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Extraction of a hydrophilic compound from water into liquid CO2 using dendritic surfactants

Nature volume 389, pages 368–371 (1997)Cite this article

Abstract

Dendrimers are well defined, highly branched polymers1,2,3,4,5 that adopt a roughly spherical, globular shape in solution. Their cores are relatively loosely packed and can trap guest molecules5,6,7, and by appropriate functionalization of the branch tips the macromolecules can act as unimolecular micelle-like entities6. Here we show that dendrimers with a fluorinated shell are soluble in liquid carbon dioxide and can transport CO2-insoluble molecules into this solvent within their cores. Specifically, we demonstrate the extraction of a polar ionic dye, methyl orange, from water into CO2 using these fluorinated dendrimers. This observation suggests possible uses of such macromolecules for the remediation of contaminated water, the extraction of pharmaceutical products from fermentation vessels, the selective encapsulation of drugs for targeted delivery6,7 and the transport of reagents for chemical reactions (such as polymerization8,9,10,11) in liquid and supercritical CO2 solvents.

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Figure 1: Synthesis of the unimolecular dendritic micelle.
Figure 2: iffusion of methyl orange (5) from aqueous solution (upper phase in figure) into a unimolecular dendritic micelle 3 in liquid CO2 (lower phase) at 23.5 °C, 340 atm.
Figure 3: a, Ultraviolet–visible spectra illustrating the diffusion of methyl orange (5) from an aqueous phase into a unimolecular dendritic micelle 3 in liquid CO2 (24.9 °C, 340 atm).
Figure 4: Plot of Kd[dΣ/dΩ(0)]−1 versus concentration (c) for the dendritic micelle 3 in liquid CO2 (23.7C, 340 atm); see text.

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Acknowledgements

A.I.C. thanks the Royal Commission for The Exhibition of 1851 for a research fellowship (1995–96); J.D.L. thanks the NSF for support through the University of Tennessee. We also acknowledge support from the NSF for a Presidential Faculty Fellowship (J.M.D., 1993–97) as well as from the Consortium on Synthesis and Processing of Polymeric Materials in CO2, which is sponsored by the NSF, the Environmental Protection Agency, DuPont, Hoechst-Celanese, Air Products and Chemicals, B. F. Groodrich, Eastman Chemical, Bayer and Xerox. We also thank the Division of Material Sciences, US Department of Energy under contract with Lockheed-Martin Research Corporation, and the Exxon Education Fundation for support.

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Authors and Affiliations

  1. Department of Chemistry, CB#3290, Venable and Kenan Laboratories, University of North Carolina, Chapel Hill, Chapel Hill, 27599-3290, North Carolina, USA

    A. I. Cooper, J. B. McClain, E. T. Samulski, A. Dobrynin, M. Rubinstein, A. L. C. Burke & J. M. DeSimone

  2. Oak Ridge National Laboratory, Oak Ridge, 37381-6031, Tennessee, USA

    J. D. Londono, G. Wignall & J. S. Lin

  3. Department of Chemical Engineering, University of Tennessee, Knoxville, 37996-220, Tennessee, USA

    J. D. Londono

  4. Department of Chemistry, University of California-Berkeley, Berkeley, 94720, California, USA

    J. M. J. Fréchet

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Cooper, A., Londono, J., Wignall, G. et al. Extraction of a hydrophilic compound from water into liquid CO2 using dendritic surfactants. Nature 389, 368–371 (1997). https://doi.org/10.1038/38706

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