Biofuel and Green Chemistry: Mechanism of an Inherent Photoenzyme Decoded

The functioning of the enzyme FAP, valuable for green chemistry and for generating biofuels, has been solved. This event gathered a group of scientists from the world, including numerous French scientists from the CNRS, CEA, École Polytechnique, Inserm, the universities of Grenoble Alpes, Aix Marseille, European Synchrotron (ESRF), as well as the Paris-Saclay and synchrotron SOLEIL. The research was issued in Science on April 9, 2021.

The scientists explained the working mechanisms of FAP (Fatty Acid Photodecarboxylase), which is usually exists in infinitesimal algae such as Chlorella and spirulina. The enzyme had been identified in 2017 as able to use light energy from fatty acids produced by these microalgae to produce hydrocarbons. To accomplish this new result, the research group used a theoretical and experimental toolkit.

Knowing how FAP responds is crucial because this photoenzyme opens up a novel opportunity for sustainable biofuel production from fatty acids typically produced by living organisms. FAP is also extremely promising for generating high added-value compounds for fine pharmaceutics, cosmetics, and chemistry.

enzyme FAP
The scientists explained the working mechanisms of FAP (Fatty Acid Photodecarboxylase), which is usually exists in infinitesimal algae such as Chlorella and spirulina. (Science 2021). Source: Damien Sorigue

Further, due to their light-induced response, photoenzymes give access to ultrarapid phenomena that occur during enzymatic reactions. FAP, therefore, provides a new opening to understand in detail a chemical reaction taking place in living organisms.

More precisely, in this work, Scientists explain that when FAP is illuminated and absorbs a photon, an electron is displaced in 300 picoseconds from the fatty acid produced by the algae. This fatty acid is then divided into a carbon dioxide (CO2) and hydrocarbon precursor. Most of the CO2 produced is then converted into bicarbonate (HCO3-) in 100 nanoseconds within the enzyme. This action uses light but does not limit photosynthesis: the flavin molecule within the FAP, which absorbs the photon, is bent. This conformation turns the molecule’s absorption spectrum towards the red so that it utilizes photons not used for the microalgae’s photosynthetic process.

It is the combined analysis of the outcomes of several theoretical and experimental procedures by the global consortium that yields the complete, atomic-scale picture of FAP at work. This interdisciplinary research combined optical and vibrational spectroscopy, bioengineering work, static and kinetic crystallography performed with an X-ray free-electron laser or synchrotrons, as well as quantum chemistry calculations.

Journal Reference: “Mechanism and dynamics of fatty acid photodecarboxylase” by D. Sorigué, A. Bonvalet, K. Hadjidemetriou, S. Blangy, G. Gotthard, N. Coquelle, P. Samire, A. Aleksandrov, L. Antonucci, A. Benachir, S. Carbajo, R. Hienerwadel, M. Hilpert, M. Kloos, S. Cuiné, S. Boutet, M. Byrdin, S. L. Y. Moulin, D. Nurizzo, G. Peltier, M. Cammarata, R. B. Doak, M. Weik, T. Domratcheva, K. Brettel, M. Sliwa, R. L. Shoeman, T. R. M. Barends, J.-P. Colletier, X. Solinas, B. Zhuang, L. Foucar, A. Gorel, M. Grünbein, E. Hartmann, T. J. Lane, B. Légeret, P. Legrand, Y. Li-Beisson, G. Schirò, M. Joffre, A. Royant, C. Berthomieu, M. and F. Beisson, 9 April 2021, Science.

DOI: 10.1126/science.abd5687

The research involved an active collaboration of French Scientist from the Biotechnologies and Bioscience Institute of Aix-Marseille (CEA/CNRS/Aix-Marseille University), the Laboratory for Optics and Biosciences (CNRS/École Polytechnique-Institut Polytechnique de Paris/Inserm), the Institute of Structural Biology (CEA/CNRS/Grenoble Alpes University), Reactivity and the Environment (CNRS/University of Lille), the Institute for Integrative Biology of the Cell (CEA/CNRS/Paris-Saclay University), the Advanced Spectroscopy Laboratory for Interactions, the SOLEIL synchrotron and also from the European Synchrotron (ESRF) and the Laue Langevin Institute (ILL), two major European instruments based in Grenoble, France. Financially supported by the French National Research Agency. The research also involved scientists from the Moscow State University (Russia), the SLAC National Accelerator Laboratory (USA), and Max Planck Institute in Heidelberg (Germany).

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