Abstract
This chapter describes the theory and application of paramagnetic probes in nuclear magnetic resonance (NMR) experiments with macromolecules by highlighting several examples from the literature. Numerous experiments have been conducted with paramagnetic probes. First, the influence of the electron-nuclear dipolar interactions on the NMR spectra of nuclei in macromolecules has been reported for several systems; second, the paramagnetic influence of metal ions on the protons of water in enzyme-metal ion and nucleic acid-metal ion complexes have been reported; third, the influence of paramagnetic probes on the nuclei of small molecules (substrates and substrate analogs) interacting with the macromolecule-probe complex has been used to determine structures of active-site complexes. The description of the electron-nuclear dipolar relaxation that follows applies to all the above situations. This chapter discusses a brief overview of the use of paramagnetic probes to study structural features of macromolecules. When applied with caution and intelligent experimental design, these methods can provide structural information that can be a substantial aid in relating structure to function in biological macromolecules.
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