Separation of poly(acrylic acid) salts according to topology using capillary electrophoresis in the critical conditions
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RESEARCH PAPER
Separation of poly(acrylic acid) salts according to topology using capillary electrophoresis in the critical conditions Alison R. Maniego & Dale Ang & Yohann Guillaneuf & Catherine Lefay & Didier Gigmes & Janice R. Aldrich-Wright & Marianne Gaborieau & Patrice Castignolles
Received: 10 April 2013 / Revised: 30 April 2013 / Accepted: 8 May 2013 # Springer-Verlag Berlin Heidelberg 2013
Abstract Branching was detected in polyacrylates synthesised through radical polymerization via solutionstate NMR, while inconsistencies have been reported for the determination of the molar mass of hydrophilic polyacrylates using aqueous-phase and organic-phase sizeexclusion chromatography. In this work, poly(sodium acrylate)s, PNaAs, of various topologies were separated for the first time using free-solution capillary electrophoresis (CE). Free-solution CE does not separate the PNaAs by their molar mass, similarly to separations by liquid chromatography in the critical conditions, rather by different topologies (linear, star branched, and hyperbranched). The electrophoretic mobility of PNaAs increases as the degree of branching decreases. Separation is shown to be not only by the topology but also by the end groups as expected for a
separation in the critical conditions: replacing a relatively bulky nitroxide end group with hydrogen atom yielded a higher electrophoretic mobility. This novel method, capillary electrophoresis in the critical conditions enabled, for the first time, the separation of hydrophilic polyacrylates according to their topology (branching) and their chain ends. This will allow meaningful and accurate characterization of their branched topologies as well as molar masses and progress in for advanced applications such as drug delivery or flocculation. Keywords Poly(acrylic acid) . Branching . Topology . Capillary electrophoresis . Chain end analysis
Introduction Published in the topical collection Separation and Characterization of Natural and Synthetic Macromolecules with guest editors Albena Lederer and Peter J. Schoenmakers. Electronic supplementary material The online version of this article (doi:10.1007/s00216-013-7059-y) contains supplementary material, which is available to authorized users. A. R. Maniego : D. Ang : P. Castignolles (*) University of Western Sydney (UWS), Australian Centre for Research on Separation Sciences (ACROSS), School of Science and Health, Parramatta campus, Locked Bag 1797, Penrith, NSW 2751, Australia e-mail: [email protected] A. R. Maniego : D. Ang : J. R. Aldrich-Wright : M. Gaborieau University of Western Sydney (UWS), School of Science and Health, Nanoscale Organisation and Dynamics group, Locked Bag 1797, Penrith, NSW 2751, Australia Y. Guillaneuf : C. Lefay : D. Gigmes Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR 7273, 13397, Marseille, France
Water-soluble polyacrylates represent an important type of industrial polymer which is found in many applications ranging from commodity use to high-value materials [1]. In particular,
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