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Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong

Harnoor Singh Sachar1, Vishal Sankar Sivasankar1, Sai Ankit Etha1

  • 1Department of Mechanical Engineering, University of Maryland, College Park, MD, USA.

Electrophoresis
|September 22, 2019
PubMed
Summary

This study quantifies ionic current in nanochannels with pH-responsive polyelectrolyte brushes using an advanced theory. Results show current depends on pH, salt concentration, and brush density, offering insights for nanochannel applications.

Keywords:
ionic currentnanochannelpolyelectrolyte brushstrong stretching theory

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Nanochannels with pH-responsive polyelectrolyte (PE) brushes are crucial for tunable ionic transport.
  • Existing models for ionic current in such systems lack a coupled configuration-electrostatic description of PE brushes.
  • Accurate modeling is needed to understand and predict ionic current modulation by PE brushes.

Purpose of the Study:

  • To develop a theory quantifying ionic current in nanochannels grafted with pH-responsive PE brushes.
  • To incorporate excluded volume interactions and an extended mass action law into PE brush modeling.
  • To investigate the influence of PE brush grafting density, pH, salt concentration, and chargeable site density on ionic current.

Main Methods:

  • Utilized a recently proposed augmented strong stretching theory (SST) model for PE brushes.
  • Incorporated excluded volume interactions and an extended mass action law into the SST model.
  • Derived theoretical expressions for ionic current as a function of system parameters.

Main Results:

  • Ionic current (I) increases linearly with salt concentration (Cs) for large Cs, becoming independent of PE charge.
  • Ionic current (I) is independent of salt concentration (Cs) at small Cs, dominated by hydrogen ions.
  • Enhanced ionic current (I) observed for lower pH and higher grafting density at low/moderate Cs; PECS density has minimal effect except for weakly grafted brushes.

Conclusions:

  • The augmented SST model provides the first coupled configuration-electrostatic description for PE brushes in nanochannels.
  • The study quantifies ionic current, revealing dependencies on pH, Cs, and grafting density.
  • This theoretical framework is foundational for applications involving brush-modified ionic current in nanochannels.