Biosensor ferrocene mediated

Di Gleiia K, Hill HAO, McNeil CJ, Green MJ (1986) Homogeneous ferrocene mediated amperometiic biosensors. Anal Chem 58 1203-1205... 

Scheme 2. Principle of the ferrocene-mediated thermal glucose biosensor, Aq indicates the heat produced in the reaction...

First ferrocene-mediated amperometric glucose biosensor by Cass et al. [135]. The work led to the development of the first electronic blood glucose measuring system which was commercialized by MediSense Inc. (later bought by Abbott Diagnostics) in 1987. 

Vidal, J.C., E. Garcia, and J.R. Castillo. 2002. Development of a platinized and ferrocene-mediated cholesterol amperometric biosensor based on electropolymerization of polypyrrole in a flow system. Anal Sci 18 (5) 537. 

Enzyme sensors are based primarily on the immobilization of an enzyme onto an electrode, either a metallic electrode used in amperometry (e.g., detection of the enzyme-catalyzed oxidation of glucose) or an ISE employed in potentiometry (e.g., detection of the enzyme-catalyzed liberation of hydronium or ammonium ions). The first potentiometric enzyme electrode, which appeared in 1969 due to Guilbault and Montalvo [140], was a probe for urea with immobilized urease on a glass electrode. Hill and co-workers [141] described in 1986 the second-generation biosensor using ferrocene as a mediator. This device was later marketed as the glucose pen . The development of enzyme-based sensors for the detection of glucose in blood represents a major area of biosensor research. 

The second-generation 02" biosensors are mainly based on the electron transfer of SOD shuttled by surface-confined or solution-phase mediators, as shown in Scheme 2(b). In 1995, Ohsaka et al. found that methyl viologen could efficiently shuttle the electron transfer between SOD and the glassy carbon electrode and proposed that such a protocol could be useful for developing 02 biosensors [125], Recently, Endo et al. reported an 02, biosensor based on mediated electrochemistry of SOD [148], In that case, ferrocene-carboxaldehyde was used as the mediator for the redox process of SOD. The as-developed 02 biosensor showed a high sensitivity, reproducibility, and durability. A good linearity was obtained in the range of 0 100 pM. In the flow cell system, tissue-derived 02 was measured. 

Attempts to reduce interference and minimize the effect of variations in oxygen tension have resulted in the development of biosensors with improved linear ranges which operate at lower electrode potentials. They incorporate artificial electron acceptors, called mediators, to transfer electrons from the flavoenzyme (e.g. glucose oxidase) to the electrode and thus are not dependent on oxygen. Ferrocene (bis(i75-cyclopentadienyl)iron) and its derivatives are examples of redox mediators for flavoenzymes. The reaction now becomes... 

As far as the use of ferrocene molecules as amperometric sensors is concerned, they have found wide use as redox mediators in the so-called enzymatic electrodes, or biosensors. These are systems able to determine, in a simple and rapid way, the concentration of substances of clinical and physiological interest. The methodology exploits the fact that, in the presence of enzyme-catalysed reactions, the electrode currents are considerably amplified.61 Essentially it is an application of the mechanism of catalytic regeneration of the reagent following a reversible charge transfer , examined in detail in Chapter 2, Section 1.4.2.5 ... 

Several variants of the biosensor in Scheme 5 have been proposed. One is a CPE containing at its tip a paste of graphite powder loaded with HRP and ferrocene ([Cp Fe(II) Cp]) mediator, which is further covered with a cellulose acetate film coated with Nafion. The biosensor is mounted on a FIA system in a three-electrode setup, as working electrode at a potential of 4-100 mV vs. SCSE and a Pt counterelectrode. The LOD (SNR 6) for H2O2 is 200 fmol (20 p,L injection of 10 nM solution), with linearity up to 25 In... 

Biosensors constructed for ethanol and D-glucose measurements in beverages were built using ferrocene compounds as electron transfer mediators between the coenzyme PQQ of immobilized enzymes glucose (GDH) and alcohol (ADH) dehydrogenases and a carbon electrode surface <2003JOM(668)83>. 

An alternative biosensor system has been developed by Hart et al. [44] which involves the use of the NAD+-dependent GDH enzyme. The first step of the reaction scheme involves the enzymatic reduction of NAD+ to NADH, which is bought about by the action of GDH on glucose. The analytical signal arises from the electrocatalytic oxidation of NADH back to NAD+ in the presence of the electrocatalyst Meldola s Blue (MB), at a potential of only 0Y. Biosensors utilising this mediator have been reviewed elsewhere [1,17]. Razumiene et al. [45] employed a similar system using both GDH and alcohol dehydrogenase with the cofactor pyrroloquinoline quinone (PQQ), the oxidation of which was mediated by a ferrocene derivative. 

L.S. Bean, L.Y. Heng, B.M. Yamin and M. Ahmad, Photocurable ferrocene-containing poly(2-hydroxyl ethyl methacrylate) films for mediated amperometric glucose biosensor, Thin Solid Films, 477 (2005) 104-110. 

Perhaps the original hope for these polymers was that they would act simultaneously as immobilisation matrix and mediator, facilitating electron transfer between the enzyme and electrode and eliminating the need for either O2 or an additional redox mediator. This did not appear to be the case for polypyrrole, and in fact while a copolymer of pyrrole and a ferrocene modified pyrrole did achieve the mediation (43), the response suggested that far from enhancing the charge transport, the polypyrrole acted as an inert diffusion barrier. Since these early reports, other mediator doped polypyrroles have been reported (44t45) and curiosity about the actual role of polypyrrole or any other electrochemically deposited polymer, has lead to many studies more concerned with the kinetics of the enzyme linked reactions and the film transport properties, than with the achievement of a real biosensor. 

Electron-Mediated Biosensor. Electropolymerization of 1,3-diaminobenzene (1,3-DAB), followed by adsorption of l,r-dimethylferrocene (1,1 -DMF), and immobilization of glucose oxidase, results in an easily and quickly (<2 h) constructed glucose biosensor with excellent linearity and stability (>3 months). Figure 5 shows a proposed schematic of the sensing layer consisting of film/mediator/enzyme. The ferrocene is depicted as circles... 

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