Electrochemical amperometric detection

Electrochemical (amperometric) detection is used especially for ftHPLC and offers high sensitivity and... 

To date, electrochemical (amperometric) detection of NO is the only available technique sensitive enough to detect relevant concentrations of NO in real time and in vivo and suffers minimally from potential interfering species such as nitrite, nitrate, dopamine, ascorbate, and L-arginine. Also, because electrodes can be made on the micro- and nano-scale these techniques also have the benefit of being able to measure NO concentrations in living systems without any significant effects from electrode insertion. 

Electrochemical (amperometric) detection is also the method of choice for the analysis of nitroaromatic explosives on microchip devices since it offers up to three orders of magnitude higher sensitivity than indirect laser-induced fluorescence. ° Microfluidic device for detection of five TNT-related explosive compounds with exchangeable carbon thick-film screen-printed amperometric detector can be mentioned in this context. ... 

HPLC method with amperometric detection was applied for detenuination of phenols in sea sediment and some dmg preparation. Peaks of phenol, guaiacol, cresols, hydroquinon and resorcinol were identified on chromatogram of birch tai. The HPLC method with electrochemical detectors was used for detenuination of some drug prepai ation of aminophenol derivate. So p-acetaminophenol (paracetamol) was determined in some drug. 

While the terms amperometric detection and coulometric detection have come into use to describe detectors of less than 100% efficiency and 100% efficiency respectively, these terms are actually misnomers. An amperometric detector is any electrochemical detector where current is plotted as a function of time, regardless of the conversion efficiency. A coulometric detector is any electrochemical detector where charge is plotted as a function of time, again regardless of the conversion efficiency. Preferred terminology should be high efficiency and low efficiency detectors to describe the two situations. 

Based on many of the advances described above in electrochemical approaches to immunoassay, it is tempting to conclude that commercialization of some of the approaches is imminent. This may be true, but the historical use of optical methods for many clinical chemistry tests coupled with their rapidly growing use in immunoassay is a difficult barrier for any radically different method to overcome, though electrochemical sensors have become more important in the clinical chemistry laboratory over the last decade. In any event, to be successful ECIA methods will have to demonstrate clear superiority over existing and emerging technologies in both cost and performance. Some of the more recently described approaches such as those using enzyme amplified amperometric detection and ecLIA appear... 

The use of non-inert and chemically modified electrodes and other strategies for the detection of species that are difficult to analyze with the normal electrode materials have been reviewed.55 Photosensitization prior to amperometric detection is another tactic that has proved useful for the analysis of substances that are normally considered to be electrochemically inert.56 The use of pulsed amperometry has recently been reviewed.57... 

Simple etching of the capillary end served to decouple the electrophoretic current from that of amperometric detection, permitting quantitation of attomole levels of catecholamines from brain microdialyzates.24 A postcolumn reactor using bromine generated electrochemically in situ has been used in the detection of peptide thiols, such as glutathione and cysteine, separated by capillary electrophoresis.25... 

Another interesting method of amperometric detection for LC is dualelectrode electrochemical detection. Instead of a single WE, one can place two WEs in series, parallel to or opposite each other. The series configuration is mostly used, mainly in the collection mode, i.e., the electroactive substance entering the detector is converted at the upstream (generator) electrode into a product that either is or is not detected at the downstream (indicator) electrode, depending on the potential of the latter. Hoogvliet et al.137,162 were easily able... 

Electrochemical detectors, which are based on the electrochemical oxidation or reduction of the analyte, can be applied to the analysis of selected compounds such as phenols. It is physically simple, but is very sensitive for catecholamines. However, the adsorption of reacted molecules on the surface of the electrodes can reduce the conductivity. To overcome this problem a pulsed voltage is applied, which cleans the electrode surface between measurements. This pulsed amperometric detection is also sensitive for carbohydrates. 

A dual electrochemical microchip detection system, based on the coupling of conductivity and amperometric detection schemes, was developed for simultaneous measurements of both nitroaromatic and ionic explosives [34], The microsystem relied on the combination of a contactless conductivity detector with an end-column thick-film carbon amperometric detector. Such ability to monitor both redox-active nitroaromatic and ionic explosives is demonstrated in Figure 13.7, which shows typical dual-detection electropherograms for a sample mixture containing the nitroaromatic explosives trinitrobenzene (TNB) (4), TNT (5), 2,4-DNB (6), and 2-Am-4,6-DNB (7), as well as the explosive-related ammonium... 

Fluorescence detection, because of the limited number of molecules that fluoresce under specific excitation and emission wavelengths, is a reasonable alternative if the analyte fluoresces. Likewise, amperometric detection can provide greater selectivity and very good sensitivity if the analyte is readily electrochemically oxidized or reduced. Brunt (37) recently reviewed a wide variety of electrochemical detectors for HPLC. Bulk-property detectors (i.e., conductometric and capacitance detectors) and solute-property detectors (i.e., amperometric, coulo-metric, polarographic, and potentiometric detectors) were discussed. Many flow-cell designs were diagrammed, and commercial systems were discussed. 

Two analytical methods for priority pollutants specified by the USEPA (38) use HPLC separation and fluorescence or electrochemical detection. Method 605, 40 CFR Part 136, determines benzidine and 3,3-dichlorobenzidine by amperometric detection at +0.80 V, versus a silver/silver chloride reference electrode, at a glassy carbon electrode. Separation is achieved with a 1 1 (v/v) mixture of acetonitrile and a pH 4.7 acetate buffer (1 M) under isocratic conditions on an ethyl-bonded reversed-phase column. Lower limits of detection are reported to be 0.05 /xg/L for benzidine and 0.1 /xg/L for 3,3-dichlorobenzidine. Method 610, 40 CFR Part 136, determines 16 PAHs by either GC or HPLC. The HPLC method is required when all 16 PAHs need to be individually determined. The GC method, which uses a packed column, cannot adequately individually resolve all 16 PAHs. The method specifies gradient elution of the PAHs from a reversed-phase analytical column and fluorescence detection with an excitation wavelength of 280 nm and an emission wavelength of 389 nm for all but three PAHs naphthalene, acenaphthylene, and acenaphthene. As a result of weak fluorescence, these three PAHs are detected with greater sensitivity by UV-absorption detection at 254 nm. Thus, the method requires that fluores-... 

Most aliphatic amines and alcohols are considered to be nonelectroactive. The reason for this is that the product of the oxidation adsorbs to the electrode surface, fouling the electrode. Therefore, most reactions of these compounds at noble metal electrodes have been transient and not amenable to direct amperometric detection. In voltammetry experiments, electrodes are cleaned between experiments by electrochemical or chemical treatment to restore the electrode response. 

Figure 27.20 Schematic drawing of CE with end-column amperometric detection A, capillary B, cathodic buffer reservoir and electrochemical cell C, carbon fiber electrode D, electrode assembly, E, micromanipulator RE, reference electrode. [Adapted with permission from Ref. 49.]...

Another approach to dealing with the nonelectrochemically active nature of most amino acids is to generate, in situ, chemical reactions at the electrode surfaces to produce electrochem-ically active products for detection. Related to this concept, is the online use of immobilized enzymes (142) to react with amino acids. A by-product of this reaction is hydrogen peroxide, which is then quantified by amperometric detection. 

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