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Motivation: Surfactants like CECHCOOH have such bulky headgroups that they cannot show the common sphere-to-cylinder transition, while surfactants like CECHCOOH are mimicking lipids and form only bilayers. Mixing these two types of surfactants allows one to investigate the competition between intramicellar segregation leading to disc-like bicelles and the temperature dependent curvature constraints imposed by the mismatch between heads and tails.
Experiments: We establish phase diagrams as a function of temperature, surfactant mole ratio, and active matter content. We locate the isotropic liquid-isotropic liquid phase separation common to all nonionic surfactant systems, as well as nematic and lamellar phases. The stability and rheology of the nematic phase is investigated. Texture determination by polarizing microscopy allows us to distinguish between the different phases. Finally, SANS and SAXS give intermicellar distances as well as micellar sizes and shapes present for different compositions in the phase diagrams.
Findings: In a defined mole ratio between the two components, intramicellar segregation wins and a viscoelastic discotic nematic phase is present at low temperature. Partial intramicellar mixing upon heating leads to disc growth and eventually to a pseudo-lamellar phase. Further heating leads to complete random mixing and an isotropic phase, showing the common liquid-liquid miscibility gap. This uncommon phase sequence, bicelles, lamellar phase, micelles, and water-poor packed micelles, is due to temperature induced mixing combined with dehydration of the headgroups. This general molecular mechanism explains also why a metastable water-poor lamellar phase quenched by cooling can be easily and reproducibly transformed into a nematic phase by gentle hand shaking at room temperature, as well as the entrapment of air bubbles of any size without encapsulation by bilayers or polymers.
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http://dx.doi.org/10.1016/j.jcis.2024.01.014 | DOI Listing |
J Colloid Interface Sci
April 2024
Institute of Physical and Theoretical Chemistry, University of Regensburg, D-93053 Regensburg, Germany. Electronic address:
Motivation: Surfactants like CECHCOOH have such bulky headgroups that they cannot show the common sphere-to-cylinder transition, while surfactants like CECHCOOH are mimicking lipids and form only bilayers. Mixing these two types of surfactants allows one to investigate the competition between intramicellar segregation leading to disc-like bicelles and the temperature dependent curvature constraints imposed by the mismatch between heads and tails.
Experiments: We establish phase diagrams as a function of temperature, surfactant mole ratio, and active matter content.
J Colloid Interface Sci
January 2024
Centro de Química Estrutural, Institute of Molecular Sciences, Instituto Superior Técnico, Departamento de Engenharia Química, Universidade de Lisboa, 1049-001 Lisbon, Portugal. Electronic address:
Hypothesis: Aqueous solutions of mixtures of hydrogenated and perfluorinated ionic surfactants are known to display anomalous aggregation behavior due to the mutual phobicity between hydrogenated and perfluorinated chains. Despite all efforts, different experimental limitations prevented so far a definite interpretation of the existing experimental results: both intermicellar and intramicellar segregation remain acceptable possibilities.
Method: The potential for segregation of mixtures of fluorinated and hydrogenated ionic surfactants in water was assessed using atomistic molecular dynamics simulations.
ACS Macro Lett
February 2012
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
The aqueous self-assembly behavior of polydisperse poly(ethylene oxide--1,4-butadiene--ethylene oxide) (OBO) macromolecular triblock amphiphiles is examined to discern the implications of continuous polydispersity in the hydrophobic block on the resulting aqueous micellar morphologies of otherwise monodisperse polymer surfactants. The chain length polydispersity and implicit composition polydispersity of these samples furnishes a distribution of preferred interfacial curvatures, resulting in dilute aqueous block copolymer dispersions exhibiting coexisting spherical and rod-like micelles with vesicles in a single sample with a O weight fraction, , of 0.18.
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