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"Like-charge attraction" between anionic polyelectrolytes: molecular dynamics simulations.

Ferenc Molnar1, Jens Rieger

  • 1BASF Aktiengesellschaft, Polymer Physics, Carl-Bosch Str. 38, 67056 Ludwigshafen, Germany. ferenc.molnar@basf-ag.be

Langmuir : the ACS Journal of Surfaces and Colloids
|January 12, 2005
PubMed
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Like-charge attraction occurs between negatively charged molecules like DNA and proteins. Divalent cations like Ca2+ cause polyanions to attract and precipitate, contrary to prior assumptions.

Area of Science:

  • Physical Chemistry
  • Biophysics
  • Materials Science

Background:

  • Like-charge attraction is observed in biological and industrial polyelectrolyte systems.
  • This phenomenon involves negatively charged macroions (polyanions) attracting each other in the presence of multivalent cations.

Purpose of the Study:

  • To elucidate the atomistic mechanisms governing like-charge attraction using molecular dynamics simulations.
  • To investigate the interaction between sodium polyacrylate (polyanions) and calcium (Ca2+) counterions as an industrially relevant example.

Main Methods:

  • Classical molecular dynamics simulations were employed.
  • The study focused on the interactions of negatively charged carboxylate groups with divalent Ca2+ counterions.

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Main Results:

  • Calcium ions initially associate with individual polyacrylate chains, influencing sodium ion distribution.
  • Shielded polyanions approach and aggregate, leading to precipitation.
  • This aggregation occurs independently of intermolecular Ca2+ bridging, challenging existing theories.

Conclusions:

  • The study reveals that Ca2+ ions mediate like-charge attraction by associating with single polyanion chains.
  • Precipitation is a consequence of shielded polyanions aggregating, not direct Ca2+ bridging.
  • Findings provide new insights into polyelectrolyte behavior and industrial applications.