Poly coated electrode

Komori and Nonaka132,133 electrochemically oxidized methyl, isopropyl, n-butyl, isobutyl, r-butyl and cyclohexyl phenyl sulfides (108) and cyclohexyl p-tolyl sulfide (109) to their sulfoxides using a variety of polyamino acid-coated electrodes to obtain the range of e.e. values shown in parentheses. The highest enantiomeric purities were obtained using an electrode doubly coated with polypyrrole and poly(L-valine), an electrode which also proved the most durable of those prepared. 

Several alkyl aryl sulfides were electrochemically oxidized into the corresponding chiral sulfoxides using poly(amino acid)-coated electrodes448. Although the levels of enan-tioselection were quite variable, the best result involved t-butyl phenyl sulfoxide which was formed in 93% e.e. on a platinum electrode doubly coated with polypyrrole and poly(L-valine). Cyclodextrin-mediated m-chloroperbenzoic acid oxidation of sulfides proceeds with modest enantioselectivity44b. 

As described in Section 3 of Chapter 4, the stabilization of n-Si electrode by coating with poly(pyrrole) has attracted much attention. The stabilization of a small bandgap n-semiconductor electrode against oxidation is of great value not only to convert visible light into chemical energy, but also to construct liquid-junction solar cells operated under visible irradiation. The poly(pyrrole) film is usually electropolymerized on the semiconductor electrode dipped in the aqueous solution of pyrrole. The remarkable stabilizing effect of poly(pyrrole) film on polycrystalline n-Si is shown in Fig. 22 67). The photocurrent obtained under irradiation in the aqueous solution of... 

One problem for the coated system is that the film is peeled off after prolonged irradiation. In order to have a more adhesive film, the surface of n-Si was modified with N-(3-trimethoxysilyIpropyl)pyrrole (22). Pyrrole was then electrodeposited on this modified electrode as shown in Eq. (24) 85). The durability of the coated poly(pyrrole) was improved by such a treatment of n-Si surface. The n-Si electrode coated only with poly(pyrrole) gave a declined photocurrent from 6.5 to 1.8 mA cm-2 in less than 18 h, while the poly(pyrrole) coated n-Si treated at first with 22 as Eq. (24) gave a stable photocurrent of 7.6 mA cm-2 for 25 h. When an n-Si electrode was coated with Pt layer before the deposition of poly(pyrrole), the stability of the semiconductor was improved remarkably (ca. 19 days)85b). A power conversion efficiency of 5.5% was obtained with iodide/iodine redox electrolytes. 

Sol-gels containing electroactive species have been used in the development of both amperometric and potentiometric electrodes. Films coated with anionic poly-(dimethyldiallylammonium chloride) (PDMDAAC) and cationic poly(vinylsulfonic acid) were used to concentrate Ru(bpy)3 + and the hexacyanoferrate anion, respectively, for use as amperometric electrodes [208a]. The detection limit by square-wave voltammetry improved by up to 50-fold compared with uncovered electrodes. In Figure 41, curve 1 corresponds to a bare graphite electrode, curve 2 to a sol-gel-covered electrode and curve 3 to a sol-gel-PDMDAAC-modified electrode after 10 min of exposure to Fe(CN)g. ... 

Alkyl aryl sulfides electrochemically oxidized on electrodes whose surfaces were modified by coating them with optically active compounds like camphoric acid [89] and poly(amino acids) [90, 91] afford mixtures of sulfoxides with variable enantiomeric excess. An optical yield of 93% is claimed when f-butyl phenyl sulfide is oxidized at a Pt electrode doubly coated with polypyrrole and poly(L-valine) [91]. 

Chiral Modified Electrode Poly-L-valine coated anode promoted enantioselective oxidation of sulfide to sufoxide in 93 % ee [12]. 

FIGURE 3.3. Schematic representation of the ejection of CP ions associated with the electrochemical reduction of the PVPy/Ru polymer in Fig. 3.1. The metal electrode (Me), coated with a PVPy/Ru film (poly), is immersed in an electrolyte (5). Electrochemical charge transfer is symbolized by e. ... 

The electrochemical polymerization method was used to prepare layers of conductive polymers on electrodes pre-coated with another conductive polymer or using films of a conductive polymer as electrode. This was the method used to prepare a composite of poly acetylene and polypyrrole [150,151] A sandwichlike composite with layers of polypyrrole adhered to polyacetylene was obtained using undoped polyacetylene electrodes. The use of doped polyacetylene induced pyrrole polymerization in the bulk of the film. A strong improvement in the stability of polyacetylene was observed exposure to ambient temperature of 30 days or to water for 20 minutes did not reduce the conductivity of both materials. 

