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Mechanism and dynamics of fatty acid photodecarboxylase.

Damien SoriguéKyprianos HadjidemetriouStéphanie BlangyGuillaume GotthardAdeline BonvaletN CoquellePoutoum-Palakiyem SamireAlexey AleksandrovLaura AntonucciA BenachirSébastien BoutetMartin ByrdinMarco CammarataSergio CarbajoStéphan CuinéR B DoakL FoucarAlexander GorelM GrünbeinE HartmannRainer HienerwadelMario HilpertM KloosThomas J LaneBertrand LégeretPierre LegrandYonghua Li-BeissonSolène L Y MoulinDidier NurizzoGilles PeltierG SchiròRobert L ShoemanM SliwaXavier SolinasBo ZhuangThomas R M BarendsJacques-Philippe ColletierManuel JoffreAntoine RoyantCatherine BerthomieuMartin WeikTatiana DomratchevaKlaus BrettelMarten H VosIlme SchlichtingPascal ArnouxPavel MüllerFrédéric Beisson
Published in: Science (New York, N.Y.) (2021)
Fatty acid photodecarboxylase (FAP) is a photoenzyme with potential green chemistry applications. By combining static, time-resolved, and cryotrapping spectroscopy and crystallography as well as computation, we characterized Chlorella variabilis FAP reaction intermediates on time scales from subpicoseconds to milliseconds. High-resolution crystal structures from synchrotron and free electron laser x-ray sources highlighted an unusual bent shape of the oxidized flavin chromophore. We demonstrate that decarboxylation occurs directly upon reduction of the excited flavin by the fatty acid substrate. Along with flavin reoxidation by the alkyl radical intermediate, a major fraction of the cleaved carbon dioxide unexpectedly transformed in 100 nanoseconds, most likely into bicarbonate. This reaction is orders of magnitude faster than in solution. Two strictly conserved residues, R451 and C432, are essential for substrate stabilization and functional charge transfer.
Keyphrases
  • fatty acid
  • high resolution
  • carbon dioxide
  • electron transfer
  • transcription factor
  • mass spectrometry
  • magnetic resonance
  • risk assessment
  • single molecule
  • structural basis
  • human health
  • drug discovery
  • contrast enhanced