Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Riggleman, Robert A.; Kumar, Rajeev; Fredrickson, Glenn H.

doi:10.1063/1.3674305

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Journal Article · Fri Jan 13 23:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3674305· OSTI ID:1081978

Riggleman, Robert A.; Kumar, Rajeev; Fredrickson, Glenn H.

Complex coacervation, a liquid-liquid phase separation that occurs when two oppositely charged polyelectrolytes are mixed in a solution, has the potential to be exploited for many emerging applications including wet adhesives and drug delivery vehicles. The ultra-low interfacial tension of coacervate systems against water is critical for such applications, and it would be advantageous if molecular models could be used to characterize how various system properties (e.g., salt concentration)affect the interfacial tension. In this article we use field-theoretic simulations to characterize the interfacial tension between a complex coacervate and its supernatant. After demonstrating that our model is free of ultraviolet divergences (calculated properties converge as the collocation grid is refined), we develop two methods for calculating the interfacial tension from field-theoretic simulations. One method relies on the mechanical interpretation of the interfacial tension as the interfacial pressure, and the second method estimates the change in free energy as the area between the two phases is changed. These are the first calculations of the interfacial tension from full field theoretic simulation of which we are aware, and both the magnitude and scaling behaviors of our calculated interfacial tension agree with recent experiments.

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1081978

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 136; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

References (52)

