University CrestBlock Copolymer Micelles, 'Schizophrenic' Diblock Copolymers and Novel Polymeric SurfactantsArmes Research Group
Current Location:  Research > Block Copolymer Micelles, 'Schizophrenic' Diblock Copolymers and Novel Polymeric Surfactants
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  4 September 2005

Since 1996 we have synthesised a wide range of hydrophilic-hydrophilic diblock copolymers using various chemistries (group transfer polymerisation, living cationic polymerisation, nitroxide-mediated polymerisation, and atom transfer radical polymerisation). In many cases the less hydrophilic block can be tuned to become hydrophobic by controlling the solution pH, temperature or ionic strength [S. Liu and S. P. Armes, Curr. Opinion Colloid Interface Sci., 2001]. Thus both interfacial activity and supramolecular self-assembly into colloidal aggregates (micelles) in aqueous solution can be tuned and also made reversible. Recently we have designed novel AB diblock copolymers which can form both conventional micelles ('A' block in the core) and reverse/inverted micelles ('B' block in the core) in aqueous solution. Since two micellar states can be formed, we have coined the phrase 'schizophrenic' to describe these block copolymers [S. Liu et al., Angewandte Chem., 2001]. We were the first to report an example of a pH-responsive zwitterionic diblock copolymer that can be switched between two micellar states at ambient temperature solely by adjusting the solution pH [S. Liu and S. P. Armes, Angewandte Chem., 2002]. We have also reported the synthesis of purely thermo-responsive 'schizophrenic' diblock copolymers [J. V. M. Weaver et al., Chem. Commun., 2002]. Very recently we described the fascinating aqueous solution behaviour of a novel ABC triblock copolymer that can form a 'trinity' of micelles in aqueous solution simply by adjusting the solution pH. Moreover, the driving force for micellisation is different in each case: at high pH the micelle cores are hydrophobic, at intermediate pH polyion complexation occurs and at low pH hydrogen-bonded micelles are formed [Y. Cai and S. P. Armes, Macromolecules, 2004]. This emerging field has recently been reviewed [S. P. Armes and co-workers, Reactive Functional Polymers, 2005, in the press].

Selected Publications
"pH-responsive behavior of selectively quaternized diblock copolymers adsorbed at the silica/aqueous solution interface"
K. Sakai, E. G. Smith, G. B. Webber, M. Baker, E. J. Wanless, V. Butun, S. P. Armes, S. Biggs
Journal of Colloid and Interface Science 2007, 314, 381
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"Direct Visualization of a Self-Organized Multilayer Film of Low Tg Diblock Copolymer Micelles"
E. G. Smith, G. B. Webber, K. Sakai, S. Biggs, S. P. Armes, E. J. Wanless
Journal of Physical Chemistry B 2007, 111, 5536
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"Probing the micellization kinetics of pyrene end-labeled diblock copolymers via a combination of stopped-flow light-scattering and fluorescence techniques"
J. Zhang, Y. Li, S. P. Armes, S. Liu
Journal of Physical Chemistry B 2007, 111, 12111
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"Synthesis of Zwitterionic Diblock Copolymers without Protecting Group Chemistry"
C. D. Vo, S. P. Armes, D. P. Randall, K. Sakai, S. Biggs
Macromolecules 2007, 40, 157
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"A New Class of Biochemically Degradable, Stimulus-Responsive Triblock Copolymer Gelators"
C. Li, J. Madsen, S. P. Armes and A. L. Lewis
Angewandte Chemie, International Edition 2006, 45, 3510
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"Effects of copolymer concentration and chain length on the pH-responsive behavior of diblock copolymer micellar films."
K. Sakai, E.G. Smith, G.B. Webber, E. J. Wanless, V. B》], S.P. Armes, S. Biggs
Journal of Colloid and Interface Science 2006, 303, 372
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"Reversible Activation of Diblock Copolymer Monolayers at the Interface by pH Modulation, 2: Membrane Interactions at the Solid/Liquid Interface"
F. Rehfeldt, R. Steitz, S. P. Armes, R. von Klitzing, A. P. Gast, M. Tanaka
Journal of Physical Chemistry B 2006, 110, 9177
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"Reversible Activation of Diblock Copolymer Monolayers at the Interface by pH Modulation, 1: Lateral Chain Density and Conformation"
F. Rehfeldt, R. Steitz, S. P. Armes, R. von Klitzing, A. P. Gast, and M. Tanaka
Journal of Physical Chemistry B 2006, 110, 9171
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"pH-Responsive Diblock Copolymer Micelles at the Silica/Aqueous Solution Interface: Adsorption Kinetics and Equilibrium Studies."
K. Sakai, E.G. Smith, G.B. Webber, C. Schatz, E. J. Wanless, V. B》], S.P. Armes, S. Biggs
Journal of Physical Chemistry B 2006, 110, 14744
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"Characterizing the pH-Responsive Behavior of Thin Films of Diblock Copolymer Micelles at the Silica/Aqueous Solution Interface."
K. Sakai, E.G. Smith, G.B. Webber, M. Baker, E. J. Wanless, V. B》], S.P. Armes, S. Biggs
Langmuir 2006, 22, 8435
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"Neutron Reflection Study of a Water-Soluble Biocompatible Diblock Copolymer Adsorbed at the Air/Water Interface: The Effects of pH and Polymer Concentration."
Q. S. Mu, J. R. Lu, Y. H. Ma, M. V. Paz de Banez, K.L. Robinson, S. P. Armes, A. L. Lewis, R. K. Thomas
Langmuir 2006, 22, 6153
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"Comparison of the Adsorption of Cationic Diblock Copolymer Micelles from Aqueous Solution onto Mica and Silica"
K. Sakai, E. G. Smith, G. B. Webber, C. Schatz, E. J. Wanless, V. B》], S. P. Armes, S. Biggs
Langmuir 2006, 22, 5328
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"Preparation and Aqueous Solution Properties of New Thermoresponsive Biocompatible ABA Triblock Copolymer Gelators."
J. Madsen, S.P. Armes, A.L. Lewis
Macromolecules 2006, 39, 7455
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"Micelle Formation and Inversion Kinetics of a Schizophrenic Diblock Copolymer."
D. Wang, J. Yin, Z. Zhu, Z. Ge, H. Liu, S. P. Armes, S. Liu
Macromolecules 2006, 39, 7378
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"UV irradiation-induced shell cross-linked micelles with pH-responsive cores using ABC triblock copolymers."
X. Jiang, S. Luo, S. P. Armes, W. Shi, S. Liu
Macromolecules 2006, 39, 5987
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"Synthesis and Solid State Properties of a Poly(methyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)-block-poly(methyl methacrylate) Triblock Copolymer."
P. D. Topham, J. R. Howse, O. O. Mykhaylyk, S. P. Armes, R. A. L. Jones, A. J. Ryan
Macromolecules 2006, 39, 5573
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"Dynamic Light Scattering vs 1H NMR Investigation of pH-Responsive Diblock Copolymers in Water."
M. Vamvakaki, D. Palioura, A. Spyros, S.P. Armes, S. H. Anastasiadis
Macromolecules 2006, 39, 5106
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"Synthesis of Reversible Shell Cross-Linked Micelles for Controlled Release of Bioactive Agents"
Y. Li, B. S. Lokitz, S. P. Armes and C. L. McCormick
Macromolecules 2006, 39, 2726
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"ATR-FTIR studies of a thermo-responsive ABA triblock copolymer gelator in aqueous solution."
C. Sammon, C. Li, S. P. Armes, A. L. Lewis
Polymer 2006, 47, 6123
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"New folate-functionalized biocompatible block copolymer micelles as potential anti-cancer drug delivery systems"
M. Licciardi, G. Giammona, J. Du, S. P. Armes,Y. Tang, A. L. Lewis
Polymer 2006, 47, 2946
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"Controlled growth of poly (2-(diethylamino)ethyl methacrylate) brushes via atom transfer radical polymerisation on planar silicon surfaces"
P. D. Topham, J. R. Howse, C. J. Crook 1, A. J. Parnell, M. Geoghegan, R. A. L. Jones, A. J. Ryan
Polymer International 2006, 55, 808
"A brief review of 'schizophrenic' block copolymers"
V. B》], S. Liu, J. V. M. Weaver, X. Bories-Azeau, Y. Cai, S. P. Armes
Reactive & Functional Polymers 2006, 66, 157
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"Synthesis and characterization of biocompatible thermo-responsive gelators based on ABA triblock copolymers"
C. M. Li, Y. Q. Tang, S. P. Armes, C. J. Morris, S. F. Rose, A. W. Lloyd and A. L. Lewis
Biomacromolecules 2005, 6, 994
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"Synthesis of novel folic acid-functionalized biocompatible block copolymers by atom transfer radical polymerization for gene delivery and encapsulation of hydrophobic drugs"
M. Licciardi, Y. Tang, N. C. Billingham and S. P. Armes
Biomacromolecules 2005, 6, 1085
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"pH-sensitive vesicles based on a biocompatible zwitterionic diblock copolymer"
J. Z. Du, Y. P. Tang, A. L. Lewis, S. P. Armes
Journal of the American Chemical Society 2005, 127, 17982
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"pH-Responsive Vesicles Based on a Hydrolytically Self-Cross-Linkable Copolymer"
J. Du and S. P. Armes
Journal of the American Chemical Society 2005, 127, 12800
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"Biomimetic Stimulus-Responsive Star Diblock Gelators"
Y. Li, Y. Tang, R. Narain, A. L. Lewis and S. P. Armes
Langmuir 2005, 21, 9946
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"Synthesis and Characterization of Shell Cross-Linked Micelles with Hydroxy-Functional Coronas: A Pragmatic Alternative to Dendrimers?"