For nonaqueous electrochemistry, lUPAC recommended the use of a redox couple such as ferrocene/ferrocenium ion (Fc/Fc" ) as an internal standard [26]. An alternative to the liquid junction electrode is one based on an entirely solid-state design. Peerce and Bard [27] fabricated such an electrode by coating poly (vinylferrocene) (PVFc) on platinum. The polymer-coated electrode was brought to a 1 1 ratio of ferrocene to ferrocenium by poising the electrode at the PVTc/Fc" half-wave potential (0.39 V vs. SCE). Although this electrode maintained a constant, reproducible potential in deaerated acetonitrile over 21 h, it was unstable in other... 

Fig. 20.38 Illustration of the electric potential distribution (< ) across the interface between a metal electrode (Me) coated with a neutral polymer (poly) film and an electrolyte solution containing ions that are partitioned into the polymer. El, E2, E3 are three applied electrode potentials at which the polymer is neither oxidized nor reduced. The electrical double layers (1) and (2) correspond to two different bulk concentrations of ions in the polymer, d.p. is the distribution potential.

By 1988, a number of devices such as a MOSFET transistor had been developed by the use of poly(acetylene) (Burroughes et al. 1988), but further advances in the following decade led to field-effect transistors and, most notably, to the exploitation of electroluminescence in polymer devices, mentioned in Friend s 1994 survey but much more fully described in a later, particularly clear paper (Friend et al. 1999). The polymeric light-emitting diodes (LEDs) described here consist in essence of a polymer film between two electrodes, one of them transparent, with careful control of the interfaces between polymer and electrodes (which are coated with appropriate films). PPV is the polymer of choice. 

FIGURE 4-18 Permselective coatings flow injection response of a poly(l,2-diaminoben-zene)-coated electrode to the following a, hydrogen peroxide (1 mM) b, ascorbic acid (1 mM) c, uric acid (1 mM) d, L-cysteine (1 mM) and e, control human serum. (Reproduced with permission from reference 63.)... 

Very low asymmetric induction (e.e. 0.3-2.5%) was noted when unsymmetrical sulphides were electrochemically oxidized on an anode modified by treatment with (— )camphoric anhydride or (S)-phenylalanine methyl ester299. Much better results were obtained with the poly(L-valine) coated platinum electrodes300. For example, t-butyl phenyl sulphide was converted to the corresponding sulphoxide with e.e. as high as 93%, when electrode coated with polypyrrole and poly(L-valine) was used. 

Figure 2. Cyclic voltammograms of a poly(2,2 -bithiophene)-coated electrode in acetonitrile containing 0.1 M Bu4NC 04.34 (Reprinted from G. Zotti, C. Schiavon, and S. Zecchin, Irreversible processes in the electrochemical reduction of polythiophenes. Chemical modifications of the polymer and charge-trapping phenomena, Synth. Met. 72 (3) 275-281, 1995, with kind permission from Elsevier Sciences S.A.)...

Theoretical aspects of mediation and electrocatalysis by polymer-coated electrodes have most recently been reviewed by Lyons.12 In order for electrochemistry of the solution species (substrate) to occur, it must either diffuse through the polymer film to the underlying electrode, or there must be some mechanism for electron transport across the film (Fig. 20). Depending on the relative rates of these processes, the mediated reaction can occur at the polymer/electrode interface (a), at the poly-mer/solution interface (b), or in a zone within the polymer film (c). The equations governing the reaction depend on its location,12 which is therefore an important issue. Studies of mediation also provide information on the rate and mechanism of electron transport in the film, and on its permeability. 

ControlW potential electrolyses of dibromostilbenes at poly-7i coated platinum foils gave results similar to those previously observed The electrodes lose... 

Subsequently, a number of reactions at poly-L-valine coated carbon electrodes 237-243) gj.g reported to yield optically active products. Reductions, e.g. of citraconic acid or l,l-dibromo-2,2-diphenylcyclopropane as well as the oxidation of aryl-alkyl sulfides proceeded with chiral induction at such electrodes... 

TaUe 4. Asymmrtric electrochemical reactions at poly-L-valine coated carbon electrodes... 

The bridging polymer is a conducting poly(3-methyIthiophene) or polyaniline and the solid state redox conduction between all electrodes is accomplished by a common coating with poly(ethyleneoxide)/Li" CF3S03- or poly(vinyl alcohol)/ The polyaniline based molecular transistor proved as a very sensitive moisture detector it works well in a dry argon atmosphere but in water saturated argon the device cuts out... 

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