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Title: Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory

Abstract

We present small angle neutron scattering (SANS) measurements of deuterium oxide (D2O) solutions of linear and star sodium poly(styrene sulfonate) (NaPSS) as a function of polyelectrolyte concentration. Emphasis is on understanding the dependence of their SANS coherent scattering cross section I(Q) on the molecular architecture of single polyelectrolyte. The key finding is that for a given concentration, star polyelectrolytes exhibit more pronounced characteristic peaks in I(Q), and the position of the first peak occurs at a smaller Q compared to their linear counterparts. Based on a model of integral equation theory, we first compare the SANS experimental I(Q) of salt free polyelectrolyte solutions with that predicted theoretically. Having seen their satisfactory qualitative agreement, the dependence of counterion association behavior on polyelectrolyte geometry and concentration is further explored. Our predictions reveal that the ionic environment of polyelectrolyte exhibits a strong dependence on polyelectrolyte geometry at lower polyelectrolyte concentration. However, when both linear and star polyelectrolytes exceed their overlap concentrations, the spatial distribution of counterion is found to be essentially insensitive to polyelectrolyte geometry due to the steric effect.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [3];  [1]
  1. ORNL
  2. National Institute of Standards and Technology (NIST)
  3. City University of New York (CUNY)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1047026
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
The Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 137; Journal Issue: 2; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; ARCHITECTURE; COHERENT SCATTERING; CROSS SECTIONS; GEOMETRY; HEAVY WATER; INTEGRAL EQUATIONS; NEUTRONS; SCATTERING; SODIUM; SPATIAL DISTRIBUTION; STARS

Citation Formats

Chen, Wei-Ren, Do, Changwoo, Hong, Kunlun, Liu, Yun, Porcar, L., Shew, Chwen-Yang, and Smith, Greg. Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory. United States: N. p., 2012. Web. doi:10.1063/1.4732516.
Chen, Wei-Ren, Do, Changwoo, Hong, Kunlun, Liu, Yun, Porcar, L., Shew, Chwen-Yang, & Smith, Greg. Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory. United States. doi:10.1063/1.4732516.
Chen, Wei-Ren, Do, Changwoo, Hong, Kunlun, Liu, Yun, Porcar, L., Shew, Chwen-Yang, and Smith, Greg. Sun . "Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory". United States. doi:10.1063/1.4732516.
@article{osti_1047026,
title = {Conformational effect on small angle neutron scattering behavior of interacting polyelectrolyte solutions: a perspective of integral equation theory},
author = {Chen, Wei-Ren and Do, Changwoo and Hong, Kunlun and Liu, Yun and Porcar, L. and Shew, Chwen-Yang and Smith, Greg},
abstractNote = {We present small angle neutron scattering (SANS) measurements of deuterium oxide (D2O) solutions of linear and star sodium poly(styrene sulfonate) (NaPSS) as a function of polyelectrolyte concentration. Emphasis is on understanding the dependence of their SANS coherent scattering cross section I(Q) on the molecular architecture of single polyelectrolyte. The key finding is that for a given concentration, star polyelectrolytes exhibit more pronounced characteristic peaks in I(Q), and the position of the first peak occurs at a smaller Q compared to their linear counterparts. Based on a model of integral equation theory, we first compare the SANS experimental I(Q) of salt free polyelectrolyte solutions with that predicted theoretically. Having seen their satisfactory qualitative agreement, the dependence of counterion association behavior on polyelectrolyte geometry and concentration is further explored. Our predictions reveal that the ionic environment of polyelectrolyte exhibits a strong dependence on polyelectrolyte geometry at lower polyelectrolyte concentration. However, when both linear and star polyelectrolytes exceed their overlap concentrations, the spatial distribution of counterion is found to be essentially insensitive to polyelectrolyte geometry due to the steric effect.},
doi = {10.1063/1.4732516},
journal = {The Journal of Chemical Physics},
issn = {0021-9606},
number = 2,
volume = 137,
place = {United States},
year = {2012},
month = {7}
}

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