Hydrogen amperometric sensor

V. Lvovich and A. Scheeline, Amperometric sensors for simultaneous superoxide and hydrogen peroxide detection. Anal. Chem. 69, 454-462 (1997). 

R. Garjonyte and A. Malinauskas, Operational stability of amperometric hydrogen peroxide sensors, based on ferrous and copper hexacyanoferrates. Sens. Actuators, B B56, 93—97 (1999). 

There are several species in this reaction that can be used for electrochemical sensing. Detection of proton released from the gluconic acid was used in the poten-tiometric glucose electrode (Section 6.2.1). The amperometric sensor can be based on oxidation of hydrogen peroxide, on reduction of oxygen, or on the oxidation of the reduced form of glucose oxidase itself. 

If one wishes to verify whether the prewave can form the basis for an amperometric sensor, one would preferably dispose of as much information as possible concerning the nature and the properties of this wave. An obvious technique for diagnosis is cyclic voltammetry. Hydrogen peroxide can be oxidised as well as reduced at glassy-carbon electrodes however, the potential ranges within which the reactions occur are situated relatively distant from each other, as can be seen in Fig. 4.3 and Fig. 4.5. 

In this chapter, the development of an amperometric sensor will be explained and discussed. The principle of the analysis method will be based on the results described in Chapter4 this means that use will be made of the oxidation reaction of hydrogen peroxide in the prewave, and that the concentration will be determined using the rate equation. In addition to measurement of the electrical current response, temperature and pH will therefore also be measured. Accordingly, it is interesting to start with an investigation of the temperature influence. 

A. Malinauskas, R. Araminaite, G. Mickeviciute and R. Garjonyte, Evaluation of operational stability of Prussian blue and cobalt hexacyanofer-rate-based amperometric hydrogen peroxide sensors for biosensing application, Mater. Sci. Eng. C, 24 (2004) 513-519. 

Figure 8 is a possible redox cycle occurring in an amperometric sensor for hydrogen peroxide involving enzyme-wiring of a typical enzyme (Horseradish peroxidase, HRP) with polyaniline. HRP immobilized on the electrode surface can be oxidized by H2O2 to compound I that contains an oxyferryl centre with the iron in the ferryl state (Fclv = O), and a porphyrin 7r cation radical, followed by further direct (mediatorless) electroreduction of compound I at the electrode surface to the initial HRP state [106], The electrode is considered as an electron donor. 

Amperometric sensors for hydrogen, nitrous oxides, and carbon dioxide have been developed by modification of the Clark-type electrode (Hanus et al., 1980 Albery and Barron, 1982). 

It is evident from the equation that potentiometric CO2 electrodes as well as amperometric O2 or H2O2 electrodes can be used as transducers. Both potentiometric and amperometric sensors have been covered by a layer of oxalate oxidase protected by a dialysis membrane (Bradley and Rechnitz, 1986 Rahni et al.f 1986a). The sensors had a pH optimum at pH 3.5-4. Diffusion control was reached at 1 U oxalate oxidase per electrode. Oxalate determination was not affected by ascorbic acid or amino acids. The hydrogen peroxide-detecting sensor (Rahni et al., 1986a) has been used to measure oxalate in urine diluted 1 40. 

The above authors coimmobilized choline oxidase and AChE on a nylon net which was fixed to a hydrogen peroxide probe so that the esterase was adjacent to the solution. The apparent activities were 200-400 mU/cm2 for choline oxidase and 50-100 mU/cm2 for AChE. The sensitivity of the sequence electrode for ACh was about 90% of that for choline, resulting in a detection limit of 1 pmol/l ACh. The response time was 1-2 min. The parameters of this amperometric sensor surpass those of potentiometric enzyme electrodes for ACh (see Section 3.1.25). Application to brain extract analysis has been announced. 

Low temperature carbon monoxide sensors based on the reversible carbon monoxide adsorptive poisoning of precious metal electrodes are also being developed by Los Alamos National Laboratory. The addition of metals such as ruthenium to the platinum electrode material greatly improves the hydrogen oxidation kinetics in the presence of CO. An amperometric sensor that senses the CO inhibition of the hydrogen oxidation can be fabricated from a platinum electrode, a proton conductor and a platinum ruthenium alloy electrode. While the... 

Antiochia, R. Lavagnini, I. Magno, F. Electrocatalytic oxidation of dihydronicotinamide adenine dinucleotide with ferrocene carboxylic acid by diaphorase from Clostridium kluveri. Remarks on the kinetic approaches usually adopted. Ekctroanalysis 1999, 11, 129-133. Sanchez, P. D. Ordieres, A. J. M. Garcia, A. G. Blanco, P. T. Peroxidase ferrocene modified carbon paste electrode as an amperometric sensor for the hydrogen-peroxide assay. Ekctroanalysis 1991, 3, 281—285. 

Qian J, Liu Y, Liu H et al. Characterization of regenerated silk fibroin membrane for immobilisation of peroxidase and construction of an amperometric hydrogen peroxide sensor employing phenazine methosulphate as electron shuttle. J Electroanal Chem 1995 397 157-162. 

Amperometric sensors for electroactive compounds Advanced sensor for hydrogen peroxide... 

Y.F. Yang and S.L. Mu, Determination of hydrogen peroxide using amperometric sensor of polyaniline doped with ferrocenesulfonic acid. Biosens. Bioelectron., 21, lA-1% (2005). 

The best-known amperometric sensor is the Clark oxygen cell, developed by Clark in 1956. A wide range of biosensors have been reported in the literature in which the concentration of an enzyme substrate is measured indirectly through the consumption of oxygen by oxidase-catalyzed reactions or, in a similar manner, by the generation of hydrogen peroxide, i.e.,... 

The choline electrode usually consists of an amperometric transducer and immobilized choline oxidase. The most frequently used electrochemical transducers are hydrogen peroxide electrodes (26-28,33-36). The amperometric signal in this case is due to electrooxidation of hydrogen peroxide, which is the co-product of the enzymatic choline oxidation (equation 2). Oxygen amperometric sensors (Qark-type electrodes) have been also used as basic transducers for choline electrode construction (29, 32, 37). The signal in this case is based on the reduction of molecular oxygen which is the co-reactant in reaction (equation 2). Redox mediators hexacyanoferrate (26), ferrocene derivatives (38) and tetracyanoquinodimethane (39) have also been used in the construction of choline electrodes. 

Fig. 1.5 Schematic diagrams of electrochemicai gas sensors (a) amperometric sensor with iiquid eiectroiyte ruid three-eiectrode configurations (b) potentiometric poiymer-based sensor for hydrogen detection (c) mixed-potentiai-type sensor using YSZ-based soiid eiectroiyte and ZnO-Pt electrode (d) chip-type YSZ-based sensor attached with CdO and SnOj eiectrodes (Reprinted with permission from (a, b) Korotcenkov et ai. (2(X)9). Copyright 2009 American Chemicai Society (c) Lu et al. (1996). Copyright 1996 Elsevier and (d) Miura et al. (1998a, b). Copyright 1998 Elsevier)...

Chao Y, Buttner WJ, Yao S, Stetter JR (2005) Amperometric sensor for selective and stable hydrogen measurement. Sens Actuators B 106 784-790... 

Ramesh C, Murugesan N, Krishnaiah MV, Ganesan V, Periaswami GJ (2(X)8) Improved Nafion-based amperometric sensor for hydrogen in argon. J Solid State Electrochem 12(9) 1109-1116 Reemts J, Paris J, Schlettwein D (2004) Electrochemictil growth of gas-sensitive polyaniline thin films across an insulating gap. Thin Solid Films 466 320-325... 

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