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Tunable Synthesis of Prussian Blue in Exponentially Growing Polyelectrolyte Multilayer Films

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Centre National de la Recherche Scientifique, Unité Propre de Recherche 22, Institut Charles Sadron, 23 rue du Loess, BP 84047, 67034 Strasbourg Cedex 2, France
Institut National de la Santé et de la Recherche Médicale, Unité 977, 11 rue Humann, 67085 Strasbourg Cedex, France
§ Université de Strasbourg, Faculté de Chirurgie Dentaire, 1 Place de l’Hôpital, 67000 Strasbourg, France
Centre National de la Recherche Scientifique - Université de Strasbourg, Unité Mixte de Recherche 7504, Institut de Physique et Chimie des Matériaux de Strasbourg, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France
*Corresponding author. Phone: +33 (0)3 90 24 32 58; fax: +33 (0)3 90 24 33 79; e-mail: [email protected] (V.B.). Phone: +33 (0)3 88 41 40 12; e-mail: [email protected] (P.S.).
Cite this: Langmuir 2009, 25, 24, 14030–14036
Publication Date (Web):August 13, 2009
Copyright © 2009 American Chemical Society

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Abstract Image

Polyelectrolyte multilayer (PEM) films have become very popular for surface functionalization and the design of functional architectures such as hollow polyelectrolyte capsules. It is known that properties such as permeability to small ionic solutes are strongly dependent on the buildup regime of the PEM films. This permeability can be modified by tuning the ionization degree of the polycations or polyanions, provided the film is made from weak polyelectrolytes. In most previous investigations, this was achieved by playing on the solution pH either during the film buildup or by a postbuildup pH modification. Herein we investigate the functionalization of poly(allylamine hydrochloride)/poly(glutamic acid) (PAH/PGA) multilayers by ferrocyanide and Prussian Blue (PB). We demonstrate that dynamic exchange processes between the film and polyelectrolyte solutions containing one of the component polyelectrolyte allow one to modify its Donnan potential and, as a consequence, the amount of ferrocyanide anions able to be retained in the PAH/PGA film. This ability of the film to be a tunable reservoir of ferrocyanide anions is then used to produce a composite film containing PB particles obtained by a single precipitation reaction with a solution containing Fe3+ cations in contact with the film. The presence of PB in the PEM films then provides magnetic as well as electrochemical properties to the whole architecture.

Part of the “Langmuir 25th Year: Self-assembled polyelectrolyte multilayers: structure and function” special issue.

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Evolution of the oxidation and reduction charge of FCIV-filled MPS−(PAH/PGA)10 films depending on the number of measurement cycles and the duration of the rest time between successive scanning cycles, the influence of the post-treatment of a PEI−(PGA/PAH)10 film with PGA or PAH solutions on its ATR-FTIR spectrum, and CV and ATR-FTIR spectrum of PEM films containing PB. Evaluation of the number of available amino groups in an MPS−(PAH/PGA)10 film. This material is available free of charge via the Internet at

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Cited By

This article is cited by 31 publications.

