Amperometric detection organic analytes

Recent applications of nonconducting polymers, such as PPD and overoxidized poly(pyrrole), as permselective and biocompatible membranes hold great promise for the future of biosensors used for in vivo monitoring. Also the suitability of polymeric films (e.g., Eastman AQ 55) for organic-phase biosensors has led to a new opportunity for amperometric detection of analytes in real nonaqueous matrices. Since enzymes are stable in nonaqueous media, many analytes can be detected amperometrically with organic-phase biosensors. 

Because the sensitivity of the detector decreases with decreasing analyte ionization, the pH of the mobile phase should be chosen to maximize solute dissociation. For example, anions with pKa values above 7 are not detectable by conductivity detection. However, conductivity detection is often the preferred method for organic acids with carboxylate, sulfonate, or phospho-nate functional groups, since the pKa values are below 5. For cations, most aliphatic amines have pKa values around 10 and are readily detected by conductivity detection. The pKa values of aromatic amines, however, are in the range 2 to 7, which is too low to be detected by suppressed conductivity. Sensitivity by nonsuppressed conductivity is also poor, so these amines are monitored by UV absorption or pulsed amperometric detection. 

Table 2. Organic analytes detected amperometrically in the oxidative mode [50]...

Microchip Electrophoresis with Amperometric Detection for Organic Food Analytes... 

Most compounds can be detected directly as they are able to produce a direct analytical signal. Photometric detection, especially UV (including diode array and multi-wavelength UV detection) is by far the most frequently applied detection technique. The application of mass spectrometry (MS) detection in CE is attractive as it can provide structural information [44]. Hologram-based refractive index detection [45] and electrochemical detection [46,47] were also reported. Conductivity [41,48-50] and amperometric [51,52] detection has shown to have advantages for the analysis of both organic and inorganic compounds. 

As was mentioned previously, photometric detection is the most frequently applied detection technique. Most of the commercial CE-systems are equipped with at least a UV detector. Some compounds, such as low molecular weight organic and inorganic ions [57-60], do not produce a direct analytical signal. In such cases indirect detection, by indirect UV or fluorescence [59-64] is applied. Besides photometric detection, an application of indirect amperometric [65] detection was also reported. When the analytical signal results from a decrease in... 

Enzyme sensors can measure analytes that are the substrates of enzymatic reactions. Thermometric sensors can measure the heat produced by the enzyme reaction [31], while optical or electrochemical transducers measure a product produced or cofactor consumed in the reaction. For example, several urea sensors are based on the hydrolysis of urea by urease producing ammonia, which can be detected by an ammonium ion-selective ISE or ISFET [48] or a conductometric device [49]. Amperometric enzyme sensors are based on the measurement of an electroactive product or cofactor [50] an example is the glucose oxidase-based sensor for glucose, the most commercially successful biosensor. Enzymes are incorporated in amperometric sensors in functionalised monolayers [51], entrapped in polymers [52], carbon pastes [53] or zeolites [54]. Other catalytic biological systems such as micro-organisms, abzymes, organelles and tissue slices have also been combined with electrochemical transducers. 

Selected examples involving ME for the separation of organic and inorganic food-related analytes, using amperometric and conductimetric detection, as well as involving MCs as biosensing platforms will be separately discussed in the following sections. 

---