Potentiometric glucose electrodes

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. 

Enzyme electrodes with amperometric indication have certain advantages over potentiometric sensors, chiefly because the product of the enzymic reaction is consumed at the electrode and thus the response time is decreased. For this reason, the potentiometric glucose enzyme electrode, based on reaction (8.1) followed by the reaction of HjO, with iodide ions sensed by an iodide ISE [39], has not found practical use. 

How analytical methods deal with interferences is one of the more ad hoc aspects of method validation. There is a variety of approaches to studying interference, from adding arbitrary amounts of a single interferent in the absence of the analyte to establish the response of the instrument to that species, to multivariate methods in which several interferents are added in a statistical protocol to reveal both main and interaction effects. The first question that needs to be answered is to what extent interferences are expected and how likely they are to affect the measurement. In testing blood for glucose by an enzyme electrode, other electroactive species that may be present are ascorbic acid (vitamin C), uric acid, and paracetamol (if this drug has been taken). However, electroactive metals (e.g., copper and silver) are unlikely to be present in blood in great quantities. Potentiometric membrane electrode sensors (ion selective electrodes), of which the pH electrode is the... 

On-wafer membrane deposition and patterning is an important aspect of the fabrication of planar, silicon based (bio)chemical sensors. Three examples are presented in this paper amperometric glucose and free chlorine sensors and a potentiometric ISRET based calcium sensitive device. For the membrane modified ISFET, photolithographic definition of both inner hydrogel-type membrane (polyHEMA) and outer siloxane-based ion sensitive membrane, of total thickness of 80 pm, has been performed. An identical approach has been used for the polyHEMA deposition on the free chlorine sensor. On the other hand, the enzymatic membrane deposition for a glucose electrode has been performed by either a lift-off technique or by an on-chip casting. 

In order to maintain the advantage of the microfabrication approach which is intended for a reproducible production of multiple devices, parallel development of membrane deposition technology is of importance. Using modified on-wafer membrane deposition techniques and commercially available compounds an improvement of the membrane thickness control as well as the membrane adhesion can be achieved. This has been presented here for three electrochemical sensors - an enzymatic glucose electrode, an amperometric free chlorine sensor and a potentiometric Ca + sensitive device based on a membrane modified ISFET. Unfortunately, the on-wafer membrane deposition technique could not yet be applied in the preparation of the glucose sensors for in vivo applications, since this particular application requires relatively thick enzymatic membranes, whilst the lift-off technique is usable only for the patterning of relatively thin membranes. 

Third-Generation Glucose Electrodes Potentiometric Urea Elearode... 

Enzymes are often employed in the chemical layer to impart the selectivity needed. We saw an example of this in Chapter 13 when discussing potentiometric enzyme electrodes. An example of an amperometric enzyme electrode is the glucose electrode, illustrated in Figure 15.4. The enzyme glucose oxidase is immobilized in a gel (e.g., acrylamide) and coated on the surface of a platinum wire cathode. The gel also contains a chloride salt and makes contact with silver-silver chloride ring to complete the electrochemical cell. Glucose oxidase enzyme catalyzes the aerobic oxidation of glucose as follows ... 

Many potentiometric en2yme electrodes for widely different analyte species can be prepared merely by choosing the appropriate ISE transducer and immobilized enzymatic reagent. Table 5 summarizes the enzymes and ISEs/gas sensors used to construct biosensors for a number of important biomolecules, ranging from urea and creatinine to amino acids, nucleotides, and even glucose and penicillin. In the... 

Cholesterol is de mined using an ampoometric microbial electrode [235]. In contrast, glucose is determined using a potentiometric bacterial electrode, employing the reduction of lipoic acid in the presence of Escherichia coli [236]. The latter is based on bacterial growth, and the response time is very long, between 1 and 2 hours. 

Lvova et al. [100] Caffeine, catechines, sugar, amino acid L-arginine Natural coffee, black tea and different sorts of green teas Glucose oxidase/with glutaraldehyde and BSA, then covered with an aromatic polyurethane membrane Carbon paste screen-printed electrodes/ potentiometric (different active components on each of 30 sensors to construct an array) Iron hexacyanoferrate Prussian Blue, Fein[Fen(CN)6]3... 

Another approach is the use of the potentiometric principle with planar thin film electrodes on a separate chip but in close vicinity to a FET input amplifier. Glucose and urea chips are now on the market commercialized by the company i-stat. These sensors are based on ion selective electrodes. The problems of stability are circumvented by a simple on chip calibration procedure and by the use of such microelectronic electrodes as disposable single shot probes for measuring Na, K, Cl, BUN, Glucose,iCa,pH,pC02 and Hct [56,57]. 

During the past 40 years there have been numerous exciting extensions of electrochemistry to the field of analytical chemistry. A series of selective-ion potentiometric electrodes have been developed, such that most of the common ionic species can be quantitatively monitored in aqueous solution. A highly effective electrolytic moisture analyzer provides continuous online assays for water in gases. Another practical development has been the voltammetric membrane electrode for dioxygen (02), which responds linearly to the partial pressure of 02, either in the gas phase or in solution. The use of an immobilized enzyme (glucose oxidase) on an electrode sensor to assay glucose in blood is another extension of electrochemistry to practical analysis. 

Enzymatic reactions may also be followed manometrically (evolution or uptake of a gas), polarimetrically, potentiometrically, fluorimetrically, and by use of ion selective electrodes. The glucose oxidase-catalyzed oxidation of glucose (Equation 10) ... 

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