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  12. Vincent Ball. Phase Diagram of Sodium Hexametaphosphate and Poly(allylamine hydrochloride) Mixtures and In Situ Monitoring of Step-by-Step Deposition in This Polyelectrolyte System. Macromolecular Chemistry and Physics 2015, 216 (1) , 85-94.
  13. Felix A. Plamper. Changing Polymer Solvation by Electrochemical Means: Basics and Applications. 2014, 125-212.
  14. Vincent Ball. Donnan potential of polyelectrolyte multilayer films made from poly-l-glutamic/polyallylamine hydrochloride and the stability of hexacyanoferrate retained in the films. Physical Chemistry Chemical Physics 2013, 15 (38) , 16249.
  15. E. Guzmán, M. Ruano, R.G. Rubio, F. Ortega. Polyelectrolyte assemblies for drug storage and delivery: multilayers, nanocapsules and multicapsules. 2013, 94-145.
  16. Vincent Ball. Organic and Inorganic Dyes in Polyelectrolyte Multilayer Films. Materials 2012, 5 (12) , 2681-2704.
  17. Andre G. Skirtach, Dmitry V. Volodkin, Helmuth Möhwald. Remote and Self‐Induced Release from Polyelectrolyte Multilayer Capsules and Films. 2012, 925-950.
  18. Ernesto. J. Calvo. Electrochemically Active LbL Multilayer Films: From Biosensors to Nanocatalysts. 2012, 1003-1038.
  19. Marc Michel, Vincent Ball. Diffusion of Nanoparticles and Biomolecules into Polyelectrolyte Multilayer Films: Towards New Functional Materials. 2012, 691-710.
  20. Raphael Zahn, Géraldine Coullerez, János Vörös, Tomaso Zambelli. Effect of polyelectrolyte interdiffusion on electron transport in redox-active polyelectrolyte multilayers. Journal of Materials Chemistry 2012, 22 (22) , 11073.
  21. Qinglin Sheng, Ruixiao Liu, Jianbin Zheng. Prussian blue nanospheres synthesized in deep eutectic solvents. Nanoscale 2012, 4 (21) , 6880.
  22. Julien Petersen, Marc Michel, Valérie Toniazzo, David Ruch, Guy Schmerber, Dris Ihiawakrim, Dominique Muller, Aziz Dinia, Vincent Ball. Atmospheric plasma polymer films as templates for inorganic synthesis to yield functional hybrid coatings. RSC Advances 2012, 2 (26) , 9860.
  23. Mihaela Delcea, Helmuth Möhwald, André G. Skirtach. Stimuli-responsive LbL capsules and nanoshells for drug delivery. Advanced Drug Delivery Reviews 2011, 63 (9) , 730-747.
  24. Eduardo Guzmán, Hernán Ritacco, Francisco Ortega, Ramón G. Rubio. Evidence of the influence of adsorption kinetics on the internal reorganization of polyelectrolyte multilayers. Colloids and Surfaces A: Physicochemical and Engineering Aspects 2011, 384 (1-3) , 274-281.
  25. Philippe Lavalle, Jean-Claude Voegel, Dominique Vautier, Bernard Senger, Pierre Schaaf, Vincent Ball. Dynamic Aspects of Films Prepared by a Sequential Deposition of Species: Perspectives for Smart and Responsive Materials. Advanced Materials 2011, 23 (10) , 1191-1221.
  26. Wei Qi, Li Duan, Junbai Li. Fabrication of glucose-sensitive protein microcapsules and their applications. Soft Matter 2011, 7 (5) , 1571-1576.
  27. Cosette Betscha, Vincent Ball. Large distribution in the Donnan potential of hexacyanoferrate anions permeating in and partially dissolving (PAH-HA)n polyelectrolyte multilayer films. Soft Matter 2011, 7 (5) , 1819.
  28. Eduardo Guzmán, Raquel Chuliá-Jordán, Francisco Ortega, Ramón G. Rubio. Influence of the percentage of acetylation on the assembly of LbL multilayers of poly(acrylic acid) and chitosan. Physical Chemistry Chemical Physics 2011, 13 (40) , 18200.
  29. Raphael Zahn, János Vörös, Tomaso Zambelli. Swelling of electrochemically active polyelectrolyte multilayers. Current Opinion in Colloid & Interface Science 2010, 15 (6) , 427-434.
  30. Riadh Zouari, Marc Michel, Jean Di Martino, Vincent Ball. Production of free standing composite membranes or of patterned films after sol–gel reactions in an exponential layer-by-layer architecture. Materials Science and Engineering: C 2010, 30 (8) , 1291-1297.
  31. Mario Tagliazucchi, Federico J. Williams, Ernesto J. Calvo. Metal-ion responsive redox polyelectrolyte multilayers. Chemical Communications 2010, 46 (47) , 9004.

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