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Open AccessArticle

Influence of Polycation Composition on Electrochemical Film Formation

1
Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, 52056 Aachen, Germany
2
Department of Biomedical Engineering-FB40, University of Groningen, University Medical Center Groningen, A. Deusinglaan 1, 9713 AV Groningen, The Netherlands
3
DWI Leibniz-Institute for Interactive Materials, RWTH Aachen University, Forckenbeckstr. 50, 52056 Aachen, Germany
*
Author to whom correspondence should be addressed.
Polymers 2018, 10(4), 429; https://doi.org/10.3390/polym10040429
Received: 12 March 2018 / Revised: 4 April 2018 / Accepted: 5 April 2018 / Published: 12 April 2018
(This article belongs to the Special Issue Microgels and Hydrogels at Interfaces)
The effect of polyelectrolyte composition on the electrodeposition onto platinum is investigated using a counterion switching approach. Film formation of preformed polyelectrolytes is triggered by oxidation of hexacyanoferrates(II) (ferrocyanide), leading to polyelectrolyte complexes, which are physically crosslinked by hexacyanoferrate(III) (ferricyanide) ions due to preferential ferricyanide/polycation interactions. In this study, the electrodeposition of three different linear polyelectrolytes, namely quaternized poly[2-(dimethylamino)ethyl methacrylate] (i.e., poly{[2-(methacryloyloxy)ethyl]trimethylammonium chloride}; PMOTAC), quaternized poly[2-(dimethylamino)ethyl acrylate] (i.e., poly{[2-(acryloyloxy)ethyl]trimethylammonium chloride}; POTAC), quaternized poly[N-(3-dimethylaminopropyl)methacrylamide] (i.e., poly{[3-(methacrylamido)propyl]trimethylammonium chloride}; PMAPTAC) and different statistical copolymers of these polyelectrolytes with N-(3-aminopropyl)methacrylamide (APMA), are studied. Hydrodynamic voltammetry utilizing a rotating ring disk electrode (RRDE) shows the highest deposition efficiency DE for PMOTAC over PMAPTAC and over POTAC. Increasing incorporation of APMA weakens the preferred interaction of the quaternized units with the hexacyanoferrate(III) ions. At a sufficient APMA content, electrodeposition can thus be prevented. Additional electrochemical quartz crystal microbalance measurements reveal the formation of rigid polyelectrolyte films being highly crosslinked by the hexacyanoferrate(III) ions. Results indicate a different degree of water incorporation into these polyelectrolyte films. Hence, by adjusting the polycation composition, film properties can be tuned, while different chemistries can be incorporated into these electrodeposited thin hydrogel films. View Full-Text
Keywords: polyelectrolyte; gel; electrodeposition; interface; electrostatic interactions; thin films; hydrodynamic voltammetry polyelectrolyte; gel; electrodeposition; interface; electrostatic interactions; thin films; hydrodynamic voltammetry
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MDPI and ACS Style

Schneider, S.; Janssen, C.; Klindtworth, E.; Mergel, O.; Möller, M.; Plamper, F. Influence of Polycation Composition on Electrochemical Film Formation. Polymers 2018, 10, 429.

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