Modeling of ionization and conformations of starlike weak polyelectrolytes

F. Uhlik, P. Kosovan, Z. Limpouchova, K. Prochazka, O.V. Borisov, F.A.M. Leermakers

Research output: Contribution to journalArticleAcademicpeer-review

31 Citations (Scopus)

Abstract

The target of this work is to study conformational properties of starlike polyelectrolytes with pH-sensitive (annealed) dissociation in salt-free solutions. We confront hybrid Monte Carlo (HMC) simulations with computationally less expensive approximate numerical self-consistent field (SCF) calculations and with analytical theories. We demonstrate when the mean-field results are reliable and their advantage over MC in terms of efficiency can be exploited and when not. In the interior of the star, where inter-arm interactions dominate over intra-arm ones, the mean-field approximation works well and SCF agrees with the MC results. Intra-arm interactions dominate at star periphery, and their role is underestimated by the mean field. Here, conformations and dissociation resemble those of linear polyelectrolytes. Consequently, the dissociation profile along the chain contour is qualitatively different between MC and SCF. Comparison of the two methods and a distinction between intra-arm and inter-arm contributions to interactions enables us to understand the transition in behavior from linear to starlike chain topology.
Original languageEnglish
Pages (from-to)4004-4016
Number of pages12
JournalMacromolecules
Volume47
DOIs
Publication statusPublished - 2014

Keywords

  • monte-carlo simulations
  • consistent-field theory
  • branched polyelectrolytes
  • titrating polyelectrolytes
  • annealed polyelectrolytes
  • poly(acrylic acid)
  • charge-distribution
  • aqueous-solutions
  • polymers
  • brushes

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