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Self-Assembly of Charged Amphiphilic Diblock Copolymers with Insoluble Blocks of Decreasing Hydrophobicity: From Kinetically Frozen Colloids to Macrosurfactants

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Complex Fluids Laboratory, CNRS UMR 166, Rhodia Research Center, 350 George Patterson Boulevard, Bristol, Pennsylvania 19007, United States
Université de Strasbourg, Institut Charles Sadron, CNRS UPR 22, 23 rue du Loess, BP 84047, F-67034 Strasbourg Cedex 2, France
§ Institut des Biomolécules Max Mousseron (UMR 5247 CNRS - Université de Montpellier 1 - Université de Montpellier 2), place Eugène Bataillon CC 1706, 34095 Montpellier Cedex 5, France
Laboratoire Adhésion et Inflammation, INSERM U600, CNRS UMR 6212, Case 937, 163 Avenue de Luminy, Marseille F-13009, France
Aix/Marseille Université, Faculté des Sciences/de Médecine ou de Pharmacie, Marseille F-13000, France
*To whom correspondence should be addressed. Tel: +33 (0)4 91 82 88 69. Fax/Tel: +33 (0)4 91 82 88 51. E-mail:[email protected]
Cite this: Langmuir 2010, 26, 24, 18681–18693
Publication Date (Web):November 24, 2010
Copyright © 2010 American Chemical Society

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We have investigated the self-assembly properties in aqueous solution of amphiphilic diblock copolymers with insoluble blocks of different hydrophobicity and demonstrated that the condition to obtain dynamic micelles is to design samples with insoluble blocks of low enough hydrophobicity. We focus here on results with new water-soluble amphiphilic diblock copolymers poly(diethyleneglycol ethylether acrylate)-b-poly(acrylic acid), or PDEGA-b-PAA. The physical characteristics of PDEGA-b-PAA micelles at high ionization have been determined by small angle neutron scattering (SANS). We show that PDEGA-b-PAA samples form micelles at thermodynamic equilibrium. The critical micelle concentrations (CMCs) decrease strongly with ionic strength and temperature due to a solvent quality decrease for, respectively, the corona and the core. This behavior of reversible aggregation is remarkable as compared to the behavior of kinetically frozen aggregation that has been widely observed with samples of similar architecture and different hydrophobic blocks, for example, poly(styrene)-b-poly(acrylic acid), PS-b-PAA, and poly(butyl acrylate)-b-poly(acrylic acid), PBA-b-PAA. We have measured the interfacial tension between water and the homopolymers PDEGA and PBA at, respectively, 3 and 20 mN/m at room temperature, which permits one to estimate the energy cost to extract a unimer from a micelle. The results are consistent with a micelle association that is fast for PDEGA-b-PAA and kinetically frozen PBA-b-PAA. Hence, PDEGA-b-PAA samples form a new system of synthetic charged macrosurfactant with unique properties of fast dynamic association, tunable charge, and water solubility even at temperatures and NaCl concentrations as high as 65 °C and 1 M.

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Plots of SANS data of a PDEGA-b-d3PAA 8k−8k solution and of the best fits obtained by the Pedersen-Gerstenberg model with polydisperse micelles and without adding the core fluctuation term. There is clearly a deficit of scattering at high q values. This material is available free of charge via the Internet at

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