The First Targeted Delivery of siRNA in Humans via a Self-Assembling, Cyclodextrin Polymer-Based Nanoparticle: From Concept to Clinic Davis, Mark E. Molecular Pharmaceutics, Vol. 6, Issue 3 https://doi.org/10.1021/mp900015y	journal	April 2009
Precipitation of oppositely charged polyelectrolytes in salt solutions Kudlay, Alexander; Olvera de la Cruz, Monica The Journal of Chemical Physics, Vol. 120, Issue 1 https://doi.org/10.1063/1.1629271	journal	January 2004
Free Energy Evaluation in Field-Theoretic Polymer Simulations Lennon, Erin M.; Katsov, Kirill; Fredrickson, Glenn H. Physical Review Letters, Vol. 101, Issue 13 https://doi.org/10.1103/PhysRevLett.101.138302	journal	September 2008
Complex coacervates as a foundation for synthetic underwater adhesives Stewart, Russell J.; Wang, Ching Shuen; Shao, Hui Advances in Colloid and Interface Science, Vol. 167, Issue 1-2 https://doi.org/10.1016/j.cis.2010.10.009	journal	September 2011
Complexation between oppositely charged polyelectrolytes: Beyond the Random Phase Approximation Castelnovo, M.; Joanny, J. -F. The European Physical Journal E, Vol. 6, Issue 5, p. 377-386 https://doi.org/10.1007/s10189-001-8051-7	journal	December 2001
Effects of ion solvation on phase equilibrium and interfacial tension of liquid mixtures Wang, Rui; Wang, Zhen-Gang The Journal of Chemical Physics, Vol. 135, Issue 1 https://doi.org/10.1063/1.3607969	journal	July 2011
Interfacial tension between a complex coacervate phase and its coexisting aqueous phase Spruijt, Evan; Sprakel, Joris; Cohen Stuart, Martien A. Soft Matter, Vol. 6, Issue 1 https://doi.org/10.1039/b911541b	journal	January 2010
Field-theoretic simulations of polymer solutions: Finite-size and discretization effects Alexander-Katz, Alfredo; Moreira, André G.; Sides, Scott W. The Journal of Chemical Physics, Vol. 122, Issue 1 https://doi.org/10.1063/1.1827211	journal	January 2005
Surface tension, adsorption and surface entropy of liquid-vapour systems by atomistic simulation Salomons, E.; Mareschal, M. Journal of Physics: Condensed Matter, Vol. 3, Issue 20 https://doi.org/10.1088/0953-8984/3/20/025	journal	May 1991
Numerical coarse-graining of fluid field theories Villet, Michael C.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 132, Issue 3 https://doi.org/10.1063/1.3289723	journal	January 2010
A statistical theory of globular polyelectrolyte complexes Borue, V. Yu.; Erukhimovich, I. Ya. Macromolecules, Vol. 23, Issue 15 https://doi.org/10.1021/ma00217a015	journal	July 1990
Catch and Release of DNA in Coacervate-Dispersed Gels Ohsugi, Asami; Furukawa, Hidemitsu; Kakugo, Akira Macromolecular Rapid Communications, Vol. 27, Issue 15 https://doi.org/10.1002/marc.200600234	journal	August 2006
Polymorphic transitions in single crystals: A new molecular dynamics method Parrinello, M.; Rahman, A. Journal of Applied Physics, Vol. 52, Issue 12 https://doi.org/10.1063/1.328693	journal	December 1981
Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites Decher, G. Science, Vol. 277, Issue 5330 https://doi.org/10.1126/science.277.5330.1232	journal	August 1997
Phase Separation in Symmetric Mixtures of Oppositely Charged Rodlike Polyelectrolytes Kumar, Rajeev; Audus, Debra; Fredrickson, Glenn H. The Journal of Physical Chemistry B, Vol. 114, Issue 31 https://doi.org/10.1021/jp101413a	journal	August 2010
Complex coacervate core micelles Voets, Ilja K.; de Keizer, Arie; Cohen Stuart, Martien A. Advances in Colloid and Interface Science, Vol. 147-148 https://doi.org/10.1016/j.cis.2008.09.012	journal	March 2009
Cement Proteins of the Tube-building Polychaete Phragmatopoma californica Zhao, Hua; Sun, Chengjun; Stewart, Russell J. Journal of Biological Chemistry, Vol. 280, Issue 52 https://doi.org/10.1074/jbc.M508457200	journal	October 2005
A statistical theory of weakly charged polyelectrolytes: fluctuations, equation of state and microphase separation Borue, V. Yu.; Erukhimovich, I. Ya. Macromolecules, Vol. 21, Issue 11 https://doi.org/10.1021/ma00189a019	journal	November 1988
Improved numerical algorithm for exploring block copolymer mesophases Rasmussen, K. �.; Kalosakas, G. Journal of Polymer Science Part B: Polymer Physics, Vol. 40, Issue 16 https://doi.org/10.1002/polb.10238	journal	July 2002
The stress tensor in thermodynamics and statistical mechanics Rossi, G. C.; Testa, M. The Journal of Chemical Physics, Vol. 132, Issue 7 https://doi.org/10.1063/1.3316134	journal	February 2010
Fluctuation in electrolyte solutions: The self energy Wang, Zhen-Gang Physical Review E, Vol. 81, Issue 2 https://doi.org/10.1103/PhysRevE.81.021501	journal	February 2010
Efficient computation of the structural phase behavior of block copolymers Tzeremes, G.; Rasmussen, K. Ø.; Lookman, T. Physical Review E, Vol. 65, Issue 4 https://doi.org/10.1103/PhysRevE.65.041806	journal	April 2002
A new look at the atomic level virial stress: on continuum-molecular system equivalence Zhou, Min Proceedings of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, Vol. 459, Issue 2037 https://doi.org/10.1098/rspa.2003.1127	journal	September 2003
Strain fluctuations and elastic constants Parrinello, M.; Rahman, A. The Journal of Chemical Physics, Vol. 76, Issue 5 https://doi.org/10.1063/1.443248	journal	March 1982
Complex coacervation: A field theoretic simulation study of polyelectrolyte complexation Lee, Jonghoon; Popov, Yuri O.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 128, Issue 22 https://doi.org/10.1063/1.2936834	journal	June 2008
Complexation of oppositely charged polyelectrolytes: Effect of discrete charge distribution along the chain Potemkin, Igor I.; Palyulin, Vladimir V. Physical Review E, Vol. 81, Issue 4 https://doi.org/10.1103/PhysRevE.81.041802	journal	April 2010
Field-Theoretic Computer Simulation Methods for Polymers and Complex Fluids Fredrickson, Glenn H.; Ganesan, Venkat; Drolet, François Macromolecules, Vol. 35, Issue 1 https://doi.org/10.1021/ma011515t	journal	January 2002
