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Title: Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory

Abstract

Here, we provide a theory to quantify the ionic current (iion) in nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. We consider the PE brushes to be modelled by our recently proposed augmented strong stretching theory (SST) model that improves the existing SST models by incorporating the effects of excluded volume interactions and an extended mass action law. Use of such augmented SST for this problem implies that this is the first study on computing iion in PE-brush-grafted nanochannels accounting for the appropriate coupled con guration-electrostatic description of the PE brushes. iion is obtained as functions of PE brush grafting density, medium pH and salt concentration (c), and the density of polyelectrolyte chargeable sites (PECS). For large c, iion increases linearly with c (as for such c, iion becomes independent of the PE charge and is dominated by the bulk mobility and number density of the electrolyte ions), while iion is independent of c at small c (where the EDL electrostatics and the total number of ions in the system is dominated by the hydrogen ions). We further witness an enhancement of iion for smaller pH and larger grafting density at low and moderate c, while there is little to nomore » effect of the PECS density on the ionic current except for weakly grafted brushes at low c. We believe that this study will serve as a theoretical foundation for a large number of applications that are based on the brush-induced modification of the ionic current in a nanochannel.« less

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Maryland, College Park, MD (United States)
  2. Princeton Univ., NJ (United States)
Publication Date:
Research Org.:
Univ. of Maryland, College Park, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595335
Grant/Contract Number:  
SC0017741
Resource Type:
Accepted Manuscript
Journal Name:
Electrophoresis
Additional Journal Information:
Journal Volume: 41; Journal Issue: 7-8; Journal ID: ISSN 0173-0835
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING; ionic current; nanochannel; polyelectrolyte brush; strong stretching theory

Citation Formats

Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, Etha, Sai Ankit, Chen, Guang, and Das, Siddhartha. Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory. United States: N. p., 2019. Web. https://doi.org/10.1002/elps.201900248.
Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, Etha, Sai Ankit, Chen, Guang, & Das, Siddhartha. Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory. United States. https://doi.org/10.1002/elps.201900248
Sachar, Harnoor Singh, Sivasankar, Vishal Sankar, Etha, Sai Ankit, Chen, Guang, and Das, Siddhartha. Sat . "Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory". United States. https://doi.org/10.1002/elps.201900248. https://www.osti.gov/servlets/purl/1595335.
@article{osti_1595335,
title = {Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory},
author = {Sachar, Harnoor Singh and Sivasankar, Vishal Sankar and Etha, Sai Ankit and Chen, Guang and Das, Siddhartha},
abstractNote = {Here, we provide a theory to quantify the ionic current (iion) in nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. We consider the PE brushes to be modelled by our recently proposed augmented strong stretching theory (SST) model that improves the existing SST models by incorporating the effects of excluded volume interactions and an extended mass action law. Use of such augmented SST for this problem implies that this is the first study on computing iion in PE-brush-grafted nanochannels accounting for the appropriate coupled con guration-electrostatic description of the PE brushes. iion is obtained as functions of PE brush grafting density, medium pH and salt concentration (c∞), and the density of polyelectrolyte chargeable sites (PECS). For large c∞, iion increases linearly with c∞ (as for such c∞, iion becomes independent of the PE charge and is dominated by the bulk mobility and number density of the electrolyte ions), while iion is independent of c∞ at small c∞ (where the EDL electrostatics and the total number of ions in the system is dominated by the hydrogen ions). We further witness an enhancement of iion for smaller pH and larger grafting density at low and moderate c∞, while there is little to no effect of the PECS density on the ionic current except for weakly grafted brushes at low c∞. We believe that this study will serve as a theoretical foundation for a large number of applications that are based on the brush-induced modification of the ionic current in a nanochannel.},
doi = {10.1002/elps.201900248},
journal = {Electrophoresis},
number = 7-8,
volume = 41,
place = {United States},
year = {2019},
month = {9}
}

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