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Generating dihydrogen by tethering an [FeFe]hydrogenase via a molecular wire to the A1A/A1B sites of photosystem I

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Abstract

Photosystem I complexes from the menB deletion mutant of Synechocystis sp. PCC 6803 were previously wired to a Pt nanoparticle via a molecular wire consisting of 15-(3-methyl-1,4-naphthoquinone-2-yl)]pentadecyl sulfide. In the presence of a sacrificial electron donor and an electron transport mediator, the PS I-NQ(CH2)15S-Pt nanoconstruct generated dihydrogen at a rate of 44.3 µmol of H2 mg Chl−1 h−1 during illumination at pH 8.3. The menB deletion strain contains an interruption in the biosynthetic pathway of phylloquinone, which results in the presence of a displaceable plastoquinone-9 in the A1A/A1B sites. The synthesized quinone contains a headgroup identical to the native phylloquinone along with a 15-carbon long tail that is terminated in a thiol. The thiol on the molecular wire is used to bind the Pt nanoparticle. In this short communication, we replaced the Pt nanoparticle with an [FeFe]H2ase variant from Clostridium acetobutylicum that contains an exposed iron on the distal [4Fe-4S] cluster afforded by mutating the surface exposed Cys97 residue to Gly. The thiol on the molecular wire is then used to coordinate the corner iron atom of the iron–sulfur cluster. When all three components are combined and illuminated in the presence of a sacrificial electron donor and an electron transport mediator, the PS I-NQ(CH2)15S-[FeFe]H2ase nanoconstruct generated dihydrogen at a rate of 50.3 ± 9.96 μmol of H2 mg Chl−1 h−1 during illumination at pH 8.3. This successful in vitro experiment sets the stage for assembling a PS I-NQ(CH2)15S-[FeFe]H2ase nanoconstruct in vivo in the menB mutant of Synechocystis sp. PCC 6803.

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Acknowledgements

We would like to acknowledge Dr. Paul King and Dr. Carolyn Lubner (National Renewable Energy Labs) for providing the plasmids used in this study as well as guidance in the expression, purification, and handling of the [FeFe]H2ase enzyme. This work was supported by the US Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE‐SC0018087.

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Authors and Affiliations

  1. Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, PA, 16802, USA

    Michael Gorka & John H. Golbeck

  2. Department of Chemistry, The Pennsylvania State University, University Park, PA, 16802, USA

    John H. Golbeck

  3. Department of Biochemistry and Molecular Biology, The Pennsylvania State University, S328 Frear Building, University Park, PA, 16802, USA

    John H. Golbeck

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  1. Michael Gorka
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Correspondence to John H. Golbeck.

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Gorka, M., Golbeck, J.H. Generating dihydrogen by tethering an [FeFe]hydrogenase via a molecular wire to the A1A/A1B sites of photosystem I. Photosynth Res 143, 155–163 (2020). https://doi.org/10.1007/s11120-019-00685-y

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