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Application of a Synthetic Ferredoxin-Inspired [4Fe4S]-Peptide Maquette as the Redox Partner for an [FeFe]-Hydrogenase |
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| Authors: | Andrea Bombana Dr Muralidharan Shanmugam Prof David Collison Dr Alexander J Kibler Dr Graham N Newton Dr Christof M Jäger Prof Anna K Croft Dr Simone Morra Dr Nicholas J Mitchell |
| Affiliation: | 1. School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK;2. Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL UK;3. The GlaxoSmithKline Carbon Neutral Labs for Sustainable Chemistry, University of Nottingham Jubilee Campus, Triumph Road, Nottingham, NG7 2TU UK;4. Data Science and Modelling, Pharmaceutical Sciences, R&D, AstraZeneca Gothenburg, Pepparedsleden 1, 431 83 Mölndal, Sweden;5. Department of Chemical Engineering, School of AACME, Loughborough University, Loughborough, LE11 3TU UK;6. Department of Chemical and Environmental Engineering, University of Nottingham, University Park, Nottingham, NG7 2RD UK |
| Abstract: | ‘Bacterial-type’ ferredoxins host a cubane 4Fe4S]2+/+ cluster that enables these proteins to mediate electron transfer and facilitate a broad range of biological processes. Peptide maquettes based on the conserved cluster-forming motif have previously been reported and used to model the ferredoxins. Herein we explore the integration of a 4Fe4S]-peptide maquette into a H2-powered electron transport chain. While routinely formed under anaerobic conditions, we illustrate by electron paramagnetic resonance (EPR) analysis that these maquettes can be reconstituted under aerobic conditions by using photoactivated NADH to reduce the cluster at 240 K. Attempts to tune the redox properties of the iron-sulfur cluster by introducing an Fe-coordinating selenocysteine residue were also explored. To demonstrate the integration of these artificial metalloproteins into a semi-synthetic electron transport chain, we utilize a ferredoxin-inspired 4Fe4S]-peptide maquette as the redox partner in the hydrogenase-mediated oxidation of H2. |
| Keywords: | Iron-sulfur Peptide Maquette Hydrogenase EPR |