Unraveling the Agglomeration Mechanism in Charged Block Copolymer and Surfactant Complexes

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.; Goswami, Monojoy

doi:10.1021/acs.macromol.6b02319

Unraveling the Agglomeration Mechanism in Charged Block Copolymer and Surfactant Complexes

Journal Article · Thu Jan 26 23:00:00 EST 2017 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b02319· OSTI ID:1346670

Borreguero, Jose M. ^[1]; Pincus, Philip A. ^[2]; ^[3]; ^[3]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Data Analysis and Visualization
Univ. of California, Santa Barbara, CA (United States). Dept. of Materials Science
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences and Computer Science and Mathematics Division

Here, we report a molecular dynamics simulation investigation of self-assembly and complex formation of charged-neutral double hydrophilic and hydrophobic-hydrophilic block copolymers (BCP) with oppositely charged surfactants. Furthermore, the structure of the surfactant micelles and the BCP aggregation on the micelle surface is systematically studied for five different BCP volume fractions that also mimics a reduction of the surfactant concentration. The local electrostatic interactions between the oppositely charged species encourage the formation of core-shell structures between the surfactant micelles where the surfactants form the cores and the charged blocks of the BCP form the corona. The emergent morphologies of these aggregates are contingent upon the nature of the BCP neutral blocks. The hydrophilic neutral blocks agglomerate with the micelles as hairy colloidal structures while the hydrophobic neutrals agglomerate in lamellar structures with the surfactant micelles. The distribution of counterion charges along the simulation box show a close-to-normal density distribution for the hydrophilic neutral blocks and a binodal distribution for hydrophobic neutral blocks. No specific surfactant concentration dependent scaling relation is observed as opposed to the simpler case of homo-polyelectrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Spallation Neutron Source; Oak Ridge Leadership Computing Facility (OLCF); Joint Institute for Computational Sciences (JICS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1346670

