Electron spin resonance spectroscopy analytical applications

The application of analytical methods to speciation measurements in complicated systems has remained rather limited, despite the considerable technological progress during the past 25 years. The characterisation methods (e.g. spectroscopy, nuclear magnetic resonance) are often limited to the study of isolated compounds at relatively high concentrations. They, therefore, necessitate the prior employment of sophisticated separation and pre-concentration methods which introduce severe risks of perturbation. The trace analysis methods are often insensitive to the chemical form of the elements measured (e.g. atomic absorption, neutron activation). Those which possess sufficient element specificity (e.g. electron spin resonance, fluorescence, voltammetry) still require significant development before their full potential can be realised. 

Electrochemically generated intermediates are usually easier to detect spectroscopically than the substrate material itself. The electrochemical reduction or oxidation of many organic materials yields products, which are often coloured with high absorption coefficients (UV/Vis), or which give a characteristic radical signature in electron spin resonance (ESR) spectroscopy [42], Based on this highly sensitive detection, spectroelectrochemical detectors have been proposed and employed for analytical applications [43],... 

In the last three decades, nuclear magnetic resonance has become a powerful tool for investigating the structural and physical properties of matter. Today, nuclear magnetic resonance is the physical method most widely used in analytical chemistry. For special applications, e.g. relaxation time measurements, there is available a variety of modifications of the basic nuclear magnetic resonance experiments such as pulse and spin-echo methods. In the course of this development and when electronic computers were provided at a reasonable price, Fourier transform spectroscopy was applied to nuclear magnetic resonance in the middle of the sixties. At that time, Fourier methods were already used to a large extent in far infrared spectroscopy (see Refs. and references cited therein). 

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