The entropy of water in swelling PGA/PAH polyelectrolyte multilayersElectronic supplementary information (ESI) available: Experimental section including details about used materials, film preparation and measurement techniques; influence of ionic strength and anion species on the magnitude of the electrochemical multilayer swelling (Fig. S1); influence of the ionic strength on the magnitude of the electrochemical multilayer swelling for KCl and TBACl (Fig. S2); simplified schematic of the home-b
We investigated the thermodynamical properties of water exchanged in poly( l -glutamic acid)/poly(allylamine)hydrochloride (PGA/PAH) polyelectrolyte multilayers containing ferrocyanide. Oxidation/reduction of the ferrocyanide in the multilayer caused a reversible swelling/contraction of the film due...
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Language | English |
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03.01.2014
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Abstract | We investigated the thermodynamical properties of water exchanged in poly(
l
-glutamic acid)/poly(allylamine)hydrochloride (PGA/PAH) polyelectrolyte multilayers containing ferrocyanide. Oxidation/reduction of the ferrocyanide in the multilayer caused a reversible swelling/contraction of the film due to the uptake/release of counter ions and water. We used electrochemical quartz crystal microbalance and electrochemical microcalorimetry to correlate the amount of water with the accompanying entropy changes during electrochemical swelling of the multilayer for a series of different anions at different concentrations. The number of exchanged water molecules was highly dependent on the ionic strength and the type of anion in the buffer solution. However, the entropy change per exchanged water molecule was found to be independent of these two parameters. The water molecules in the polyelectrolyte multilayer have reduced the entropy compared to that of bulk water ( −1 J mol
−1
K
−1
). A comparison of hydration entropies for free polyelectrolytes and PGA/PAH multilayers suggests that such systems are mainly stabilized by water release during multilayer construction.
The entropy of water in polyelectrolyte multilayers is determined by combining electrochemical quartz crystal microbalance and electrochemical microcalorimetry. |
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AbstractList | We investigated the thermodynamical properties of water exchanged in poly(
l
-glutamic acid)/poly(allylamine)hydrochloride (PGA/PAH) polyelectrolyte multilayers containing ferrocyanide. Oxidation/reduction of the ferrocyanide in the multilayer caused a reversible swelling/contraction of the film due to the uptake/release of counter ions and water. We used electrochemical quartz crystal microbalance and electrochemical microcalorimetry to correlate the amount of water with the accompanying entropy changes during electrochemical swelling of the multilayer for a series of different anions at different concentrations. The number of exchanged water molecules was highly dependent on the ionic strength and the type of anion in the buffer solution. However, the entropy change per exchanged water molecule was found to be independent of these two parameters. The water molecules in the polyelectrolyte multilayer have reduced the entropy compared to that of bulk water ( −1 J mol
−1
K
−1
). A comparison of hydration entropies for free polyelectrolytes and PGA/PAH multilayers suggests that such systems are mainly stabilized by water release during multilayer construction.
The entropy of water in polyelectrolyte multilayers is determined by combining electrochemical quartz crystal microbalance and electrochemical microcalorimetry. |
Author | Kuhn, Frank M Bickel, Katrin R Reichenbach, Judith Schuster, Rolf Zambelli, Tomaso Vörös, János Zahn, Raphael |
AuthorAffiliation | Karlsruhe Institute of Technology Laboratory of Biosensors and Bioelectronics ETH Zurich Institute for Biomedical Engineering Institute for Physical Chemistry |
AuthorAffiliation_xml | – name: ETH Zurich – name: Karlsruhe Institute of Technology – name: Institute for Biomedical Engineering – name: Institute for Physical Chemistry – name: Laboratory of Biosensors and Bioelectronics |
Author_xml | – sequence: 1 givenname: Raphael surname: Zahn fullname: Zahn, Raphael – sequence: 2 givenname: Katrin R surname: Bickel fullname: Bickel, Katrin R – sequence: 3 givenname: Tomaso surname: Zambelli fullname: Zambelli, Tomaso – sequence: 4 givenname: Judith surname: Reichenbach fullname: Reichenbach, Judith – sequence: 5 givenname: Frank M surname: Kuhn fullname: Kuhn, Frank M – sequence: 6 givenname: János surname: Vörös fullname: Vörös, János – sequence: 7 givenname: Rolf surname: Schuster fullname: Schuster, Rolf |
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DOI | 10.1039/c3sm52489b |
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Notes | Electronic supplementary information (ESI) available: Experimental section including details about used materials, film preparation and measurement techniques; influence of ionic strength and anion species on the magnitude of the electrochemical multilayer swelling (Fig. S1); influence of the ionic strength on the magnitude of the electrochemical multilayer swelling for KCl and TBACl (Fig. S2); simplified schematic of the home-built cell used for the electrochemical microcalorimetry measurements (Fig. S3); potential, current and temperature transients for a typical microcalorimetric experiment (Fig. S4). See DOI 10.1039/c3sm52489b |
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References_xml | – issn: 1963 publication-title: Advances in Electrochemistry and Electrochemical Engineering doi: Agar – issn: 2003 publication-title: Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials doi: Decher Schlenoff – issn: 1980 issue: vol. 2 publication-title: Electrochemical methods: fundamentals and applications doi: Bard Faulkner – issn: 2010 publication-title: CRC handbook of chemistry and physics: a ready-reference book of chemical and physical data doi: Haynes – issn: 1997 publication-title: Ion Properties doi: Marcus – issn: 1960 publication-title: An introduction to statistical thermodynamics doi: Hill – issn: 2008 issue: vol. 134 end-page: p 30-38 publication-title: Progress in Colloid and Polymer Science: Surface and Interfacial Forces - From Fundamentals to Applications doi: Kolasi ska Krastev Gutberlet Warszy ski |
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Title | The entropy of water in swelling PGA/PAH polyelectrolyte multilayersElectronic supplementary information (ESI) available: Experimental section including details about used materials, film preparation and measurement techniques; influence of ionic strength and anion species on the magnitude of the electrochemical multilayer swelling (Fig. S1); influence of the ionic strength on the magnitude of the electrochemical multilayer swelling for KCl and TBACl (Fig. S2); simplified schematic of the home-b |
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