The solubility of Ls-54 surfactant in supercritical CO(2) was determined. It was found that the surfactant was highly soluble in SC CO(2) and the water-in-CO(2) microemulsions could be formed, despite it being a non-fluorous and non-siloxane nonionic surfactant. The main reasons for the high solubility and formation of the microemulsions may be that the surfactant has four CO(2)-philic groups (propylene oxide) and five hydrophilic groups (ethylene oxide) and its molecular weight are relatively low. The results of this work provide useful information for designing CO(2)-soluble non-fluorous and non-siloxane surfactants. The phase behavior of the CO(2)/Ls-54/H(2)O system, solvatochromic probe study, and the UV spectrum of lysozyme proved the existence of water domains in the SC CO(2) microemulsions. The method of synchrotron radiation small-angle X-ray scattering was used to obtain the structural information on the Ls-54 based water-in-CO(2) reverse micelles. By using the Guinier plot (ln I(q) versus q (2)) on the data sets in a defined small q range (0.022-0.040 A(-1)), the radii of the reverse micelles were obtained at different pressures and molar ratio of water to surfactant, W(0), which were in the range of 20.4-25.2 A.
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http://dx.doi.org/10.1002/1521-3765(20020315)8:6<1356::aid-chem1356>3.0.co;2-n | DOI Listing |
Langmuir
February 2016
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom.
An oxygen-rich hydrocarbon (HC) amphiphile has been developed as an additive for supercritical CO2 (scCO2). The effects of this custom-designed amphiphile have been studied in water-in-CO2 (w/c) microemulsions stabilized by analogous fluorocarbon (FC) surfactants, nFG(EO)2, which are known to form spherical w/c microemulsion droplets. By applying contrast-variation small-angle neutron scattering (CV-SANS), evidence has been obtained for anisotropic structures in the mixed systems.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2014
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdom. Electronic address:
Hypothesis: The formation, stability and structural properties of normal liquid phase microemulsions, stabilized by hydrocarbon surfactants, comprising water and hydrocarbon oils can be interpreted in terms of the film bending rigidity (energy) model. Here, this model is tested for unusual water-in-CO2 (w/c) microemulsions, formed at high pressure with supercritical CO2 (sc-CO2) as a solvent and fluorinated surfactants as stabilizers. Hence, it is possible to explore the generality of this model for other types of microemulsions.
View Article and Find Full Text PDFLangmuir
January 2014
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, U.K.
The ability to induce morphological transitions in water-in-oil (w/o) and water-in-CO2 (w/c) microemulsions stabilized by a trichain anionic surfactant 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) with simple hydrotrope additives has been investigated. High-pressure small-angle neutron scattering (SANS) has revealed the addition of a small mole fraction of hydrotrope can yield a significant elongation in the microemulsion water droplets. For w/o systems, the degree of droplet growth was shown to be dependent on the water content, the hydrotrope mole fraction, and chemical structure, whereas for w/c microemulsions a similar, but less significant, effect was seen.
View Article and Find Full Text PDFLangmuir
June 2013
Department of Frontier Materials Chemistry, Graduate School of Science and Technology, Hirosaki University, Hirosaki, Aomori 036-8561, Japan.
High-pressure small-angle neutron scattering (HP-SANS) studies were conducted to investigate nanostructures and interfacial properties of water-in-supercritical CO2 (W/CO2) microemulsions with double-fluorocarbon-tail anionic surfactants, having different fluorocarbon chain lengths and linking groups (glutarate or succinate). At constant pressure and temperature, the microemulsion aqueous cores were found to swell with an increase in water-to-surfactant ratio, W0, until their solubilizing capacities were reached. Surfactants with fluorocarbon chain lengths of n = 4, 6, and 8 formed spherical reversed micelles in supercritical CO2 even at W0 over the solubilizing powers as determined by phase behavior studies, suggesting formation of Winsor-IV W/CO2 microemulsions and then Winsor-II W/CO2 microemulsions.
View Article and Find Full Text PDFJ Am Chem Soc
February 2008
Department of Biotechnology, Indian Institute of Technology Madras, Chennai 600036, India.
Molecular dynamics simulations of random quaternary mixtures of protein-water-CO2-fluorosurfactants show the self-assembly of reverse micelles in supercritical carbon dioxide where the protein becomes entrapped inside the aqueous pool. Analyses show that the protein native state remains intact in the water pool. This is because of the bulk nature of the enclosed water that provides a suitable environment for the extracted protein.
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