L. N. Pilon, S. P. Armes, P. Findlay and S. P. Rannard
Langmuir 2005, 21, 3808
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"Synthesis and Characterization of Biocompatible, Thermoresponsive ABC and ABA Triblock Copolymer Gelators"
C. Li, N. J. Buurma, I. Haq, C. Turner, S. P. Armes, V. Castelletto, I.W. Hamley, A.L. Lewis
Langmuir 2005, 21, 11026
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"pH-Induced Micellization Kinetics of ABC Triblock Copolymers Measured by Stopped-Flow Light Scattering"
Z. Zhu, S. P. Armes and S. Liu
Macromolecules 2005, 38, 9803
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"Synthesis of well-defined Y-shaped zwitterionic block copolymers via atom-transfer radical polymerization"
Y. Cai and S. P. Armes
Macromolecules 2005, 38, 271
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"Direct synthesis and aqueous solution properties of Y-shaped, stimulus-responsive block copolymer surfactants"
Y. Cai, C. Burguiere, S. P. Armes
Chemical Communications 2004, 7, 802
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"Direct synthesis and stimulus-responsive micellization of Y-shaped hydrophilic block copolymers"
Y. Cai, Y. Tang and S. P. Armes
Macromolecules 2004, 37, 9728
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"A zwitterionic ABC triblock copolymer that forms a "Trinity" of micellar aggregates in aqueous solution"
Y. L. Cai and S. P. Armes
Macromolecules 2004, 37, 7116
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"Stimulus-responsive water-soluble polymers based on 2-hydroxyethyl methacrylate"
J. V. M. Weaver, I. Bannister, K. L. Robinson, X. Bories-Azeau and S. P. Armes
Macromolecules 2004, 37, 2395
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"Facile synthesis of zwitterionic diblock copolymers without protecting group chemistry"
X. Bories-Azeau, S. P. Armes, and H. J. W. van den Haak
Macromolecules 2004, 37, 2348
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"Synthesis and aqueous solution behaviour of a pH-responsive schizophrenic diblock copolymer"
S. Y. Liu, S. P. Armes
Langmuir 2003, 19, 4432
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"A ?holy trinity? of micelles formed in aqueous solution at ambient temperature: unprecedented self-assembly behavior from a binary mixture of a neutral-cationic diblock copolymer and an anionic polyelectrolyte"
J. V. M. Weaver, S. P. Armes, and S. Liu
Macromolecules 2003, 36, 9994
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"Polymeric surfactants for the new millenium: a pH-responsive, zwitterionic, schizophrenic diblock copolymer"
S. Liu and S. P. Armes
Angewandte Chemie, International Edition 2002, 41, 1413
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"Synthesis and aqueous solution properties of a well-defined thermo-responsive schizophrenic diblock copolymer"
J. V. M. Weaver, S. P. Armes, and V. Butun
Chemical Communications 2002, 18, 2122
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"A schizophrenic water-soluble diblock copolymer"
S. Liu, N. C. Billingham and S. P. Armes
Angewandte Chemie, International Edition 2001, 40, 2328
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"Recent advances in the synthesis of polymeric surfactants"
S. Liu and S. P. Armes
Current Opinion in Colloid and Interface Science 2001, 6, 249
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"Characterizing the structure of pH-dependent polyelectrolyte block copolymer micelles"
A. S. Lee, A. P. Gast, V. Butun and S. P. Armes
Macromolecules 1999, 32, 4302
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"Unusual aggregation behaviour of a novel tertiary amine methacrylate-based diblock copolymer: formation of micelles and reverse micelles in aqueous solution"
V. Butun, N. C. Billingham and S. P. Armes
Journal of the American Chemical Society 1998, 120, 11818
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Related Presentations
> "Controlled polymerisation of 2-hydroxypropyl methacrylate (HPMA) by ATRP at ambient temperature in alcohol / water mixtures" [PDF; 149KB]
Macro Group 2002, Warwick
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> "Synthesis and Aqueous Solution Properties of a Well-Defined Thermo-Responsive Schizophrenic Diblock Copolymer" [PDF; 261KB]
ACS 2003, New Orleans
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