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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
https://doi.org/10.1021/la103391p
Copyright © 2010 American Chemical Society
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Abstract

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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 http://pubs.acs.org.

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  5. C. Adrian Figg, R. Nicholas Carmean, Kyle C. Bentz, Soma Mukherjee, Daniel A. Savin, and Brent S. Sumerlin . Tuning Hydrophobicity To Program Block Copolymer Assemblies from the Inside Out. Macromolecules 2017, 50 (3) , 935-943. https://doi.org/10.1021/acs.macromol.6b02754
  6. Dustin Sprouse, Yaming Jiang, Jennifer E. Laaser, Timothy P. Lodge, and Theresa M. Reineke . Tuning Cationic Block Copolymer Micelle Size by pH and Ionic Strength. Biomacromolecules 2016, 17 (9) , 2849-2859. https://doi.org/10.1021/acs.biomac.6b00654
  7. Lionel Lauber, Christophe Chassenieux, Taco Nicolai, and Olivier Colombani . Highlighting the Role of the Random Associating Block in the Self-Assembly of Amphiphilic Block–Random Copolymers. Macromolecules 2015, 48 (20) , 7613-7619. https://doi.org/10.1021/acs.macromol.5b01626
  8. Patrizio Raffa, Diego Armando Zakarias Wever, Francesco Picchioni, and Antonius A. Broekhuis . Polymeric Surfactants: Synthesis, Properties, and Links to Applications. Chemical Reviews 2015, 115 (16) , 8504-8563. https://doi.org/10.1021/cr500129h
  9. Lianwei Li, Manqing Yan, Guangzhao Zhang, and Chi Wu . Self-Assembly Assisted Polypolymerization (SAAP) of Diblock Copolymer Chains with Two Reactive Groups at Its Insoluble End. Macromolecules 2013, 46 (20) , 8152-8160. https://doi.org/10.1021/ma401675q
  10. Lianwei Li, Jinxian Yang, and Jianfeng Zhou . Linear-, Cyclic-, and Multiblock Amphiphilic Polyelectrolytes as Surfactants in Emulsion Polymerization: Role of Topological Structure. Macromolecules 2013, 46 (7) , 2808-2817. https://doi.org/10.1021/ma3022025
  11. Gabriel. Landazuri, V. V. A Fernandez, J. F. A. Soltero, and Y. Rharbi . Kinetics of the Sphere-to-Rod like Micelle Transition in a Pluronic Triblock Copolymer. The Journal of Physical Chemistry B 2012, 116 (38) , 11720-11727. https://doi.org/10.1021/jp3009089
  12. Niki Baccile, Florence Babonneau, Jacques Jestin, Gerard Pehau-Arnaudet, and Inge Van Bogaert . Unusual, pH-Induced, Self-Assembly Of Sophorolipid Biosurfactants. ACS Nano 2012, 6 (6) , 4763-4776. https://doi.org/10.1021/nn204911k
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  25. Xia Dong, Wei Zhang, Qiuyan Zong, Qiong Liu, Jinxin He. Physicochemical and emulsifying properties of “extended” triblock copolymers. Colloid and Polymer Science 2015, 293 (2) , 369-379. https://doi.org/10.1007/s00396-014-3420-8
  26. Wei Zhang, Jinxin He, Haifeng Bao, Xia Dong. Polymeric Janus nanoparticles from triblock terpolymer micellar dimers. RSC Advances 2015, 5 (126) , 104223-104227. https://doi.org/10.1039/C5RA17384A
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  28. Hideki Matsuoka, Tomoyuki Onishi, Arjun Ghosh. pH-responsive non-surface-active/surface-active transition of weakly ionic amphiphilic diblock copolymers. Colloid and Polymer Science 2014, 292 (4) , 797-806. https://doi.org/10.1007/s00396-013-3125-4
