Only EPR detects unpaired electrons unambiguously. Other techniques such as fluorescence may provide indirect evidence of free radicals, but EPR alone yields incontrovertible evidence of their presence. In addition, EPR has the unique power to identify the paramagnetic species that is detected. EPR samples are very sensitive to local environments. Therefore, the technique sheds light on the molecular structure near the unpaired electron. Sometimes, the EPR spectra exhibit dramatic lineshape changes, giving insight into dynamic processes such as molecular motions or fluidity. The EPR spin-trapping technique, which detects short-lived, reactive free radicals, very nicely illustrates how EPR detection and identification of radicals can be exploited. This technique has been vital in the biomedical field for elucidating the role of free radicals in many pathologies and toxicities. EPR spin-labelling is a technique used by biochemists whereby a paramagnetic molecule (i.e., the spin label) is used to “tag” macromolecules in specific regions. From the EPR spectra reported by the spin label, they can determine the type of environment (hydropho¬bicity, pH, fluidity, etc.) in which the spin label is located.
ESEEM and ENDOR are two EPR methods that measure the interactions of the electron with the surrounding nuclei. They are extremely powerful techniques for probing the structure of “active sites” in metalloproteins. Another important application for quantitative EPR is radiation dosimetry. Among its uses are dose measurements for sterilization of medical goods and foods, detection of irradiated foods, and the dating of early human artifacts.