesic
Sarah E. Rogers
Shirin Alexander
Frédéric Guittard
Christopher Hill
Julian Eastoe
format Journal article
container_title Langmuir
container_volume 36
container_issue 26
container_start_page 7418
publishDate 2020
institution Swansea University
issn 0743-7463
1520-5827
doi_str_mv 10.1021/acs.langmuir.0c00970
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
document_store_str 1
active_str 0
description To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 μEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water–CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 μEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445−3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 μEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 μEs (maximum W0 = 60–80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 μEs with high stability and water solubilization.
published_date 2020-07-07T04:08:41Z
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score 11.037056

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