Polymer-modified electrodes Nafion

Yoon el al. [112] reported an all-solid-state sensor for blood analysis. The sensor consists of a set of ion-selective membranes for the measurement of H+, K+, Na+, Ca2+, and Cl. The metal electrodes were patterned on a ceramic substrate and covered with a layer of solvent-processible polyurethane (PU) membrane. However, the pH measurement was reported to suffer severe unstable drift due to the permeation of water vapor and carbon dioxide through the membrane to the membrane-electrode interface. For conducting polymer-modified electrodes, the adhesion of conducting polymer to the membrane has been improved by introducing an adhesion layer. For example, polypyrrole (PPy) to membrane adhesion is improved by using an adhesion layer, such as Nafion [60] or a composite of PPy and Nafion [117],... 

Electrodes obtained by coating Nafion and cellulose acetate on electrode surface or the combination of Nafion/NO selective membranes and nonconducting polymer-modified electrode. 

The surface of a carbon electrode was at first coated with a thin film of an anionic polymer such as sodium poly(styrene-sulfonate) 95) or nafion 96) (thickness thousand A) then the cationic Ru(bpy)2+ was adsorbed in the anionic layer electrostatically. The modification was also made by coating water insoluble polymer pendant Ru(bpy)2 + ( ) from its DMF solution 97). These Ru(bpy) +/polymer modified electrode gave a photoresponse in the MV2+ solution with the Pt counter electrode 95-97) The time-current behaviours induced by irradiation and cutoff of the light under argon are shown in Fig. 28. It is interesting to see that the direction of the photocurrent reversed at the electrode potential of ca. 0.4 V (vs. Ag—AgCl) under... 

H.S. White, J. Leddy and A. Bard, Polymer films on electrodes. 8. Investigation of charge-transfer mechanism in Nation polymer modified electrodes, J. Am. Chem. Soc., 1982, 104, 4811-4817 F.C. Anson, D.N. Blauch, J.-M. Saveant and C.-F. Shu, Ion association and electric field effects on electron hopping in redox polymers. Application to the Os(bpy)33+/2+ couple in Nafion, J. Am. Chem. Soc., 1991, 113, 1922-1932. 

Investigation of charge transport mechanisms in nafion polymer modified electrodes, J.Am.Chem.Soc., 104 4817 (1982). 

More recently the advent of chemically modified electrodes, particularly polymer-modified electrodes, has greatly increased the scope of recognition and preconcentration modes available. For example, nafion [116]... 

Fewer examples are reported for organic electrode reactions some alkyl halides were catalytically reduced at electrodes coated with tetrakis-p-aminophenylporphy-rin carboxylate ions are oxidized at a triarylamine polymer and Os(bipy)3 in a Nafion film catalytically oxidizes ascorbic acid Frequently, modified electrodes fail to give catalytic currents for catalyst substrate combinations that do work in the homogeneous case even when good permeability of the film is proven... 

Research into chemically modified electrodes has led to a number of new ways to build chemical selectivity into films that can be coated onto electrode surfaces. Perhaps the simplest example is the use of the polymer Nafion (see Table 13.2) to make selective electrodes for basic research in neurophysiology [88]. Starting with the pioneering investigations by Ralph Adams, electrochemists have become interested in the electrochemical detection of a class of amine-based neurotransmitters in living organisms. The quintessential example of this class of neurotransmitters is the molecule dopamine, which can be electrochemically oxidized via the following redox reaction ... 

Modified electrodes for this analytical purpose have mostly been formed by electrode adsorption of the mediator systems on the electrode surface or by electropolymerization [24,116]. Recently, for example, NAD(P)H oxidations have been performed on platinum or gold electrodes modified with a monolayer of pyrroloquinoline quinone (PQQ) [117] or on poly(methylene blue)-modified electrodes with different dehydrogenases entrapped in a Nafion film for the amperometric detection of glucose, lactate, malate, or ethanol [118]. In another approach, carbon paste electrodes doped with methylene green or meldola blue together with diaphorase were used for the NADH oxidation [119]. A poly(3-methylthio-phene) conducting polymer electrode was efficient for the oxidation of NADH [120]. By electropolymerization of poly(aniline) in the presence of poly(vinylsulfonate) counterions. 

High temperatures are required to melt the crystalline domains in the high-EW samples and promote dissolution. Martin et have recently found that Nafions with EWs of 1100 and 1200 dissolve in both 50 50 propanol-water and 50 50 ethanol-water, at 250°C and elevated pressure, because the crystallites of the materials are eliminated. McCain and Covitch have also reported a similar dissolution technique. The ionic membrane was chemically converted into the nonionic precursor (sulfonyl fluoride) form prior to the dissolution process. Due to the nonionic nature of the precursor, it dissolves under relatively mild conditions. These dissolution techniques for Nafion polymers provide an important means for preparation of chemically modified electrodes and membranes of any desired geometry. ... 

Recently, several interesting studies of the electrochemical properties of electrodes coated with thin films of Nafion have been reported. These chemically modified electrodes are prepared using low-EW polymers which are alcohol soluble, or using a solution of a 1100-EW polymer which has been dissolved at high pressure and temperature. Electrochemical studies for cations such as the Ru(bpy)3 couple yielded estimates of ionic diffusion coefficients in the polymer films. However, results also indicate that these films are far more porous than conventional Nafion membranes, so it is not possible to compare values directly with those discussed above. 

Studies on various electrodes functionalized by polyelectrolytes have been reported chemiluminescene of Nafion-coated membranes,334 behavior of violo-gen-based chemically modified electrodes,335 and polymer electrodes with incorporated tetrathiafulvalenium in a Nafion membrane.336... 

Application of transition metal hexacyanoferrates for development of biosensors was first announced by our group in 1994 [118]. The goal was to substitute platinum as the most commonly used hydrogen peroxide transducer for Prussian blue-modified electrode. The enzyme glucose oxidase was immobilized on the top of the transducer in the polymer (Nafion) membrane. The resulting biosensor showed advantageous characteristics of both sensitivity and selectivity in the presence of commonly tested reductants, such as ascorbate and paracetamol. 

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