Alternate ID(s):: OSTI ID: 1484360

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 3 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Recent Applications of Conjugated Polyelectrolytes in Optoelectronic Devices Hoven, Corey V.; Garcia, Andres; Bazan, Guillermo C. Advanced Materials, Vol. 20, Issue 20 https://doi.org/10.1002/adma.200800533	journal	October 2008
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Particle motions in sheared suspensions XXVII. Transient and steady deformation and burst of liquid drops Torza, S.; Cox, R. G.; Mason, S. G. Journal of Colloid and Interface Science, Vol. 38, Issue 2 https://doi.org/10.1016/0021-9797(72)90255-X	journal	February 1972
Surfactants in microbiology and biotechnology: Part 2. Application aspects Singh, Ajay; Van Hamme, Jonathan D.; Ward, Owen P. Biotechnology Advances, Vol. 25, Issue 1 https://doi.org/10.1016/j.biotechadv.2006.10.004	journal	January 2007
Association and structure formation in oppositely charged polyelectrolyte–surfactant mixtures Kogej, Ksenija Advances in Colloid and Interface Science, Vol. 158, Issue 1-2 https://doi.org/10.1016/j.cis.2009.04.003	journal	July 2010
Controlling electrostatic co-assembly using ion-containing copolymers: From surfactants to nanoparticles Berret, J. -F. Advances in Colloid and Interface Science, Vol. 167, Issue 1-2 https://doi.org/10.1016/j.cis.2011.01.008	journal	September 2011
A review of the formation and classification of amphiphilic block copolymer nanoparticulate structures: micelles, nanospheres, nanocapsules and polymersomes Letchford, Kevin; Burt, Helen European Journal of Pharmaceutics and Biopharmaceutics, Vol. 65, Issue 3 https://doi.org/10.1016/j.ejpb.2006.11.009	journal	March 2007
Block copolymer pervaporation membrane for in situ product removal during acetone–butanol–ethanol fermentation Shin, Chaeyoung; Baer, Zachary C.; Chen, X. Chelsea Journal of Membrane Science, Vol. 484 https://doi.org/10.1016/j.memsci.2015.03.005	journal	June 2015
Theory of polyelectrolytes in solutions and at surfaces Dobrynin, A.; Rubinstein, M. Progress in Polymer Science, Vol. 30, Issue 11 https://doi.org/10.1016/j.progpolymsci.2005.07.006	journal	November 2005
Surfactant-Mediated Polyelectrolyte Self-Assembly in a Polyelectrolyte–Surfactant Complex Goswami, Monojoy; Borreguero, Jose M.; Pincus, Philip A. Macromolecules, Vol. 48, Issue 24 https://doi.org/10.1021/acs.macromol.5b02145	journal	November 2015
Modulation of the Mechanical Properties of Hydrophobically Modified Supramolecular Hydrogels by Surfactant-Driven Structural Rearrangement Wang, Chao; Wiener, Clinton G.; Cheng, Ziwei Macromolecules, Vol. 49, Issue 23 https://doi.org/10.1021/acs.macromol.6b01813	journal	November 2016
Chemical Sensors Based on Amplifying Fluorescent Conjugated Polymers Thomas, Samuel W.; Joly, Guy D.; Swager, Timothy M. Chemical Reviews, Vol. 107, Issue 4 https://doi.org/10.1021/cr0501339	journal	April 2007
Determination of Critical Micelle Concentration of Some Surfactants by Three Techniques Dominguez, Ana; Fernandez, Aurora; Gonzalez, Noemi Journal of Chemical Education, Vol. 74, Issue 10 https://doi.org/10.1021/ed074p1227	journal	October 1997
The size, shape, and hydration of nonionic surfactant micelles. Triton X-100 Robson, Robert J.; Dennis, Edward A. The Journal of Physical Chemistry, Vol. 81, Issue 11 https://doi.org/10.1021/j100526a010	journal	June 1977
Environmentally Responsive “Hairy” Nanoparticles: Mixed Homopolymer Brushes on Silica Nanoparticles Synthesized by Living Radical Polymerization Techniques Li, Dejin; Sheng, Xia; Zhao, Bin Journal of the American Chemical Society, Vol. 127, Issue 17 https://doi.org/10.1021/ja0422561	journal	May 2005
Colloidal Complexes Obtained from Charged Block Copolymers and Surfactants: A Comparison between Small-Angle Neutron Scattering, Cryo-TEM, and Simulations Berret, Jean-François; Hervé, Pascal; Aguerre-Chariol, Olivier The Journal of Physical Chemistry B, Vol. 107, Issue 32 https://doi.org/10.1021/jp027740+	journal	June 2003
