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Proposed lipoic acid biosynthetic mechanism. In lipoic acid biosynthesis, a radical SAM enzyme LipA mediates the transfer of sulfurs from an auxiliary [4Fe-4S] cluster to octanoyl-LCP substrate 22. The auxiliary [4Fe-4S] cluster is then replenished for the next cycle by the iron–sulfur cluster maturation system, e.g., iron–sulfur cluster delivered by IscU or Nfu protein.
