Autocatalytic effect boosts the production of medium-chain hydrocarbons by fatty acid photodecarboxylase

Ongoing climate change is driving the search for renewable and carbon-neutral alternatives to fossil fuels. Photocatalytic conversion of fatty acids to hydrocarbons by fatty acid photodecarboxylase (FAP) represents a promising route to green fuels. However, the alleged low activity of FAP on C2 to C12 fatty acids seemed to preclude the use for synthesis of gasoline-range hydrocarbons. Here, we reveal that FAP ( FAP) can convert -octanoic acid in vitro four times faster than -hexadecanoic acid, its best substrate reported to date. In vivo, this translates into a FAP-based production rate over 10-fold higher for -heptane than for -pentadecane. Time-resolved spectroscopy and molecular modeling demonstrate that FAP's high catalytic activity on -octanoic acid is, in part, due to an autocatalytic effect of its -heptane product, which fills the rest of the binding pocket. These results represent an important step toward a bio-based and light-driven production of gasoline-like hydrocarbons.