Local Water Dynamics in Coacervated Polyelectrolytes Monitored through Dynamic Nuclear Polarization-Enhanced ¹ H NMR Kausik, Ravinath; Srivastava, Aasheesh; Korevaar, Peter A. Macromolecules, Vol. 42, Issue 19 https://doi.org/10.1021/ma901137g	journal	October 2009
On complex probabilities Parisi, Giorgio Physics Letters B, Vol. 131, Issue 4-6 https://doi.org/10.1016/0370-2693(83)90525-7	journal	November 1983
Calculation of surface tension via area sampling Errington, Jeffrey R.; Kofke, David A. The Journal of Chemical Physics, Vol. 127, Issue 17 https://doi.org/10.1063/1.2795698	journal	November 2007
Molecular dynamics simulation of the orthobaric densities and surface tension of water Alejandre, José; Tildesley, Dominic J.; Chapela, Gustavo A. The Journal of Chemical Physics, Vol. 102, Issue 11 https://doi.org/10.1063/1.469505	journal	March 1995
Test-area simulation method for the direct determination of the interfacial tension of systems with continuous or discontinuous potentials Gloor, Guy J.; Jackson, George; Blas, Felipe J. The Journal of Chemical Physics, Vol. 123, Issue 13 https://doi.org/10.1063/1.2038827	journal	October 2005
Efficient estimation of free energy differences from Monte Carlo data Bennett, Charles H. Journal of Computational Physics, Vol. 22, Issue 2 https://doi.org/10.1016/0021-9991(76)90078-4	journal	October 1976
A Langevin approach to fermion and quantum spin correlation functions Klauder, J. R. Journal of Physics A: Mathematical and General, Vol. 16, Issue 10 https://doi.org/10.1088/0305-4470/16/10/001	journal	July 1983
Direct experimental validation of the Jones–Ray effect Petersen, Poul B.; Johnson, Justin C.; Knutsen, Kelly P. Chemical Physics Letters, Vol. 397, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.08.048	journal	October 2004
Microencapsulation Luzzi, Louis A. Journal of Pharmaceutical Sciences, Vol. 59, Issue 10 https://doi.org/10.1002/jps.2600591002	journal	October 1970
Mechanism of Polyelectrolyte Multilayer Growth: Charge Overcompensation and Distribution Schlenoff, Joseph B.; Dubas, Stephan T. Macromolecules, Vol. 34, Issue 3 https://doi.org/10.1021/ma0003093	journal	January 2001
Field-theoretic simulations in the Gibbs ensemble Riggleman, Robert A.; Fredrickson, Glenn H. The Journal of Chemical Physics, Vol. 132, Issue 2 https://doi.org/10.1063/1.3292004	journal	January 2010
Regimes of Conformational Transitions of a Diblock Polyampholyte Wang, Zuowei; Rubinstein, Michael Macromolecules, Vol. 39, Issue 17 https://doi.org/10.1021/ma0607517	journal	August 2006
Scaling Theory of Diblock Polyampholyte Solutions Shusharina, N. P.; Zhulina, E. B.; Dobrynin, A. V. Macromolecules, Vol. 38, Issue 21 https://doi.org/10.1021/ma051324g	journal	October 2005
Multilayered polyelectrolyte assemblies as platforms for the delivery of DNA and other nucleic acid-based therapeutics☆ Jewell, C.; Lynn, D. Advanced Drug Delivery Reviews, Vol. 60, Issue 9 https://doi.org/10.1016/j.addr.2008.02.010	journal	June 2008
Complexation of Oppositely Charged Polyelectrolytes: Effect of Ion Pair Formation Kudlay, Alexander; Ermoshkin, Alexander V.; Olvera de la Cruz, Monica Macromolecules, Vol. 37, Issue 24 https://doi.org/10.1021/ma048519t	journal	November 2004
Charge regularization in phase separating polyelectrolyte solutions Muthukumar, M.; Hua, Jing; Kundagrami, Arindam The Journal of Chemical Physics, Vol. 132, Issue 8 https://doi.org/10.1063/1.3328821	journal	February 2010
Reduction of the glass transition temperature in polymer films: A molecular-dynamics study Varnik, F.; Baschnagel, J.; Binder, K. Physical Review E, Vol. 65, Issue 2 https://doi.org/10.1103/PhysRevE.65.021507	journal	January 2002
Biomimetic Underwater Adhesives with Environmentally Triggered Setting Mechanisms Shao, Hui; Stewart, Russell J. Advanced Materials, Vol. 22, Issue 6 https://doi.org/10.1002/adma.200902380	journal	February 2010
Collapse of flexible polyelectrolytes in multivalent salt solutions Solis, Francisco J.; de la Cruz, Monica Olvera The Journal of Chemical Physics, Vol. 112, Issue 4 https://doi.org/10.1063/1.480763	journal	January 2000
Numerical Solutions of the Complex Langevin Equations in Polymer Field Theory Lennon, Erin M.; Mohler, George O.; Ceniceros, Hector D. Multiscale Modeling & Simulation, Vol. 6, Issue 4 https://doi.org/10.1137/070689401	journal	January 2008
Field-theoretic simulations of polyelectrolyte complexation Popov, Yuri O.; Lee, Jonghoon; Fredrickson, Glenn H. Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 24 https://doi.org/10.1002/polb.21334	journal	January 2007
Thermomechanical continuum representation of atomistic deformation at arbitrary size scales Zhou, Min Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 461, Issue 2063 https://doi.org/10.1098/rspa.2005.1468	journal	August 2005
Complexation in Asymmetric Solutions of Oppositely Charged Polyelectrolytes: Phase Diagram Oskolkov, Nikolay N.; Potemkin, Igor I. Macromolecules, Vol. 40, Issue 23 https://doi.org/10.1021/ma0709304	journal	November 2007
A Water-Borne Adhesive Modeled after the Sandcastle Glue of P. californica Shao, Hui; Bachus, Kent N.; Stewart, Russell J. Macromolecular Bioscience, Vol. 9, Issue 5 https://doi.org/10.1002/mabi.200800252	journal	May 2009
The Surface Tension of Solutions of Electrolytes as a Function of the Concentration. I. A Differential Method for Measuring Relative Surface Tension Jones, Grinnell; Ray, Wendell A. Journal of the American Chemical Society, Vol. 59, Issue 1 https://doi.org/10.1021/ja01280a048	journal	January 1937

Similar Records

Interfacial Tension of Polyelectrolyte Complex Coacervate Phases

Journal Article · Tue Jun 17 00:00:00 EDT 2014 · ACS Macro Letters · OSTI ID:1393976

Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Journal Article · Tue Jul 06 00:00:00 EDT 2021 · Macromolecules · OSTI ID:1815825

Investigation of the interfacial tension of complex coacervates using field-theoretic simulations

Citation Formats

References (52)

Similar Records

Related Subjects