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The emergence of systems biology in the post-genomic era has led to investigating increasingly complex macromolecular assemblies, emphasising holistic approaches in structural biology. This changing philosophy is prefaced on the understanding that pathologies are often borne-out of dysregulated, multifaceted interactions within wider biological networks. However, while accurate characterisation of such biomolecular interactions in a biologically valid context is important, this dramatically increases the experimental complexity. In this purview, electron paramagnetic resonance (EPR) is particularly appealing because it is one of few techniques not overwhelmed by the increasing complexity of biomacromolecules in their native context or supramolecular networks. In a variety of ways EPR can additionally detect and quantify interactions, intimately coupling structural information and binding events within the biological or structural context.

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