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This chapter provides an overview of naturally occurring and chemically introduced paramagnetic centers in biomolecules. It discusses examples of paramagnetic metal ions in metalloproteins, where paramagnetic metals can act as intrinsic paramagnetic probes. Furthermore, biotechnological methods for the introduction of specific binding sites for paramagnetic metal ions are presented. Finally, the wide range of synthetic paramagnetic probes are discussed that have recently been developed for site-specific attachment to biomolecules.

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