Using a metagenomics approach, we have cloned a piece of environmental DNA from the Sargasso Sea that encodes an [NiFe] hydrogenase showing 60% identity to the large subunit and 64% to the small subunit of a Thiocapsa roseopersicina O2-tolerant [NiFe] hydrogenase. The DNA sequence of the hydrogenase identified by the metagenomic approach was subsequently found to be 99% identical to the hyaA and hyaB genes of an Alteromonas macleodii hydrogenase, indicating that it belongs to the Alteromonas clade. We were able to express our new Alteromonas hydrogenase in T. roseopersicina. Expression was accomplished by coexpressing only two accessory genes, hyaD and hupH, without the need to express any of the hyp accessory genes (hypABCDEF). These results suggest that the native accessory proteins in T. roseopersicina could substitute for the Alteromonas counterparts that are absent in the host to facilitate the assembly of a functional Alteromonas hydrogenase. To further compare the complex assembly machineries of these two [NiFe] hydrogenases, we performed complementation experiments by introducing the new Alteromonas hyaD gene into the T. roseopersicina hynD mutant. Interestingly, Alteromonas endopeptidase HyaD could complement T. roseopersicina HynD to cleave endoproteolytically the C-terminal end of the T. roseopersicina HynL hydrogenase large subunit and activate the enzyme. This study refines our knowledge on the selectivity and pleiotropy of the elements of the [NiFe] hydrogenase assembly machineries. It also provides a model for functionally analyzing novel enzymes from environmental microbes in a culture-independent manner.
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http://dx.doi.org/10.1128/AEM.00580-09 | DOI Listing |
J Chem Theory Comput
January 2025
Max-Planck-Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany.
A new method to perform complete active space second-order perturbation theory on top of large active spaces optimized with full configuration quantum Monte Carlo is presented. Computing the three- and Fock-contracted four-particle density matrix from imaginary-time-averaged wave functions is found to resolve fermionic positivity violations and to ensure numerical stability. The protocol is applied to [NiFe]-hydrogenase, [CuO]-oxidase and Fe-porphyrin model systems up to 26 electrons in 27 orbitals and benchmarked against DMRG-CASPT2.
View Article and Find Full Text PDFJ Chem Inf Model
January 2025
Institute of Chemistry, Technische Universität Berlin, Straße des 17. Juni 135, Berlin 10623, Germany.
Machine learning (ML) is a powerful tool for the automated data analysis of molecular dynamics (MD) simulations. Recent studies showed that ML models can be used to identify protein-ligand unbinding pathways and understand the underlying mechanism. To expedite the examination of MD simulations, we constructed PathInHydro, a set of supervised ML models capable of automatically assigning unbinding pathways for the dissociation of gas molecules from [NiFe] hydrogenases, using the unbinding trajectories of CO and H from [NiFe] hydrogenase as a training set.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
December 2024
Department of Pharmaceutical Analysis, School of Pharmaceutical Sciences, Zhengzhou University, Zhengzhou 450001, People's Republic of China.
Inflammatory bowel disease (IBD) is often associated with excessive inflammatory response and highly dysregulated gut microbiota. Traditional treatments utilize drugs to manage inflammation, potentially with probiotic therapy as an adjuvant. However, current standard practices often suffer from detrimental side effects, low bioavailability, and unsatisfactory therapeutic outcomes.
View Article and Find Full Text PDFChem Commun (Camb)
November 2024
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, UK.
The ability of hydrogenase enzymes to activate H with excellent selectivity leads to many interesting possibilities for biotechnology driven by H as a clean reductant. Here, we review examples where hydrogenase enzymes have been used to drive native and non-native hydrogenation reactions in solution or as part of a redox cascade on a conductive support, with a focus on the developments we have contributed to this field. In all of the examples discussed, hydrogenation reactions are enabled by coupled redox reactions: the oxidation of H at a hydrogenase active site, linked electronically ( relay clusters in the enzyme and/or conductive support) to the site of a reduction reaction, and we note how this parallels developments in site-separated reactivity in heterogeneous catalysis.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
[NiFe]-hydrogenases catalyze the reversible activation of H using a unique NiFe(CN)CO metal site, which is assembled by a sophisticated multiprotein machinery. The [4Fe-4S] cluster-containing HypCD complex, which possesses an ATPase activity with a hitherto unknown function, serves as the hub for the assembly of the Fe(CN)CO subfragment. HypCD is also thought to be responsible for the subsequent transfer of the iron fragment to the apo-form of the catalytic hydrogenase subunit, but the underlying mechanism has remained unexplored.
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