[en] The formation of spherical micelles in aqueous solutions of poly(N-methyl-2-vinyl pyridinium iodide)-block-poly(ethylene oxide), P2MVP-b-PEO and poly(acrylic acid)-block-poly(vinyl alcohol), PAA-b-PVOH has been investigated with light scattering-titrations, dynamic and static light scattering, and 1H 2D Nuclear Overhauser Effect Spectroscopy. Complex coacervate core micelles, also called PIC micelles, block ionomer complexes, and interpolyelectrolyte complexes, are formed in thermodynamic equilibrium under charge neutral conditions (pH 8, 1 mM NaNO3, T = 25 °C) through electrostatic interaction between the core-forming P2MVP and PAA blocks. 2D 1H NOESY NMR experiments show no cross-correlations between PEO and PVOH blocks, indicating their segregation in the micellar corona. Self-consistent field calculations support the conclusion that these C3Ms are likely to resemble a ‘patched micelle’; that is, micelles featuring a ‘spheres-on-sphere’ morphology.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Voets, Ilja K.; Wageningen University (The Netherlands) and Adolphe Merkle Institute, at the University of Fribourg (Switzerland) > Laboratory of Physical Chemistry and Colloid Science (The Netherlands)
de Keizer, Arie; Wageningen University, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
Leermakers, Frans A. M.; Wageningen University, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
Debuigne, Antoine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Cohen Stuart, Martien A.; Wageningen University, The Netherlands > Laboratory of Physical Chemistry and Colloid Science
Language :
English
Title :
Electrostatic hierarchical co-assembly in aqueous solutions of two oppositevely charged double hydrophilic diblock copolymers
F.R.S.-FNRS - Fonds de la Recherche Scientifique BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique the SONS Eurocores program the EU Polyamphi/Marie Curie program (FP6-2002, proposal 505027) NWO - Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Cohen Stuart M.A., Hofs B., Voets I.K., and de Keizer A. Assembly of polyelectrolyte-containing block copolymers in aqueous media. Curr Opin Colloid Interface Sci 10 1-2 (2005) 30-36
Harada A., and Kataoka K. Effect of charged segment length on physicochemical properties of core-shell type polyion complex micelles from block ionomers. Macromolecules 36 13 (2003) 4995-5001
Chen W., Chen H.R., Hu J.H., Yang W.L., and Wang C.C. Synthesis and characterization of polyion complex micelles between poly(ethylene glycol)-grafted poly(aspartic acid) and cetyltrimethyl ammonium bromide. Colloids Surf A Physicochem Eng Aspects 278 1-3 (2006) 60-66
Harada A., and Kataoka K. On-off control of enzymatic activity synchronizing with reversible formation of supramolecular assembly from enzyme and charged block copolymers. J Am Chem Soc 121 39 (1999) 9241-9242
Solomatin S.V., Bronich T.K., Bargar T.W., Eisenberg A., Kabanov V.A., and Kabanov A.V. Environmentally responsive nanoparticles from block ionomer complexes: effects of pH and ionic strength. Langmuir 19 19 (2003) 8069-8076
Lysenko E.A., Chelushkin P.S., Bronich T.K., Eisenberg A., Kabanov V.A., and Kabanov A.V. Formation of multilayer polyelectrolyte complexes by using block ionomer micelles as nucleating particles. J Phys Chem B 108 33 (2004) 12352-12359
Gohy J.F., Varshney S.K., Antoun S., and Jerome R. Water-soluble complexes formed by sodium poly(4-styrenesulfonate) and a poly(2-vinylpyridinium)-block-poly(ethyleneoxide) copolymer. Macromolecules 33 25 (2000) 9298-9305
van der Burgh S., Fokkink R., de Keizer A., and Cohen Stuart M.A. Complex coacervation core micelles as anti-fouling agents on silica and polystyrene surfaces. Colloids Surf A Physicochem Eng Aspects 242 1-3 (2004) 167-174
Hofs B., Voets I.K., de Keizer A., and Cohen Stuart M.A. Comparison of complex coacervate core micelles from two diblock copolymers or a single diblock copolymer with a polyelectrolyte. Phys Chem Chem Phys 8 36 (2006) 4242-4251
Voets I.K., de Keizer A., Cohen Stuart M.A., and de Waard P. Core and corona structure of mixed polymeric micelles. Macromolecules 39 17 (2006) 5952-5955
Voets I.K., de Keizer A., de Waard P., Frederik P.M., Bomans P.H.H., Schmalz H., et al. Double-faced micelles from water-soluble polymers. Angew Chem Int Ed 45 40 (2006) 6673-6676
