Structural Biology

Halogens instead of hydroxyls

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Science  29 Jul 2016:
Vol. 353, Issue 6298, pp. 459-460
DOI: 10.1126/science.353.6298.459-c

Chlorine and other halogens are key constituents of many industrially important compounds. Enzyme-based approaches to transfer halogens to organic compounds are a potentially greener synthetic route, producing less harmful by-products. Mitchell et al. determined a 2.4 Å-resolution x-ray crystal structure of a bacterial halogenase protein in a complex with its precursor substrate. The structure reveals how the enzyme chlorinates the substrate through an iron-chlorine intermediate at the active site. A neighboring serine orchestrates ligand dynamics to allow for halogenation instead of hydroxylation. Engineering a related nonhalogenating hydroxylase protein with a serine in the same position makes the enzyme capable of both hydroxylation and halogenation.

Nat. Chem. Biol. 10.1038/NCHEMBIO.2112 (2016).

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