Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films
Redox polyelectrolyte multilayers have been assembled with use of the layer-by-layer (LBL) deposition technique with cationic poly(allylamine) modified with Os(bpy)2ClPyCHO (PAH-Os) and anionic poly(styrene)sulfonate (PSS) or poly(vinyl)sulfonate (PVS). Different behavior has been observed in the fo...
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todo:paper_00027863_v124_n28_p8490_Calvo2023-10-03T13:53:32Z Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films Calvo, E.J. Wolosiuk, A. Permselectivity Crystals Electrolytes Ionic strength pH effects Polystyrenes Positive ions Quartz Thin films anion cation osmium polyelectrolyte polystyrenesulfonic acid polyvinyl sulfonate unclassified drug vinyl derivative water acidity alkalinity article chemical structure concentration response crystal cyclic potentiometry electrochemistry film mass oxidation reduction potential oxidation reduction reaction pH polymerization reaction analysis structure analysis Electrochemistry Electrolytes Hydrogen-Ion Concentration Kinetics Oxidation-Reduction Permeability Polymers Redox polyelectrolyte multilayers have been assembled with use of the layer-by-layer (LBL) deposition technique with cationic poly(allylamine) modified with Os(bpy)2ClPyCHO (PAH-Os) and anionic poly(styrene)sulfonate (PSS) or poly(vinyl)sulfonate (PVS). Different behavior has been observed in the formal redox potential of the Os(II)/Os(III) couple in the polymer film with cyclic voltammetry depending on the charge of the outermost layer and the electrolyte concentration and pH. The electrochemical quartz crystal microbalance (EQCM) has been used to monitor the exchange of ions and solvent with the external electrolyte during redox switching. At low ionic strength Donnan permselectivity of anions or cations is apparent and the nature of the ion exclusion from the film is determined by the charge of the topmost layer and solution pH. At high electrolyte concentration Donnan breakdown is observed and the osmium redox potential approaches the value for the redox couple in solution. Exchange of anions and water with the external electrolyte under permselective conditions and salt and water under Donnan breakdown have been observed upon oxidation of the film at low pH for the PAH-Os terminating layer. Moreover, at high pH values and with PVS as the terminating layer EQCM mass measurements have shown that cation release was masked by water exchange. Fil:Calvo, E.J. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00027863_v124_n28_p8490_Calvo |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Permselectivity Crystals Electrolytes Ionic strength pH effects Polystyrenes Positive ions Quartz Thin films anion cation osmium polyelectrolyte polystyrenesulfonic acid polyvinyl sulfonate unclassified drug vinyl derivative water acidity alkalinity article chemical structure concentration response crystal cyclic potentiometry electrochemistry film mass oxidation reduction potential oxidation reduction reaction pH polymerization reaction analysis structure analysis Electrochemistry Electrolytes Hydrogen-Ion Concentration Kinetics Oxidation-Reduction Permeability Polymers |
| spellingShingle |
Permselectivity Crystals Electrolytes Ionic strength pH effects Polystyrenes Positive ions Quartz Thin films anion cation osmium polyelectrolyte polystyrenesulfonic acid polyvinyl sulfonate unclassified drug vinyl derivative water acidity alkalinity article chemical structure concentration response crystal cyclic potentiometry electrochemistry film mass oxidation reduction potential oxidation reduction reaction pH polymerization reaction analysis structure analysis Electrochemistry Electrolytes Hydrogen-Ion Concentration Kinetics Oxidation-Reduction Permeability Polymers Calvo, E.J. Wolosiuk, A. Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| topic_facet |
Permselectivity Crystals Electrolytes Ionic strength pH effects Polystyrenes Positive ions Quartz Thin films anion cation osmium polyelectrolyte polystyrenesulfonic acid polyvinyl sulfonate unclassified drug vinyl derivative water acidity alkalinity article chemical structure concentration response crystal cyclic potentiometry electrochemistry film mass oxidation reduction potential oxidation reduction reaction pH polymerization reaction analysis structure analysis Electrochemistry Electrolytes Hydrogen-Ion Concentration Kinetics Oxidation-Reduction Permeability Polymers |
| description |
Redox polyelectrolyte multilayers have been assembled with use of the layer-by-layer (LBL) deposition technique with cationic poly(allylamine) modified with Os(bpy)2ClPyCHO (PAH-Os) and anionic poly(styrene)sulfonate (PSS) or poly(vinyl)sulfonate (PVS). Different behavior has been observed in the formal redox potential of the Os(II)/Os(III) couple in the polymer film with cyclic voltammetry depending on the charge of the outermost layer and the electrolyte concentration and pH. The electrochemical quartz crystal microbalance (EQCM) has been used to monitor the exchange of ions and solvent with the external electrolyte during redox switching. At low ionic strength Donnan permselectivity of anions or cations is apparent and the nature of the ion exclusion from the film is determined by the charge of the topmost layer and solution pH. At high electrolyte concentration Donnan breakdown is observed and the osmium redox potential approaches the value for the redox couple in solution. Exchange of anions and water with the external electrolyte under permselective conditions and salt and water under Donnan breakdown have been observed upon oxidation of the film at low pH for the PAH-Os terminating layer. Moreover, at high pH values and with PVS as the terminating layer EQCM mass measurements have shown that cation release was masked by water exchange. |
| format |
JOUR |
| author |
Calvo, E.J. Wolosiuk, A. |
| author_facet |
Calvo, E.J. Wolosiuk, A. |
| author_sort |
Calvo, E.J. |
| title |
Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| title_short |
Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| title_full |
Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| title_fullStr |
Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| title_full_unstemmed |
Donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| title_sort |
donnan permselectivity in layer-by-layer self-assembled redox polyelectrolye thin films |
| url |
http://hdl.handle.net/20.500.12110/paper_00027863_v124_n28_p8490_Calvo |
| work_keys_str_mv |
AT calvoej donnanpermselectivityinlayerbylayerselfassembledredoxpolyelectrolyethinfilms AT wolosiuka donnanpermselectivityinlayerbylayerselfassembledredoxpolyelectrolyethinfilms |
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1782030738932105216 |