Voets I.K., de Keizer A., and Cohen Stuart M.A. Complex coacervate core micelles. Adv Colloid Interface Sci 147-48 (2009) 300-318
Nisha C.K., Manorama S.V., Kizhakkedathu J.N., and Maiti S. Water-soluble complexes from random copolymer and oppositely charged surfactant. 2. Complexes of poly(ethylene glycol)-based cationic random copolymer and bile salts. Langmuir 20 20 (2004) 8468-8475
Bronich T.K., Nguyen H.K., Eisenberg A., and Kabanov A.V. Recognition of DNA topology in reactions between plasmid DNA and cationic copolymers. J Am Chem Soc 122 35 (2000) 8339-8343
Wakebayashi D., Nishiyama N., Yamasaki Y., Itaka K., Kanayama N., Harada A., et al. Lactose-conjugated polyion complex micelles incorporating plasmid DNA as a targetable gene vector system: their preparation and gene transfecting efficiency against cultured HepG2 cells. J Control Release 95 3 (2004) 653-664
Oishi M., Nagasaki Y., Itaka K., Nishiyama N., and Kataoka K. Lactosylated poly(ethylene glycol)-siRNA conjugate through acid-labile ss-thiopropionate linkage to construct pH-sensitive polyion complex micelles achieving enhanced gene silencing in hepatoma cells. J Am Chem Soc 127 6 (2005) 1624-1625
Wu K., Shi L.Q., Zhang W.Q., An Y.L., Zhu X.X., Zhang X., et al. Formation of hybrid micelles between poly(ethylene glycol)-block-poly(4-vinylpyridinium) cations and sulfate anions in an aqueous milieu. Soft Matter 1 6 (2005) 455-459
Wu K., Shi L.Q., Zhang W.Q., An Y.L., Zhang X., Li Z.Y., et al. Thermoresponsiveness of hybrid micelles from poly(ethylene glycol)-block-poly(4-vinylpyridium) cations annul SO42- anions in aqueous solutions. Langmuir 22 4 (2006) 1474-1477
Yan Y., Besseling N.A.M., de Keizer A., Marcelis A.T.M., Drechsler M., and Cohen Stuart M.A. Hierarchical self-assembly in solutions containing metal ions, ligand, and diblock copolymer. Angew Chem Int Ed 46 11 (2007) 1807-1809
Harada A., and Kataoka K. Supramolecular assemblies of block copolymers in aqueous media as nanocontainers relevant to biological applications. Prog Polym Sci 31 11 (2006) 949-982
Kataoka K., Harada A., and Nagasaki Y. Block copolymer micelles for drug delivery: design, characterization and biological significance. Adv Drug Deliv Rev 47 1 (2001) 113-131
Kabanov A.V., and Kabanov V.A. Interpolyelectrolyte and block ionomer complexes for gene delivery: physicochemical aspects. Adv Drug Deliv Rev 30 1-3 (1998) 49-60
Voets I.K., Fokkink R., de Keizer A., May R.P., de Waard P., and Cohen Stuart M.A. On the transition between a heterogeneous and homogeneous corona in mixed polymeric micelles. Langmuir 24 21 (2008) 12221-12227
Voets I.K., Fokkink R., Hellweg T., King S.M., de Waard P., de Keizer A., et al. Spontaneous symmetry breaking: formation of Janus micelles. Soft Matter 5 5 (2009) 999-1005
Voets I.K., Moll P.M., Aqil A., Jerome C., Detrembleur C., de Waard P., et al. Temperature responsive complex coacervate core micelles with a PEO and PNIPAAm corona. J Phys Chem B 112 35 (2008) 10833-10840
Schmalz H., Lanzendorfer M.G., Abetz V., and Müller A.H.E. Anionic polymerization of ethylene oxide in the presence of the phosphazene base (BuP4)-P-t - Kinetic investigations using in-situ FT-NIR spectroscopy and MALDI-ToF MS. Macromol Chem Phys 204 8 (2003) 1056-1071
Debuigne A., Warnant J., Jerome R., Voets I., de Keizer A., Cohen Stuart M.A., et al. Synthesis of novel well-defined poly(vinyl acetate)-b-poly(acrylonitrile) and derivatized water-soluble poly(vinyl alcohol)-b-poly(acrylic acid) block copolymers by cobalt-mediated radical polymerization. Macromolecules 41 7 (2008) 2353-2360
Debuigne A., Caille J.R., Detrembleur C., and Jerome R. Effective cobalt mediation of the radical polymerization of vinyl acetate in suspension. Angew Chem Int Ed 44 22 (2005) 3439-3442
Debuigne A., Caille J.R., and Jerome R. Highly efficient cobalt-mediated radical polymerization of vinyl acetate. Angew Chem Int Ed 44 7 (2005) 1101-1104
Salomaa P., Schaleger L.L., and Long F.A. Solvent deuterium isotope effects on acid-base equilibria. J Am Chem Soc 86 1 (1964) 1-7
Lindhoud S., Norde W., and Cohen Stuart M.A. Reversibility and relaxation behavior of polyelectrolyte complex micelle formation. J Phys Chem B 113 16 (2009) 5431-5439
