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.

Energy- and angle-resolved photoionization spectra of He irradiated by linearly polarized intense 810 nm laser radiation and several of its XUV odd harmonics are investigated. The angular distribution of the odd-order peaks, produced by single-photon ionization by one harmonic, is, surprisingly, broadened by the IR field. The even-order ones, due to two-colour, two-photon ionization, show at 90° lobes which depend on the relative IR–XUV phase. Application to the characterization of attosecond pulses is suggested.