Accurate Free Energies of Micelle Formation ^† Pool, René; Bolhuis, Peter G. The Journal of Physical Chemistry B, Vol. 109, Issue 14 https://doi.org/10.1021/jp045576f	journal	April 2005
Molecular Dynamics Simulations of Polyelectrolyte−Polyampholyte Complexes. Effect of Solvent Quality and Salt Concentration Jeon, Junhwan; Dobrynin, Andrey V. The Journal of Physical Chemistry B, Vol. 110, Issue 48 https://doi.org/10.1021/jp064288b	journal	December 2006
Complexes of Polyelectrolyte-Neutral Double Hydrophilic Block Copolymers with Oppositely Charged Surfactant and Polyelectrolyte ^† Pispas, Stergios The Journal of Physical Chemistry B, Vol. 111, Issue 29 https://doi.org/10.1021/jp067437z	journal	July 2007
Breakdown of Inverse Morphologies in Charged Diblock Copolymers Goswami, Monojoy; Kumar, Rajeev; Sumpter, Bobby G. The Journal of Physical Chemistry B, Vol. 115, Issue 13 https://doi.org/10.1021/jp111001n	journal	April 2011
Mesoscopic Simulation of Polymer−Surfactant Aggregation Groot, Robert D. Langmuir, Vol. 16, Issue 19 https://doi.org/10.1021/la000010d	journal	September 2000
Response of Polyelectrolyte Complexes to Subsequent Addition of Salts with Different Cations Dautzenberg, Herbert; Kriz, Jaroslav Langmuir, Vol. 19, Issue 13 https://doi.org/10.1021/la0209482	journal	June 2003
Structure of a Hydrophilic−Hydrophobic Block Copolymer and Its Interactions with Salt and an Anionic Surfactant Wesley, Robin D.; Dreiss, Cécile A.; Cosgrove, Terence Langmuir, Vol. 21, Issue 11 https://doi.org/10.1021/la046830y	journal	May 2005
Potentials of Mean Force and Escape Times of Surfactants from Micelles and Hydrophobic Surfaces Using Molecular Dynamics Simulations Yuan, Fang; Wang, Shihu; Larson, Ronald G. Langmuir, Vol. 31, Issue 4 https://doi.org/10.1021/la5044393	journal	January 2015
Local structure of semiflexible polymer melts Honnell, Kevin G.; Curro, John G.; Schweizer, Kenneth S. Macromolecules, Vol. 23, Issue 14 https://doi.org/10.1021/ma00216a018	journal	July 1990
Polyelectrolyte−Colloid Complexes: Polarizability and Effective Interaction Dzubiella, J.; Moreira, A. G.; Pincus, P. A. Macromolecules, Vol. 36, Issue 5 https://doi.org/10.1021/ma021322l	journal	March 2003
Contact Aggregation, Bridging, and Steric Stabilization in Dense Polymer−Particle Mixtures Hooper, Justin B.; Schweizer, Kenneth S. Macromolecules, Vol. 38, Issue 21 https://doi.org/10.1021/ma051318k	journal	October 2005
Coassembly of Poly(ethylene oxide)- block -poly(methacrylic acid) and N -Dodecylpyridinium Chloride in Aqueous Solutions Leading to Ordered Micellar Assemblies within Copolymer Aggregates Uchman, Mariusz; Štěpánek, Miroslav; Prévost, Sylvain Macromolecules, Vol. 45, Issue 16 https://doi.org/10.1021/ma301510j	journal	July 2012
Thermodynamic and Kinetic Aspects of Coassembly of PEO–PMAA Block Copolymer and DPCl Surfactants into Ordered Nanoparticles in Aqueous Solutions Studied by ITC, NMR, and Time-Resolved SAXS Techniques Uchman, Mariusz; Gradzielski, Michael; Angelov, Borislav Macromolecules, Vol. 46, Issue 6 https://doi.org/10.1021/ma302503w	journal	March 2013
Dissipative Particle Dynamics Study of the pH-Dependent Behavior of Poly(2-vinylpyridine)- block -poly(ethylene oxide) Diblock Copolymer in Aqueous Buffers Posel, Zbyšek; Limpouchová, Zuzana; Šindelka, Karel Macromolecules, Vol. 47, Issue 7 https://doi.org/10.1021/ma402293c	journal	March 2014
Dissipative Particle Dynamics Study of Electrostatic Self-Assembly in Aqueous Mixtures of Copolymers Containing One Neutral Water-Soluble Block and One Either Positively or Negatively Charged Polyelectrolyte Block Šindelka, Karel; Limpouchová, Zuzana; Lísal, Martin Macromolecules, Vol. 47, Issue 17 https://doi.org/10.1021/ma501018x	journal	August 2014
Morphology–Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries Inceoglu, Sebnem; Rojas, Adriana A.; Devaux, Didier ACS Macro Letters, Vol. 3, Issue 6 https://doi.org/10.1021/mz5001948	journal	May 2014