Hofs B., de Keizer A., and Cohen Stuart M.A. On the stability of (highly aggregated) polyelectrolyte complexes containing a charged-block-neutral diblock copolymer. J Phys Chem B 111 20 (2007) 5621-5627
van der Burgh S., de Keizer A., and Cohen Stuart M.A. Complex coacervation core micelles. Colloidal stability and aggregation mechanism. Langmuir 20 4 (2004) 1073-1084
van der Burgh S. Complex coacervate core micelles in solution and at interfaces (2004), Wageningen Universiteit, Wageningen p. 128
Voets I.K., de Keizer A., Cohen Stuart M.A., Justynska J., and Schlaad H. Irreversible structural transitions in mixed micelles of oppositely charged diblock copolymers in aqueous solution. Macromolecules 40 6 (2007) 2158-2164
Hong P.D., Chou C.M., and He C.H. Solvent effects on aggregation behavior of polyvinyl alcohol solutions. Polymer 42 14 (2001) 6105-6112
Tacx J., Schoffeleers H.M., Brands A.G.M., and Teuwen L. Dissolution behavior and solution properties of polyvinylalcohol as determined by viscometry and light scattering in DMSO, ethyleneglycol and water. Polymer 41 3 (2000) 947-957
Khutoryanskiy V.V., Dubolazov A.V., Nurkeeva Z.S., and Mun G.A. pH effects in the complex formation and blending of poly(acrylic acid) with poly(ethylene oxide). Langmuir 20 9 (2004) 3785-3790
Nurkeeva Z.S., Mun G.A., Dubolazov A.V., and Khutoryanskiy V.V. PH effects on the complexation, miscibility and radiation-induced crosslinking in poly(acrylic acid)-poly (vinyl alcohol) blends. Macromol Biosci 5 5 (2005) 424-432
Khutoryanskiy V.V., Mun G.A., Nurkeeva Z.S., and Dubolazov A.V. pH and salt effects on interpolymer complexation via hydrogen bonding in aqueous solutions. Polym Int 53 9 (2004) 1382-1387
Voets I.K., van der Burgh S., Farago B., Fokkink R., Kovacevic D., Hellweg T., et al. Electrostatically driven coassembly of a diblock copolymer and an oppositely charged homopolymer in aqueous solutions. Macromolecules 40 23 (2007) 8476-8482
Kawaguchi S., Imai G., Suzuki J., Miyahara A., and Kitano T. Aqueous solution properties of oligo- and poly(ethylene oxide) by static light scattering and intrinsic viscosity. Polymer 38 12 (1997) 2885-2891
Lai W.C., and Liau W.B. Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends. J Appl Polym Sci 92 3 (2004) 1562-1568
Vijayalakshmi S.P., and Madras G. Thermal degradation of water soluble polymers and their binary blends. J Appl Polym Sci 101 1 (2006) 233-240
Wanchoo R.K., Narula M., and Thakur A. Miscibility studies on some water soluble polymer-polymer blends. J Polym Mater 24 1 (2007) 57-64
Schacher F., Walther A., Ruppel M., Drechsler M., and Mueller A.H.E. Multicompartment core micelles of triblock terpolymers in organic media. Macromolecules 42 10 (2009) 3540-3548
Uchman M, Stepanek M, Prochazka K, Mountrichas G, Pispas S, Voets IK, et al. Multicompartment nanoparticles formed by a heparin-mimicking block terpolymer in aqueous solutions. Macromolecules, in press, doi:10.1021/ma9008115.
Kubowicz S., Baussard J.F., Lutz J.F., Thunemann A.F., von Berlepsch H., and Laschewsky A. Multicompartment micelles formed by self-assembly of linear ABC triblock copolymers in aqueous medium. Angew Chem Int Ed 44 33 (2005) 5262-5265
Ritzenthaler S., Court F., David L., Girard-Reydet E., Leibler L., and Pascault J.P. ABC triblock copolymers/epoxy-diamine blends. 1. Keys to achieve nanostructured thermosets. Macromolecules 35 16 (2002) 6245-6254
Hoppenbrouwers E., Li Z., and Liu G.J. Triblock nanospheres with amphiphilic coronal chains. Macromolecules 36 3 (2003) 876-881
Kuo S.W., Tung P.H., Lai C.L., Jeong K.U., and Chang F.C. Supramolecular micellization of diblock copolymer mixtures mediated by hydrogen bonding for the observation of separated coil and chain aggregation in common solvents. Macromol Rapid Commun 29 3 (2008) 229-233
Gohy J.F., Khousakoun E., Willet N., Varshney S.K., and Jerome R. Segregation of coronal chains in micelles formed by supramolecular interactions. Macromol Rapid Commun 25 17 (2004) 1536-1539
Dan N., and Tirrell M. Effect of bimodal molecular-weight distribution on the polymer brush. Macromolecules 26 24 (1993) 6467-6473
Fleer G.J., Cohen Stuart M.A., Scheutjens J.M.H.M., Cosgrove T., and Vincent B. Polymers at interfaces (1993), Chapman & Hall, London
Hardy R.C., and Cottington R.L. Viscosity of deuterium oxide and water in the range 5 °C to 125 °C. J Res Natl Bur Stand 42 6 (1949) 573-578