Protein Scaffolds Modulate the Electronic Structure of a Common Ketyl Radical Intermediate in Thiamine Pyrophos-phate-Dependent Radical Biocatalysis: Insights from EPR and ENDOR Spectroscopy
New-to-nature radical biocatalysis has emerged as a powerful strategy for asymmetric C--C bond formation, yet the enzyme-bound radi-cal intermediates that underpin these transformations have remained largely uncharacterized. Here, we combine photo biocatalytic reaction development with multifrequency electron paramagnetic resonance (EPR), electron-nuclear double resonance (ENDOR) spectroscopy,…
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