Ferrocene electrode modification

However, because of the mostly very slow electron transfer rate between the redox active protein and the anode, mediators have to be introduced to shuttle the electrons between the enzyme and the electrode effectively (indirect electrochemical procedure). As published in many papers, the direct electron transfer between the protein and an electrode can be accelerated by the application of promoters which are adsorbed at the electrode surface [27], However, this type of electrode modification, which is quite useful for analytical studies of the enzymes or for sensor applications is in most cases not stable and effective enough for long-term synthetic application. Therefore, soluble redox mediators such as ferrocene derivatives, quinoid compounds or other transition metal complexes are more appropriate for this purpose. 

The redox reactions for supported BLMs containing vinylferrocene as an electron mediator have been investigated using cyclic voltammetry. The results have shown the following, (i) Ferrocene can be very easily immobilized in the lipid bilayer on the surface of a metallic wire (s-BLM) system. This demonstrates that the s-BLM system offers a novel approach to electrode modification by simple immobilization of compounds within BLM. (ii) Ferrocene in a BLM increases the sensitivity to the potassium ferri/ferrocyanide ion by about two orders of magnitude in comparison to that of the platinum electrode [79]. 

Poly(ionic liquid) brushes with terminated ferrocene units acted similarly, while the interfacial resistance was probed by hexacyanoferrate [457]. Chemical and electrochemical switching of local pH at an electrode-grafted poly(vinyl pyridine) brush again allowed modulation of hexacyanoferrate chemistiy (Fig. 43) [458]. Octacyanomolybdate was used as catalyst for the oxidation of ascorbic acid [459]. Even heteropolyanions (Keggin ions) could be entrapped in polymer films electrochemicaUy [460]. Further, thermoresponsive or pH-responsive cationic copolymer films modulated the hexacyanoferrate or ferrocenedicarboxyUc acid electrochemistry by temperature or variatimi of pH and perchlorate concentration, respectively [461-463]. Besides these complexes with cationic polyelectrolyte films, electroactive cationic counterions (e.g., the europium couple) interacted with anionic networks [464]. Similarly, copper ions within a PAA matrix [367] allowed the construction of actuators [465]. Besides these binary systems (poly-electrolyte/electroactive counterions), multiresponsive electrode modification with an interpenetrating gel network of poly(acrylic) acid and poly(diethyl acrylamide) allowed the modulation of hexacyanoferrate electrochemistry [368]. 

Ferrocenyl-based polymers are established as useful materials for the modification of electrodes, as electrochemical biosensors, and as nonlinear optical systems. The redox behavior of ferrocene can be tuned by substituent effects and novel properties can result for example, permethylation of the cyclopentadienyl rings lowers the oxidation potential, and the chaige transfer salt of decamethylfer-rocene with tetracyanocthylene, [FeCpJ]" (TCNE], is a ferromagnet below = 4.8 K, and electrode surfaces modified with a pentamethylferrocene derivative have been used as sensors for cytochrome c These diverse properties have provided an added impetus to studies on ferrocene dendrimers. 

The second topic of this chapter is the role of coordination compounds in advancing electrochemical objectives, particularly in the sphere of chemically modified electrodes. This involves the modification of the surface of a metallic or semiconductor electrode, sometimes by chemical reaction with surface groups and sometimes by adsorption. The attached substrate may be able to ligate, or it may be able to accept by exchange some electroactive species. Possibly some poetic licence will be allowed in defining such species since many interesting data have been obtained with ferrocene derivatives thus these organometallic compounds will be considered coordination compounds for the purpose of this chapter. 

If (23) is selected as the dihalosilane, a convenient way of modifying the nickel surface is available.64 The electrochemical properties of the treated nickel electrode are very similar to those of a similarly derivatized platinum electrode for example, both are equally effective in the elec-trocatalytic oxidation-reduction of solution ferrocene. Normally oxidation of the nickel surface would be a competing process ultimately rendering the electrode passive. The surface modification clearly eliminates this problem and opens up the possibility of using surface modified inexpensive metals as electrodes. 

J. Razumiene, V. Gureviien, A. Vilkanauskyt, L. Marcinkeviien, I. Bach-matova, R. Mekys and V. Laurinaviius, Improvement of screen-printed carbon electrodes by modification with ferrocene derivative, Sens. Actuators B Chem., 95 (2003) 378-383. 

Figure 2. Low-resolution XPS spectra of a pyrolytic graphite electrode surface. Key A, prior to modification B, following a l-h 02 rf plasma treatment C, after reduction with LiAlHi D, after modification with cyanuric chloride E, after attachment of hydroxymethyl ferrocene and F, following electrolysis in pH 7 phosphate buffer.

An electrochemical OP sensor by the nonenzymatic route was reported based on chemical modification of the surface of a gold electrode with ferrocene derivative (Fc). For this purpose, the gold electrode was modified with dithioFc derivative to form an aminoFc-monolayer-modified electrode (Khan et al, 2007). The principle of operation of the aminoFc-modified electrode for OP sensing is that chloro-or cyano-substitued OP compounds covalently bind to aminoFc moieties, by which the redox potential of the surface-confined Fc can be altered. In fact, ca. 110 and 60 mV shifts in the redox potential were observed, suggesting a possible use of the sensors for detecting OPs from the potential shifts. 

Figure 6.29 shows, as an example, the effect of surface modification on the sta-bihty of sihcon electrode in an aqueous solution. The bare sihcon surface is quickly passivated in aqueous solution under illumination. Coating the electrode with a layer of either ferrocene or polypyrrole gives an improvement in the stabihty. The stability is further improved by a two-layer coating of ferrocene/polypyrrole as shown in Fig. 6.29. 

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