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This chapter presents an overview of sample preparation techniques for in-cell NMR experiments in eukaryotic cells by exogenous macromolecular delivery approaches. Four macromolecular delivery techniques have been proposed for eukaryotic cell sample preparation: mechanical microinjection, active transduction using cell-penetrating peptides (CPPs) mediated by pyrenebutyrate, passive diffusion using pore-forming toxins and electroporation. We introduce the technical features and application examples of each delivery technique and discuss future perspectives of the exogenous macromolecular delivery approach for in-cell NMR in eukaryotic cells.

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