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The interactions of biomolecules with reciprocally-adapted shapes regulate cell function. Nuclear Magnetic Resonance (NMR) helps solve the puzzle of biomolecular interactions revealing native structures of proteins in the liquid state, yet crucial details in the spatial arrangement of atoms need fine, new tools to pinpoint. We detail in this chapter the contributions of long-lived states to follow biomolecular folding and interactions in peptides and proteins. The experiments we exemplify are useful for structural biology studies and can be employed as a starting point for further applications, such as medical imaging or spectral separation of metabolites in complex mixtures.

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