pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants

Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(<i>N</i>-dodecyl-<i>N</i>-propanesulfonate sodium)-propane (C<sub&g...

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Main Authors: Maozhang Tian, Xi Chen, Xinyuan Zou, Yuchen Qian, Zhang Liu, Yaxun Fan
Format: Article
Language:English
Published: MDPI AG 2021-08-01
Series:Molecules
Subjects:
Online Access:https://www.mdpi.com/1420-3049/26/16/5013
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author Maozhang Tian
Xi Chen
Xinyuan Zou
Yuchen Qian
Zhang Liu
Yaxun Fan
author_facet Maozhang Tian
Xi Chen
Xinyuan Zou
Yuchen Qian
Zhang Liu
Yaxun Fan
author_sort Maozhang Tian
collection DOAJ
description Surfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(<i>N</i>-dodecyl-<i>N</i>-propanesulfonate sodium)-propane (C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub>) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub>, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.
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spelling doaj.art-7b8abebc43f040509409ae47f83b06662023-11-22T08:55:20ZengMDPI AGMolecules1420-30492021-08-012616501310.3390/molecules26165013pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric SurfactantsMaozhang Tian0Xi Chen1Xinyuan Zou2Yuchen Qian3Zhang Liu4Yaxun Fan5State Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC, Beijing 100083, ChinaState Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC, Beijing 100083, ChinaState Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC, Beijing 100083, ChinaState Key Laboratory of Enhanced Oil Recovery, Research Institute of Petroleum Exploration and Development, CNPC, Beijing 100083, ChinaCAS Key Laboratory of Colloid, Interface Thermodynamics, Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, ChinaCAS Key Laboratory of Colloid, Interface Thermodynamics, Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, ChinaSurfactant aggregates have long been considered as a tool to improve drug delivery and have been widely used in medical products. The pH-responsive aggregation behavior in anionic gemini surfactant 1,3-bis(<i>N</i>-dodecyl-<i>N</i>-propanesulfonate sodium)-propane (C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub>) and its mixture with a cationic monomeric surfactant cetyltrimethylammonium bromide (CTAB) have been investigated. The spherical-to-wormlike micelle transition was successfully realized in C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> through decreasing the pH, while the rheological properties were perfectly enhanced for the formation of wormlike micelles. Especially at 140 mM and pH 6.7, the mixture showed high viscoelasticity, and the maximum of the zero-shear viscosity reached 1530 Pa·s. Acting as a sulfobetaine zwitterionic gemini surfactant, the electrostatic attraction, the hydrogen bond and the short spacer of C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> molecules were all responsible for the significant micellar growth. Upon adding CTAB, the similar transition could also be realized at a low pH, and the further transformation to branched micelles occurred by adjusting the total concentration. Although the mixtures did not approach the viscosity maximum appearing in the C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub> solution, CTAB addition is more favorable for viscosity enhancement in the wormlike-micelle region. The weakened charges of the headgroups in a catanionic mixed system minimizes the micellar spontaneous curvature and enhances the intermolecular hydrogen-bonding interaction between C<sub>12</sub>C<sub>3</sub>C<sub>12</sub>(SO<sub>3</sub>)<sub>2</sub>, facilitating the formation of a viscous solution, which would greatly induce entanglement and even the fusion of wormlike micelles, thus resulting in branched microstructures and a decline of viscosity.https://www.mdpi.com/1420-3049/26/16/5013gemini surfactantmicellar growthwormlike micelleentanglementviscoelasticity
spellingShingle Maozhang Tian
Xi Chen
Xinyuan Zou
Yuchen Qian
Zhang Liu
Yaxun Fan
pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
Molecules
gemini surfactant
micellar growth
wormlike micelle
entanglement
viscoelasticity
title pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
title_full pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
title_fullStr pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
title_full_unstemmed pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
title_short pH-Responsive Rheological Properties and Microstructure Transition in Mixture of Anionic Gemini/Cationic Monomeric Surfactants
title_sort ph responsive rheological properties and microstructure transition in mixture of anionic gemini cationic monomeric surfactants
topic gemini surfactant
micellar growth
wormlike micelle
entanglement
viscoelasticity
url https://www.mdpi.com/1420-3049/26/16/5013
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