Electrochemical techniques INDEX

This article provides some general remarks on detection requirements for FIA and related techniques and outlines the basic features of the most commonly used detection principles, including optical methods (namely, ultraviolet (UV)-visible spectrophotometry, spectrofluorimetry, chemiluminescence (CL), infrared (IR) spectroscopy, and atomic absorption/emission spectrometry) and electrochemical techniques such as potentiometry, amperometry, voltammetry, and stripping analysis methods. Very few flowing stream applications involve other detection techniques. In this respect, measurement of physical properties such as the refractive index, surface tension, and optical rotation, as well as the a-, //-, or y-emission of radionuclides, should be underlined. Piezoelectric quartz crystal detectors, thermal lens spectroscopy, photoacoustic spectroscopy, surface-enhanced Raman spectroscopy, and conductometric detection have also been coupled to flow systems, with notable advantages in terms of automation, precision, and sampling rate in comparison with the manual counterparts. 

A possibility to consider polyciystalline platinum surface as some combination of low index surfaces or as some disordered single crystalline surface surely caimot be immediately concluded from the values of zero charge potentials exclusively. Experiments with some intermediate model systems more or less reduceable to simple additive combinations of several planes, or of terraces and steps, are of increasing interest. Microfacetted electrodes, various types of nanoparticles prepared by precise non-electrochemical techniques, non-coalesced electrodeposited particles, " and single platinum microspheres deposited on micro-electrodes, as well as highly ordered templated electrdeposits can be considered as most ordered real platinum materials helpful to discover stractural effects at atomic level. However they all are still too simple to compare with, to say, platinized platinum, and attempts to electrodeposit the dispersed metallic multilayers of more and more ordered type ° are also relevant. 

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. 

Typically, sample detection in electromigration techniques is performed by on-column detection, employing a small part of the capillary as the detection cell where a property of either the analyte, such as UV absorbance, or the solution, such as refractive index or conductivity, is monitored. This section briefly describes the major detection modalities employed in capillary electromigration techniques, which are accomplished using UV-visible absorbance, fluorescence spectroscopy, and electrochemical systems. The hyphenation of capillary electromigration techniques with spectroscopic techniques employed for identification and structural elucidation of the separated compounds is also described. 

Since the development of HPLC as a separation technique, considerable effort has been spent on the design and improvement of suitable detectors. The detector is perhaps the second-most important component of an HPLC system, after the column that performs the actual separation it would be pointless to perform any separation without some means of identifying the separated components. To this end, a number of analytical techniques have been employed to examine either samples taken from a fraction collector or the column effluent itself. Although many different physical principles have been examined for their potential as chromatography detectors, only four main types of detectors have obtained almost universal application, namely, ultraviolet (UV) absorbance, refractive index (RI), fluorescence, and conductivity detectors. Today, these detectors are used in about 80% of all separations. Newer varieties of detector such as the laser-induced fluorescence (LIE), electrochemical (EC), evaporative light scattering (ELS), and mass spectrometer (MS) detectors have been developed to meet the demands set by either specialized analyses or by miniaturization. 

This volume comprises ten tables Table I, which gives information about the electrochemical behaviors of 2015 chemical compounds and about the experimental techniques and conditions employed in studying them, and nine other tables that serve to supplement, cross-index, and interpret the contents of Table I. 

Whereas the first synthesis of chemicals by electrolysis dates back over 180 years, the equipment and techniques to understand the fundamentals of these reactions were not developed until recently. This review of electrochemical citations of pyridine compounds of industrial interest is keyed to the functionality of the starting pyridine hence the electrochemistry of pyridines is indexed and not their preparation by electrolysis. 

The most commonly-used detectors are those based on spectrophotometry in the region 184-400nm, visible ultraviolet spectroscopy in the region 185-900nm, post-column derivativisation with fluorescence detection (see below), conductivity and those based on the relatively new technique of multiple wavelength ultraviolet detectors using a diode array system detector (described below). Other types of detectors available are those based on electrochemical principles, refractive index, differential viscosity and mass detection. 

For several years LC detectors were limited to refractive index and ultraviolet absorption systems. Recently introduced systems include the electrochemical detector and a moving belt interface allowing for chemical ionization-mass spectrometric detection. Both of these techniques provide a degree of selectivity not previously available. 

Current IPC detectors are on-stream monitors. HPLC detectors range from (1) non selective or universal (bulk property detectors such as the refractive index (RI) detector), characterized by limited sensitivity, (2) selective (discriminating solute property detectors such as UV-Vis detectors) to (3) specific (specific solute property detectors such as fluorescence detectors). Traditional detection techniques are based on analyte architecture that gives rise to high absorbance, fluorescence, or electrochemical activity. Mass spectrometry (MS) and evaporative light scattering detectors (ELSDs), can be considered universal types in their own right... 

For detection of carbohydrates in principle, ultraviolet (UV), laser-induced fluorescence, refractive index, electrochemical, amperometric, and mass spec-trometric detection can be used. Mass spectrometry, with its various ionization methods, has traditionally been one of the key techniques for the structural determination of proteins and carbohydrates. Fast-atom bombardment (FAB) and electrospray ionization (ESI) are the two on-line ionization methods used for carbohydrate analysis. The ESI principle has truly revolutionized the modern mass spectrometry of biological molecules, due to its high sensitivity and ability to record large-molecule entities within a relatively smaU-mass scale. 

Electrochemical detection is inherently a chemical rather than a physical technique (such as ultraviolet, infrared, fluorescence, or refractive index). It is, therefore, not surprising to hnd that many imaginative postcolumn reactions have been coupled to LC-EC. These include photochemical reactions, enzymatic reactions, halogenation reactions, and Biuret reactions. In each case, the purpose is to enhance selectivity and therefore improve limits of detection. While simplicity is sacrihced with such schemes, there are many published methods that have been quite successful. 

Ultraviolet (UV) spectroscopy, mass spectrometry (MS), refractive index (RI) detection, and electrochemical detection (ECD) are common online monitoring techniques for analytical chromatography. UV and RI are regularly used for monitoring preparative operations as well. To employ MS or ECD in a high-flow scheme, usually a side stream must be diverted from the main eluate line via a flow splitter so that what passes through the detector has a flow rate that is acceptable for an analytical-scale system. 

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