Sensor electrocatalytic

Chen, Q., Wang, J., Rayson, G., Tian, B., and Lin, Y., Sensor array for carbohydrates and amino acids based on electrocatalytic modified electrodes, Anal. Chem., 65, 251, 1993. 

Special electrochemical sensors that operate on the principle of the voltammetric cell have been developed. The area of chemically modified solid electrodes (CMSEs) is a rapidly growing field, giving rise to the development of new electroanalytical methods with increased selectivity and sensitivity for the determination of a wide variety of analytes [490]. CMSEs are typically used to preconcentrate the electroactive target analyte(s) from the solution. The use of polymer coatings showing electrocatalytic activity to modify electrode surfaces constitutes an interesting approach to fabricate sensing surfaces useful for analytical purposes [491]. 

Sensors based on the electrocatalytic oxidation of NO by a modified layer (Ir02, palladium metalloporphyrin modified electrodes). 

Electrochemical Reaction/Transport. Electrochemical reactions occur at the electrode/electrolyte interface when gas is brought to the electrode surface using a small pump. Gas diffuses through the electrode structure to the electrode/electrolyte interface, where it is electrochemically reacted. Some parasitic chemical reactions can also occur on the electrocatalytic surface between the reactant gas and air. To achieve maximum response and reproducibility, the chemical combination must be minimized and controlled by proper selection of catalyst sensor potential and cell configuration. For CO, water is required to complete the anodic reaction at the sensing electrode according to the following reaction ... 

The enhancement of electrochemical reactions usually occurs at modified electrode surfaces. The large NP surface area facilitates oxidation or reduction of small molecules at the electrode. For example, Niwa et al. modified a carbon film electrode with electrocatalytic platinum NPs to create a sensitive H2C>2 sensor.62 Co-sputtering of carbon and platinum produces platinum NPs of 2.5 nm diameter embedded in a carbon matrix. The platinum NPs catalyze the oxidation of H2O2 at the electrode... 

Since the pioneering work of Lane and Hubbard, there have been numerous examples of using chemisorption to modify electrode surfaces. For example, Anson and his coworkers have investigated chemisorption of various aromatic systems onto carbon electrodes [12]. In this case, n-electron density is shared between the electrode and the adsorbate molecule. Examples of electroactive molecules that have been used to modify electrode surfaces via this approach are shown in Table 13.1 [8]. It is of interest to note that from the very beginning, there was considerable interest in modifying electrode surfaces with biochemical substances (Table 13.1). This is because such modified electrodes seemed to be likely candidates for use in electrocatalytic processes and biochemical sensors (see Section V). 

Electrocatalytic groups such as porphyrins and phthalocyanines that act as supramolecular hosts for different metals and mimic the active sites of various proteins are commonly used in amperometric sensors [66,67]. A biomimetic sensor based on an artificial enzyme or synzyme has been demonstrated [68]. The artificial enzyme used in this study was a synthetic polymer (quaternised polyethyleneimine containing 10% primary amines) which decarboxylated oxaloacetate. The product carbon dioxide was detected potentiometrically via a gas membrane electrode. 

Porphyrins are often employed in sensors on account of their ability to act as cation hosts and, with a suitable metal ion coordinated, as redox catalysts. Electropolymerised poly(metalloporphyrin)s have been used as potentiometric anion-selective electrodes [131] and as amperometric electrocatalytic sensors for many species including phenols [132], nitrous oxide [133] and oxygen [134]. Panasyuk et al. [135] have electropolymerised [nickel-(protoporphyrin IX)dimethylester] (Fig. 18.10) on glassy carbon in the presence of nitrobenzene in an attempt to prepare a nitrobenzene-selective amperometric sensor. Following extraction of the nitrobenzene the electrode was exposed to different species and cyclic voltammetric measurements made. A response was observed at the reduction potential of nitrobenzene (the polyporphyrin film acts only to accumulate the analyte and not in a catalytic fashion). Selectivity for nitrobenzene compared with w-nitroaniline and o-nitroto-luene was enhanced compared with an untreated electrode, while a glassy carbon-... 

Figure 21. (A) The assembly of an integrated nitrate sensor electrode by the cross-linking of a microperoxidase-11-nitrate reductase (cytochrome-dependent, EC 1.9.6.1) affinity complex on an Au electrode. (B) Cyclic voltammograms of the integrated MP-ll-NR monolayer-modified Au electrode (roughness factor ca. 15). (a) 0.1 M phosphate buffer, pH 7.0 (b) in the presence of KNO3, 20 mM. Potential scan rate, 5 mV s . Inset electrocatalytic cathodic currents [E = —0.6 V vs. SCE) transduced by the modified electrode at different concentrations of KNO3. Measurements were performed under argon.

Recently, de novo-synthesized four-helix polypeptides were applied to mimic functions of cytochrome b and to tailor layered cross-linked electrocatalytic electrodes. A four-helix bundle de novo protein (14728 Da) that includes four histidine units in the respective A -helices was assembled on Au electrodes (Figure 22A). Two units of Fe(III)-protoporphyrin IX were reconstituted into the assembly to yield a vectorial electron-transfer cascade [157]. The de novo-synthesized protein assembly forms affinity complexes with the cytochrome-dependent nitrate reductase (NR) and with Co(II) protoporphyrin IX-reconstituted myoglobin [158]. The resulting layered complex of Fe(III) de novo protein-NR or Fe(lll)-de novo protein-Co(II)-reconstituted myoglobin was cross-linked with glutaric dialdehyde to yield electrically contacted electrocatalytic electrodes. The Fe(lll)-de novo protein-NR electrode assembly was applied for the electrocatalyzed reduction NO3 to NOt" and acted as an amperometric sensor (Figure 22B). The Fe(III)-de novo... 

Electrocatalytic dopants (heteropolyanions) have also been incorporated into conducting polymers with a view to developing sensors for detection of nitrite (45a) or nitrogen monoxide (45b). 

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