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Issue 7, 2018
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Chain conformation of poly(acrylic acid)-graft-poly(ethylene oxide)-graft-dodecyl in solution: an anomalous counter-ions condensation

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Abstract

A dielectric spectroscopy study on a polyelectrolyte in aqueous solutions, which contains hydrophobic groups in part of the side chains poly(acrylic acid)-graft-poly(ethylene oxide)-graft-dodecyl (PAA-g-PEO-g-dodecyl) is reported. A refined double layer polarization model was proposed to analyze the double dielectric relaxations in the dielectric spectra. Various electrical and structural parameters of the copolymers were obtained. Besides the crossover concentration, another turning point around 4 mg mL−1 was identified through the analysis of all the dielectrical parameters including dielectric increment, relaxation time and correlation length. According to the scaling relationship between the correlation length and concentration, a necklace-like structure was predicted. In addition, 4 mg mL−1 was proven to be the transition point between string-controlling with bead-controlling structure of the chains. In addition, the fraction of effective charges on the chains was illustrated by Ito's counter-ions fluctuation theory, as well as its linear dependence relationship with the zeta potential. Meanwhile, the counter-ions condensation behavior was consistent with the avalanche-like trend, which was predicted by theory for a hydrophobic polyelectrolyte with a necklace conformation. The results demonstrated that the electrostatic interactions were the main driving force of the necklace-like structure with pendant globules when the string-controlling structure was below 4 mg mL−1. While hydrophobic interactions are the main driving force of the structure of bead-controlling above 4 mg mL−1.

Graphical abstract: Chain conformation of poly(acrylic acid)-graft-poly(ethylene oxide)-graft-dodecyl in solution: an anomalous counter-ions condensation

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Publication details

The article was received on 26 Sep 2017, accepted on 02 Jan 2018 and first published on 02 Jan 2018


Article type: Paper
DOI: 10.1039/C7SM01931A
Citation: Soft Matter, 2018,14, 1130-1141
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    Chain conformation of poly(acrylic acid)-graft-poly(ethylene oxide)-graft-dodecyl in solution: an anomalous counter-ions condensation

    X. Zhou and K. Zhao, Soft Matter, 2018, 14, 1130
    DOI: 10.1039/C7SM01931A

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