Responsive Block Copolymer Photonics Triggered by Protein–Polyelectrolyte Coacervation Fan, Yin; Tang, Shengchang; Thomas, Edwin L. ACS Nano, Vol. 8, Issue 11 https://doi.org/10.1021/nn504565r	journal	November 2014
The self-assembly of copolymers with one hydrophobic and one polyelectrolyte block in aqueous media: a dissipative particle dynamics study Lísal, Martin; Limpouchová, Zuzana; Procházka, Karel Physical Chemistry Chemical Physics, Vol. 18, Issue 24 https://doi.org/10.1039/C6CP00341A	journal	January 2016
The electrostatic co-assembly in non-stoichiometric aqueous mixtures of copolymers composed of one neutral water-soluble and one polyelectrolyte (either positively or negatively charged) block: a dissipative particle dynamics study Šindelka, Karel; Limpouchová, Zuzana; Lísal, Martin Physical Chemistry Chemical Physics, Vol. 18, Issue 24 https://doi.org/10.1039/C6CP01047D	journal	January 2016
Polymer electrolytes for lithium polymer batteries Long, Lizhen; Wang, Shuanjin; Xiao, Min Journal of Materials Chemistry A, Vol. 4, Issue 26 https://doi.org/10.1039/C6TA02621D	journal	January 2016
Tunable morphologies from charged block copolymers Goswami, Monojoy; Sumpter, Bobby G.; Huang, Tianzi Soft Matter, Vol. 6, Issue 24 https://doi.org/10.1039/c0sm00733a	journal	January 2010
Asymmetrical self-assembly from fluorinated and sulfonated block copolymers in aqueous media Wang, Xiaojun; Hong, Kunlun; Baskaran, Durairaj Soft Matter, Vol. 7, Issue 18 https://doi.org/10.1039/c1sm06040f	journal	January 2011
Morphologies of block copolymers composed of charged and neutral blocks Wang, Xiaojun; Goswami, Monojoy; Kumar, Rajeev Soft Matter, Vol. 8, Issue 11 https://doi.org/10.1039/c2sm07223h	journal	January 2012
Complexes of polyelectrolytes and oppositely charged ionic surfactants von Ferber, C.; Löwen, H. The Journal of Chemical Physics, Vol. 118, Issue 23 https://doi.org/10.1063/1.1574782	journal	June 2003
Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations Ou, Zhaoyang; Muthukumar, M. The Journal of Chemical Physics, Vol. 124, Issue 15 https://doi.org/10.1063/1.2178803	journal	April 2006
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
Methods for strand-specific DNA detection with cationic conjugated polymers suitable for incorporation into DNA chips and microarrays Liu, B.; Bazan, G. C. Proceedings of the National Academy of Sciences, Vol. 102, Issue 3 https://doi.org/10.1073/pnas.0408561102	journal	January 2005
Review of flow rate estimates of the Deepwater Horizon oil spill McNutt, M. K.; Camilli, R.; Crone, T. J. Proceedings of the National Academy of Sciences, Vol. 109, Issue 50 https://doi.org/10.1073/pnas.1112139108	journal	December 2011
Entropy-driven collective interactions in DNA brushes on a biochip Bracha, D.; Karzbrun, E.; Shemer, G. Proceedings of the National Academy of Sciences, Vol. 110, Issue 12 https://doi.org/10.1073/pnas.1220076110	journal	March 2013
Polyelectrolyte surfactant complexes at interfaces and in bulk Guillot, Samuel; McLoughlin, Daragh; Jain, Nirmesh Journal of Physics: Condensed Matter, Vol. 15, Issue 1 https://doi.org/10.1088/0953-8984/15/1/328	journal	December 2002
Shear-Induced Deformation of Surfactant Multilamellar Vesicles Pommella, Angelo; Caserta, Sergio; Guida, Vincenzo Physical Review Letters, Vol. 108, Issue 13 https://doi.org/10.1103/PhysRevLett.108.138301	journal	March 2012
Induced Crystallization of Polyelectrolyte-Surfactant Complexes at the Gas-Water Interface Vaknin, D.; Dahlke, S.; Travesset, A. Physical Review Letters, Vol. 93, Issue 21 https://doi.org/10.1103/PhysRevLett.93.218302	journal	November 2004
Polymer Vesicles Discher, D. E. Science, Vol. 297, Issue 5583 https://doi.org/10.1126/science.1074972	journal	August 2002
Novel core-shell structure for colloids made of neutral/polyelectrolyte diblock copolymers and oppositely charged surfactants Hervé, P.; Destarac, M.; Berret, J. -F Europhysics Letters (EPL), Vol. 58, Issue 6 https://doi.org/10.1209/epl/i2002-00104-y	journal	June 2002

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