skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes

Abstract

Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specific interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1394040
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Polymers
Additional Journal Information:
Journal Volume: 6; Journal Issue: 6; Journal ID: ISSN 2073-4360
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; charge density; complex coacervation; ionic strength; multivalent; poly(acrylic acid); poly(allylamine); polyelectrolyte complex

Citation Formats

Perry, Sarah, Li, Yue, Priftis, Dimitrios, Leon, Lorraine, and Tirrell, Matthew. The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes. United States: N. p., 2014. Web. doi:10.3390/polym6061756.
Perry, Sarah, Li, Yue, Priftis, Dimitrios, Leon, Lorraine, & Tirrell, Matthew. The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes. United States. doi:10.3390/polym6061756.
Perry, Sarah, Li, Yue, Priftis, Dimitrios, Leon, Lorraine, and Tirrell, Matthew. Sun . "The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes". United States. doi:10.3390/polym6061756.
@article{osti_1394040,
title = {The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes},
author = {Perry, Sarah and Li, Yue and Priftis, Dimitrios and Leon, Lorraine and Tirrell, Matthew},
abstractNote = {Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specific interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.},
doi = {10.3390/polym6061756},
journal = {Polymers},
issn = {2073-4360},
number = 6,
volume = 6,
place = {United States},
year = {2014},
month = {6}
}

Works referenced in this record:

Multilayered polyelectrolyte assemblies as platforms for the delivery of DNA and other nucleic acid-based therapeutics☆
journal, June 2008


Interfacial Tension of Polyelectrolyte Complex Coacervate Phases
journal, May 2014

  • Qin, Jian; Priftis, Dimitrios; Farina, Robert
  • ACS Macro Letters, Vol. 3, Issue 6
  • DOI: 10.1021/mz500190w

Binodal Compositions of Polyelectrolyte Complexes
journal, August 2010

  • Spruijt, Evan; Westphal, Adrie H.; Borst, Jan Willem
  • Macromolecules, Vol. 43, Issue 15
  • DOI: 10.1021/ma101031t

The present state of affairs with Hofmeister effects
journal, August 2004

  • Kunz, W.; Lo Nostro, P.; Ninham, B. W.
  • Current Opinion in Colloid & Interface Science, Vol. 9, Issue 1-2
  • DOI: 10.1016/j.cocis.2004.05.004

The adhesive properties of coacervated recombinant hybrid mussel adhesive proteins
journal, May 2010


Polyelectrolyte complexes: Bulk phases and colloidal systems
journal, September 2011

  • Gucht, Jasper van der; Spruijt, Evan; Lemmers, Marc
  • Journal of Colloid and Interface Science, Vol. 361, Issue 2
  • DOI: 10.1016/j.jcis.2011.05.080

Viscosity and interfacial properties in a mussel-inspired adhesive coacervate
journal, January 2010

  • Hwang, Dong Soo; Zeng, Hongbo; Srivastava, Aasheesh
  • Soft Matter, Vol. 6, Issue 14
  • DOI: 10.1039/c002632h

Estimation of macromolecule concentrations and excluded volume effects for the cytoplasm of Escherichia coli
journal, December 1991


Hard and soft acids and bases, HSAB, part 1: Fundamental principles
journal, September 1968

  • Pearson, Ralph G.
  • Journal of Chemical Education, Vol. 45, Issue 9
  • DOI: 10.1021/ed045p581

Entropy and enthalpy of polyelectrolyte complexation: Langevin dynamics simulations
journal, April 2006

  • Ou, Zhaoyang; Muthukumar, M.
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2178803

Effects of Polymer and Salt Concentration on the Structure and Properties of Triblock Copolymer Coacervate Hydrogels
journal, February 2013

  • Krogstad, Daniel V.; Lynd, Nathaniel A.; Choi, Soo-Hyung
  • Macromolecules, Vol. 46, Issue 4
  • DOI: 10.1021/ma302299r

Complex coacervation of poly(ethylene-imine)/polypeptide aqueous solutions: Thermodynamic and rheological characterization
journal, May 2013

  • Priftis, Dimitrios; Megley, Katie; Laugel, Nicolas
  • Journal of Colloid and Interface Science, Vol. 398
  • DOI: 10.1016/j.jcis.2013.01.055

Ternary, Tunable Polyelectrolyte Complex Fluids Driven by Complex Coacervation
journal, April 2014

  • Priftis, Dimitrios; Xia, Xiaoxing; Margossian, Khatcher O.
  • Macromolecules, Vol. 47, Issue 9
  • DOI: 10.1021/ma500245j

Phase separation in polyelectrolyte solutions. Theory of complex coacervation
journal, May 1957

  • Overbeek, J. T. G.; Voorn, M. J.
  • Journal of Cellular and Comparative Physiology, Vol. 49, Issue S1
  • DOI: 10.1002/jcp.1030490404

