Electrochemical polymerization polyanilines

Functionalized conducting monomers can be deposited on electrode surfaces aiming for covalent attachment or entrapment of sensor components. Electrically conductive polymers (qv), eg, polypyrrole, polyaniline [25233-30-17, and polythiophene/23 2JJ-J4-j5y, can be formed at the anode by electrochemical polymerization. For integration of bioselective compounds or redox polymers into conductive polymers, functionalization of conductive polymer films, whether before or after polymerization, is essential. In Figure 7, a schematic representation of an amperomethc biosensor where the enzyme is covalendy bound to a functionalized conductive polymer, eg, P-amino (polypyrrole) or poly[A/-(4-aminophenyl)-2,2 -dithienyl]pyrrole, is shown. Entrapment of ferrocene-modified GOD within polypyrrole is shown in Figure 7. 

Ideal electrochemical polymerization was considered to give ideal linear and conjugated polymeric chains. The real situation is that films electrogenerated from the basic monomers are insoluble and infusible. Only polyaniline films are partially soluble in some solvents. 

Although much less so than pyrrole polymers, indole polymers are beginning to be synthesized and studied as new materials. Electropolymerized films of indole-5-carboxylic acid are well-suited for the fabrication of micro pH sensors and they have been used to measure ascorbate and NADH levels. The three novel pyrroloindoles shown have been electrochemically polymerized, and the polymeric pyrrolocarbazole has similar physical properties to polyaniline. 

The use of conjugated polymer as membranes to separate various liquid mixtures has been reported in the literature [19,20], From those, polyaniline (PANi) is one of the most interesting and studied conjugated polymers. Polyaniline is usually prepared by direct oxidative polymerization of aniline in the presence of a chemical oxidant, or by electrochemical polymerization on different electrode materials [21,22], The possible interconversions between different oxidation states and protonated and depronated states [23], figure 4, make this material remarkable for different purposes. Under most conditions, PANi... 

Apart from the insulating polymeric matrices, conductive polymers such as polypyrrole and polyaniline have been used as nanocomposite electrodes by chemical or electrochemical polymerization [13, 17, 116, 117]. Such materials provide high conductivity and stability. However, the use of insulating polymers can be more advantageous than the conductive polymers when employed in cyclic voltammetry. 

Similar approach has also been taken by Ferain and Legras [133,137,138] and De Pra et al. [139] to produce nanostructured materials based on the template of the membrane with etched pores. Polycarbonate film was also of use as the base membrane of the template, and micro- and nanopores were formed by precise control of the etching procedure. Their most resent report showed the successful formation of ultrasmall pores and electrodeposited materials of which sizes were as much as 20 nm [139]. Another attractive point of these studies is the deposited materials in the etched pores. Electrochemical polymerization of conjugated polymer materials was demonstrated in these studies, and the nanowires based on polypyrrole or polyaniline were formed with a fairly cylindrical shape reflecting the side wall structure of the etched pores. Figure 10 indicates the shape of the polypyrrole microwires with their dimension changes by the limitation of the thickness of the template. 

Kuwabata etal. [161] have prepared, via electrochemical polymerization on Au(lll), SAMs comprising aminoben-zenethiol and 3-aminophenethylthiol units. Polymerization of aminoben-zenethiol required the use of ortho and meta isomers in the molar ratio of 1 1, whereas, in contrast, 3-amino-phenethylthiol was easily polymerized as a pure substance. The monolayers obtained exhibited electrochemical properties very similar to those of polyaniline and their derivatives. 

A special feature of the polyanilines (28) is the fact that they are prepared by electrochemical polymerization in the presence of a chiral dopant (Scheme 1). Polymers prepared in the presence of enantiomeric counterions give rise to CD spectra with completely different signs. These signals are lost completely upon deprotonation of the polymer. This suggests that the helicity is maintained by hydrogenbonding and/or electrostatic interactions with the counterions. 

Interesting supports are the polymeric materials, notwithstanding their thermal instability at high temperatures. In the electrocatalysis field, the use of polypyrrole, polythiophene and polyaniline as heteropolyanion supports was reported [2]. The catalytically active species were introduced, in this case, via electrochemical polymerization. Hasik et al. [3] studied the behavior of polyaniline supported tungstophosphoric acid in the isopropanol decomposition reaction. The authors established that a HPA molecular dispersion can be attained via a protonation reaction. The different behavior of the supported catalysts with respect to bulk acid, namely, predominantly redox activity versus acid-base activity, was attributed to that effect. 

It is well Renown that organic conducting polymers such as polypyrrole, polythiophene, and polyaniline can be deposited on electrodes by means of electrochemical polymerization, which is successfully carried out through oxidation of monomers in the solution (14). 

The processability of certain CEPs has been utilized in the construction of microsystems, particularly miniature sensor systems. For example, simply dip-coating connecting platinum wires with a polyaniline formulation produces a useful humidity sensor.133 CEPs can also be screen-printed or ink-jet-printed to produce the complex shapes needed for various devices. Electrodeposition of CEPs is also a popular processing method, and this technique is compatible with conventional MEMS fabrication, where lithography and etching can be used to prepattern metal electrodes. Subsequent deposition of CEP by electrochemical polymerization produces the CEP microdevice.129... 

Conducting polymers are popular in the development of gas- and liquid-phase sensors, with polypyrrole and polyaniline being the most widely used [3], Common features of materials used to fabricate conducting polymers include the ability to make them through either chemical or electrochemical polymerization or the ability to change their conductivity through oxidation or reduction. 

Completely different monomers were called for. Before long, three of today s workhorses had been identified pyrrole, aniline and thiophene. In Japan, Yamamoto [38] and in Germany, Kossmehl [39] synthesized polythiophene doped with pentafluoroarsenate. At the same time, the possibilities of electrochemical polymerization were recognized. At the IBM Lab in San Jose, Diaz used oxidative electrochemical polymerization to prepare polypyrrole [40] and polyaniline. [41] Electrochemical synthesis forms the polymer in its doped state, with the counter-ion (usually an anion) incorporated from the electrolyte. This mechanism permits the selection of a wider range of anions, including those which are not amenable to vapor-phase processes, such as perchlorate and tetra-fluoroborate. Electrochemical doping also overcomes an issue associated with dopants... 

L. M. Santos, J. Ghilane, C. Fave, P.-C. Lacaze, H. Randriamahazaka, L. M. Abrantes, and J.-C. Lacroix, Electrografting polyaniline on carbon through the electroreduction of diazonium salts and the electrochemical polymerization of aniline, J. Phys. Chem. C, 112, 16103-16109 (2008). 

Kan s researeh group also investigated the effect of alcohols on the electrochemical polymerization of aniline at a constant potential of 0.8 V (vs. SCE) [61]. They found that the presence of alcohols favors formation of nanofibers. This is attributed to hydrogen bonding between alcohols and polyaniline chains, which results in the polymer chains being pushed apart [62]. 

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