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Title: Effect of calcium ions on the interactions between surfaces end-grafted with weak polyelectrolytes

Abstract

We study the interactions between two planar surfaces end-tethered with poly(acrylic acid) polymers in electrolyte solutions containing calcium ions, using a molecular theory. We found that by adding divalent calcium ions to an aqueous solution of monovalent ions leads to a dramatic reduction in the size and range of effective interactions between the two polymer layers. This is caused by the formation of favorable calcium bridges, i.e., complexes of one calcium ion and two carboxylic acid monomers, that reduce the effective charge of the polymer layers and, at sufficient calcium ion concentrations, can cause the polymer layers to collapse. For calcium ion concentrations above approximately 1 mM, the repulsions between the opposing end-grafted surfaces disappear and attractions occur. These attractions are correlated with the occurrence of interlayer divalent calcium bridges and do not occur for poly(acrylic acid) layers in contact with reservoir solutions containing only monovalent ions. This result indicates the suitability of divalent calcium ions to control and change the interaction range and strength, which is a useful property that is desirable in the design of stimuli-responsive nanomaterials.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Biomedical Engineering, Dept. of Chemistry, and Chemistry of Life Processes Inst.
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566650
Alternate Identifier(s):
OSTI ID: 1460128
Grant/Contract Number:  
SC0000989
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 16; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); solar (photovoltaic); bio-inspired; charge transport; mesostructured materials; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Nap, Rikkert J., and Szleifer, Igal. Effect of calcium ions on the interactions between surfaces end-grafted with weak polyelectrolytes. United States: N. p., 2018. Web. doi:10.1063/1.5029377.
Nap, Rikkert J., & Szleifer, Igal. Effect of calcium ions on the interactions between surfaces end-grafted with weak polyelectrolytes. United States. doi:10.1063/1.5029377.
Nap, Rikkert J., and Szleifer, Igal. Fri . "Effect of calcium ions on the interactions between surfaces end-grafted with weak polyelectrolytes". United States. doi:10.1063/1.5029377. https://www.osti.gov/servlets/purl/1566650.
@article{osti_1566650,
title = {Effect of calcium ions on the interactions between surfaces end-grafted with weak polyelectrolytes},
author = {Nap, Rikkert J. and Szleifer, Igal},
abstractNote = {We study the interactions between two planar surfaces end-tethered with poly(acrylic acid) polymers in electrolyte solutions containing calcium ions, using a molecular theory. We found that by adding divalent calcium ions to an aqueous solution of monovalent ions leads to a dramatic reduction in the size and range of effective interactions between the two polymer layers. This is caused by the formation of favorable calcium bridges, i.e., complexes of one calcium ion and two carboxylic acid monomers, that reduce the effective charge of the polymer layers and, at sufficient calcium ion concentrations, can cause the polymer layers to collapse. For calcium ion concentrations above approximately 1 mM, the repulsions between the opposing end-grafted surfaces disappear and attractions occur. These attractions are correlated with the occurrence of interlayer divalent calcium bridges and do not occur for poly(acrylic acid) layers in contact with reservoir solutions containing only monovalent ions. This result indicates the suitability of divalent calcium ions to control and change the interaction range and strength, which is a useful property that is desirable in the design of stimuli-responsive nanomaterials.},
doi = {10.1063/1.5029377},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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Cited by: 4 works
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