Ideal Mixing in Polyelectrolyte Complexes and Multilayers:  Entropy Driven Assembly
journal, October 2006

  • Bucur, Claudiu B.; Sui, Zhijie; Schlenoff, Joseph B.
  • Journal of the American Chemical Society, Vol. 128, Issue 42
  • DOI: 10.1021/ja064532c

Quantification and rationalization of the higher affinity of sodium over potassium to protein surfaces
journal, October 2006

  • Vrbka, L.; Vondrasek, J.; Jagoda-Cwiklik, B.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 42
  • DOI: 10.1073/pnas.0606959103

Ion hydration: Implications for cellular function, polyelectrolytes, and protein crystallization
journal, February 2006


Complex coacervates as a foundation for synthetic underwater adhesives
journal, September 2011

  • Stewart, Russell J.; Wang, Ching Shuen; Shao, Hui
  • Advances in Colloid and Interface Science, Vol. 167, Issue 1-2
  • DOI: 10.1016/j.cis.2010.10.009

Phase Behavior and Coacervation of Aqueous Poly(acrylic acid)−Poly(allylamine) Solutions
journal, March 2010

  • Chollakup, Rungsima; Smitthipong, Wirasak; Eisenbach, Claus D.
  • Macromolecules, Vol. 43, Issue 5
  • DOI: 10.1021/ma902144k

Interactions between macromolecules and ions: the Hofmeister series
journal, December 2006


Interfacial Energy of Polypeptide Complex Coacervates Measured via Capillary Adhesion
journal, May 2012

  • Priftis, Dimitrios; Farina, Robert; Tirrell, Matthew
  • Langmuir, Vol. 28, Issue 23
  • DOI: 10.1021/la300769d

Zur Lehre von der Wirkung der Salze: Dritte Mittheilung
journal, August 1888

  • Hofmeister, Franz
  • Archiv für Experimentelle Pathologie und Pharmakologie, Vol. 25, Issue 1
  • DOI: 10.1007/BF01838161

Complex coacervate core micelles
journal, March 2009

  • Voets, Ilja K.; de Keizer, Arie; Cohen Stuart, Martien A.
  • Advances in Colloid and Interface Science, Vol. 147-148
  • DOI: 10.1016/j.cis.2008.09.012

Thermodynamic Characterization of Polypeptide Complex Coacervation
journal, October 2012

  • Priftis, Dimitrios; Laugel, Nicolas; Tirrell, Matthew
  • Langmuir, Vol. 28, Issue 45
  • DOI: 10.1021/la302729r

Form and Function in Multilayer Assembly: New Applications at the Nanoscale
journal, August 2004


Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions
journal, March 2010

  • Tagliazucchi, M.; de la Cruz, M. O.; Szleifer, I.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 12
  • DOI: 10.1073/pnas.0913340107

Linear Viscoelasticity of Polyelectrolyte Complex Coacervates
journal, February 2013

  • Spruijt, Evan; Cohen Stuart, Martien A.; van der Gucht, Jasper
  • Macromolecules, Vol. 46, Issue 4
  • DOI: 10.1021/ma301730n

Micellar interpolyelectrolyte complexes
journal, January 2012

  • Pergushov, Dmitry V.; Müller, Axel H. E.; Schacher, Felix H.
  • Chemical Society Reviews, Vol. 41, Issue 21
  • DOI: 10.1039/c2cs35135h

Complex coacervation of proteins and anionic polysaccharides
journal, December 2004

  • de Kruif, Cornelus G.; Weinbreck, Fanny; de Vries, Renko
  • Current Opinion in Colloid & Interface Science, Vol. 9, Issue 5
  • DOI: 10.1016/j.cocis.2004.09.006

Effect of Polyelectrolyte Structure on Protein−Polyelectrolyte Coacervates:  Coacervates of Bovine Serum Albumin with Poly(diallyldimethylammonium chloride) versus Chitosan
journal, November 2007

  • Kayitmazer, A. Basak; Strand, Sabina P.; Tribet, Christophe
  • Biomacromolecules, Vol. 8, Issue 11
  • DOI: 10.1021/bm700645t

Structure and Dynamics of Polyelectrolyte Complex Coacervates Studied by Scattering of Neutrons, X-rays, and Light
journal, May 2013

  • Spruijt, Evan; Leermakers, Frans A. M.; Fokkink, Remco
  • Macromolecules, Vol. 46, Issue 11
  • DOI: 10.1021/ma400132s

Hard and Soft Acids and Bases
journal, November 1963

  • Pearson, Ralph G.
  • Journal of the American Chemical Society, Vol. 85, Issue 22
  • DOI: 10.1021/ja00905a001

Dynamic hydration numbers for biologically important ions
journal, October 2002


Charge density-dependent strength of hydration and biological structure
journal, January 1997


Excluded volume as a determinant of macromolecular structure and reactivity
journal, October 1981