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Significance Vast quantities of aromatic compounds enter the environment due to the natural breakdown of lignin as well as industrial and agricultural pollution. Intradiol aromatic ring-cleaving dioxygenases play a pivotal role in the biodegradation of these aromatics. Despite exhaustive study, the mechanism of intradiol dioxygenases has remained elusive because the reaction cycle intermediates in which O2 is activated and inserted into the aromatic are too fleeting to be trapped and characterized. Here the intradiol dioxygenase reaction is carried out in a crystal, allowing the two reaction cycle intermediates that most clearly define the mechanism to be trapped and their structures solved.

Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase