Redox Driven Swelling of Layer-by-layer Enzyme−Polyelectrolyte Multilayers

Forzani, Erica; Pérez, Manuel; Teijelo, M. López; Calvo, Ernesto J.

doi:10.1021/la0264419

Cited by 47 publications

(70 citation statements)

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“…It is known that the thickness can be affected by changes in the solution salt concentration (salt-induced swelling) [30,44] and in the oxidation state of the film (redox-driven swelling). [45][46][47] The magnitude of these processes in similar systems to the osmium pyridine-bipyridine derivatized poly(allylamine) (PAH-Os)/poly(vinyl sulfonate) (PVS) films studied here is less than about 30%. [30,[44][45][46][47] Since the error that would be introduced in D app by neglecting a swelling of this magnitude [48] is much smaller than the variations observed due to the nature of the outmost layer and changes in ionic strength, we will assume a constant film thickness as determined in water: [14] 1.5 nm for Au/3-mercapto-1-propanesulfonate (MPS)/PAH-Os, 10.2 nm for Au/MPS/(PAH-Os/ PVS) 4 PAH-Os, and 11.5 nm for Au/MPS/(PAH-Os/PVS) 5 .…”

Section: Model Parametersmentioning

confidence: 81%

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Tagliazucchi

Calvo

2010

ChemPhysChem

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The redox switching kinetics, that is, charge transfer and transport in layer-by-layer-deposited electroactive polyelectrolyte multilayers is systematically studied with variable-scan-rate cyclic voltammetry. The experiments are performed with films finished in the redox polycation (an osmium pyridine-bipyridine derivatized polyallylamine, PAH-Os) and the polyanion (polyvinyl sulfonate, PVS), in solutions of different electrolyte concentrations. A modified diffusion model is developed to account for the experimentally observed dependence of the average peak potential with the scan rate. This model is able to describe both the redox peak potential and the current, providing information on the electron-transfer rate constants and the diffusion coefficient for the electron-hopping mechanism. While the former does not vary with the ionic strength or the nature of the outmost layer, polyanion-capped films present an electron-hopping diffusion coefficient at low ionic strength that is three orders of magnitude smaller than that for PAH-Os-capped films. The effect is offset at high ionic strength. We discuss the possible causes of the effect and the important consequences for electrochemical devices built by layer-by-layer self-assembly, such as amperometric biosensors or electrochromic devices.

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Section: Model Parametersmentioning

confidence: 81%

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Tagliazucchi

Calvo

2010

ChemPhysChem

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“…Ellipsometric angles W and D were determined from reflection-induced changes in the state of polarization of linearly polarized light, which are related to the ellipsometric ratio [46,47]:…”

Section: Ellipsometric Measurementsmentioning

confidence: 99%

“…some polycation-polyanion interaction are exchanged by the redox anion FeðCNÞ 4À 6 and the redox cation, OsðbipyÞ 3þ 3 as studied by cyclic voltammetry and electrochemical impedance spectroscopy [10]. Redox polyelectrolyte multilayers (PEM) self-assembled LbL have been reported with different redox groups attached to polymers: viologen [11][12][13][14], ferrocene [15][16][17][18][19][20][21][22], osmium bipyridyl [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39], sulfonated polyaniline [40], polythiophene [41], cytochrome c [42], myoglobin [43], polyoxo-metalates [44], etc. Hodak et al introduced in 1997 the use of a ferrocene covalently bound to poly-(allylamine) as a molecular wire to connect electrically the enzyme glucose oxidase in a layer by layer selfassembled (LbL-SA) multilayer to generate an electrical signal in response to molecular recognition of b-D-glucose.…”

Section: Introductionmentioning

confidence: 99%

“…Hodak et al introduced in 1997 the use of a ferrocene covalently bound to poly-(allylamine) as a molecular wire to connect electrically the enzyme glucose oxidase in a layer by layer selfassembled (LbL-SA) multilayer to generate an electrical signal in response to molecular recognition of b-D-glucose. Following this first reagentless electrocatalytic active structure based on the successive alternate deposition of ferrocene modified poly(allylamine) cation and anionic glucose oxidase enzyme (GOx), an important number of authors reported similar self-contained redox mediators and enzyme strategy in amperometric biosensors [23][24][25][26][27][28][29][30][33][34][35][36][37]39,[45][46][47][48][49][50][51][52].…”

Section: Introductionmentioning

confidence: 99%

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Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers

Tagliazucchi

Calvo

2007

Journal of Electroanalytical Chemistry

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“…To name a few, multilayer films containing a ferrocene-derivatized polyallylamine hydrochloride (PAH-Fc) [185] and an osmium complex-derivatized polyallylamine hydrochlorides (PAHOs) [186] can swell by 10% of initial film thickness upon oxidation of the Os(II). Multilayer capsules with layered anionic and cationic polyferrocenylsilanes to form multilayer capsules expand and increase their permeability upon chemical oxidation of the ferrocene units [187].…”

Section: Specific Molecular Interactionmentioning

confidence: 99%

Layer‐by‐Layer Self‐Assembled Multilayer Stimuli‐Responsive Polymeric Films

Zhai

2011

Handbook of Stimuli‐Responsive Materials

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IntroductionMultilayer polymeric films fabricated through the layer-by-layer (LBL) self-assembly technique are able to integrate stimuli-responsive materials into the films through various intermolecular interactions. The ease of the fabrication process and the excellent control of the film composition and morphology, combined with the capability of coating substrates conformally, offers a wide range of multilayer films that change film properties such as permeability, wettability, color, and solubility upon external stimuli. This chapter reviews the methods of building LBL multilayer films and the approaches to control the structures of the films. These smart films provide numerous applications in controlled drug release, sensing, energy generation, and flow regulation with their unique response to external stimuli including pH and temperature change, photo irradiation, application of electrical fields, and specific molecular interactions.Stimuli-responsive coatings, also known as smart coatings, are able to change their properties upon external stimuli including temperature, pH, salt concentration, light, presence of specific molecules, and other factors. The capability of changing surface behavior in an accurate and predictable manner has generated numerous applications ranging from chemical sensing, separations, and drug delivery to various bioapplications. To name a few, smart coatings with tunable hydrophilic/hydrophobic wettability have been used in the development of microand nanofluidic devices, self-cleaning and antifog surfaces, and sensor devices [1-3]. Photochemical-responsive coatings have been applied to build a surface that releases nitric oxide [4] over nanometer length scales for photochemotherapeutic applications, and a surface that can be photoactivated for spatiotemporal control of cell adhesion during cell cultivation [5,6]. The control of the properties of these smart coatings can be achieved through the stimuli-responsive materials forming self-assembled monolayers (SAMs) and polymer films. Among various approaches to fabricate responsive polymer films, multilayered polymer films, generally referred as polyelectrolyte multilayer (PEM) films, fabricated through the LBL assembly technique, have been proven to be effective smart coatings with Handbook of Stimuli-Responsive Materials. Edited by Marek W. Urban

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Redox Driven Swelling of Layer-by-layer Enzyme−Polyelectrolyte Multilayers

Cited by 47 publications

References 65 publications

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Charge Transport in Redox Polyelectrolyte Multilayer Films: The Dramatic Effects of Outmost Layer and Solution Ionic Strength

Surface charge effects on the redox switching of LbL self-assembled redox polyelectrolyte multilayers

Layer‐by‐Layer Self‐Assembled Multilayer Stimuli‐Responsive Polymeric Films

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