  29. Alexandros Lamprou, Delong Xie, Giuseppe Storti, Hua Wu. Self-association dynamics and morphology of short polymeric PBA-b/co-PAA surfactants. Colloid and Polymer Science 2014, 292 (3) , 677-685. https://doi.org/10.1007/s00396-013-3119-2
  30. Victor Lee, Takumi Hawa. Investigation of the effect of bilayer membrane structures and fluctuation amplitudes on SANS/SAXS profile for short membrane wavelength. The Journal of Chemical Physics 2013, 139 (12) , 124905. https://doi.org/10.1063/1.4821816
  31. Céline Charbonneau, Christophe Chassenieux, Olivier Colombani, Taco Nicolai. Slow dynamics in transient polyelectrolyte hydrogels formed by self-assembly of block copolymers. Physical Review E 2013, 87 (6) https://doi.org/10.1103/PhysRevE.87.062302
  32. Bishnu Prasad Bastakoti, Kevin C.-W. Wu, Masamichi Inoue, Shin-ichi Yusa, Kenichi Nakashima, Yusuke Yamauchi. Multifunctional Core-Shell-Corona-Type Polymeric Micelles for Anticancer Drug-Delivery and Imaging. Chemistry - A European Journal 2013, 19 (15) , 4812-4817. https://doi.org/10.1002/chem.201203958
  33. Basem A. Moosa, Afnan Mashat, Wengang Li, Karim Fhayli, Niveen M. Khashab. pH Responsive Self-Assembly of Cucurbit[7]urils and Polystyrene-Block-Polyvinylpyridine Micelles for Hydrophobic Drug Delivery. Journal of Nanomaterials 2013, 2013 , 1-6. https://doi.org/10.1155/2013/719168
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  35. Hideki Matsuoka, Masahiro Hachisuka, Kyohei Uda, Tomoyuki Onishi, Shinji Ozoe. Why Ionic Amphiphilic “ Block ” Copolymer Can Be Non-surface Active? Comparison of Homopolymer, Block and Random Copolymers of Poly(styrenesulfonate). Chemistry Letters 2012, 41 (10) , 1063-1065. https://doi.org/10.1246/cl.2012.1063
  36. Fabien Dutertre, Olivier Boyron, Bernadette Charleux, Christophe Chassenieux, Olivier Colombani. Transforming Frozen Self-Assemblies of Amphiphilic Block Copolymers Into Dynamic pH-Sensitive Micelles. Macromolecular Rapid Communications 2012, 33 (9) , 753-759. https://doi.org/10.1002/marc.201200078
  37. Michelle M. Mok, Timothy P. Lodge. Temperature-based fluorescence measurements of pyrene in block copolymer micelles: Probing micelle core glass transition breadths. Journal of Polymer Science Part B: Polymer Physics 2012, 50 (7) , 500-515. https://doi.org/10.1002/polb.23029
  38. Tobias Miller, Reinhard Rachel, Ahmed Besheer, Senta Uezguen, Markus Weigandt, Achim Goepferich. Comparative Investigations on In Vitro Serum Stability of Polymeric Micelle Formulations. Pharmaceutical Research 2012, 29 (2) , 448-459. https://doi.org/10.1007/s11095-011-0555-x
  39. Hideki Matsuoka, Hao Chen, Kozo Matsumoto. Molecular weight dependence of non-surface activity for ionic amphiphilic diblock copolymers. Soft Matter 2012, 8 (35) , 9140. https://doi.org/10.1039/c2sm25710f
  40. Bishnu Prasad Bastakoti, Sudhina Guragain, Yuuichi Yokoyama, Shin-ichi Yusa, Kenichi Nakashima. Incorporation and release behavior of amitriptylene in core–shell–corona type triblock copolymer micelles. Colloids and Surfaces B: Biointerfaces 2011, 88 (2) , 734-740. https://doi.org/10.1016/j.colsurfb.2011.08.009
  41. Oleg V. Borisov, Ekaternia B. Zhulina, Frans A. M. Leermakers, Axel H. E. Müller. Self-Assembled Structures of Amphiphilic Ionic Block Copolymers: Theory, Self-Consistent Field Modeling and Experiment. 2011, 57-129. https://doi.org/10.1007/12_2011_114

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