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(BBSRC DTP) How nature reduces nitrogen – unravelling design features for a nitrogenase mimic


Project Description

Nitrogen is required for life as a crucial component of both nucleic acids and proteins. Even though nitrogen is the most abundant gas in our atmosphere, our cells can’t use it in its atmospheric form, relying on other processes to "fix" that nitrogen into a biologically available form, ammonia or ammonium. A few microorganisms possess nitrogenase enzymes that can perform this chemical reaction, and about half of the nitrogen in our bodies comes from these microorganisms. The other half comes from the Haber-Bosch industrial process that uses extreme temperatures and pressures, and is environmentally very costly using alone around 2% of the world’s demand for fossil fuels. Nitrogenase by contrast operates at atmospheric pressure and room temperature. Unlocking its mechanism is the key to discovering its secrets and producing possible mimics that can perform as efficiently in an industrial setting or lead to genetically modifying higher plants enabling them to fix their own nitrogen.
This project aims to probe the mechanistic details of nitrogen reduction by nitrogenase using a combination of modelling, synthetic chemistry and spectroscopic techniques all aimed at determining the detailed mechanism of action and applying this knowledge to provide the key design features for a synthetic mimic. The techniques employed such as high-level electron paramagnetic resonance spectroscopy can provide a unique and specific insight into the metallocatalyst active site. Combining this spectroscopy with high level electronic calculations based on density functional theory will permit a detailed mapping of the spatial and electronic structures of the reaction intermediates. Such detail is required to understand the design features which make the natural enzyme so efficient and they can ultimately be used to prepare artificial catalysts which can be applied to the industrial production of ammonia from nitrogen and reduce the Earth’s dependence on the environmentally damaging Haber-Bosch process.

Entry Requirements:
Applications are invited from UK/EU nationals only. Applicants must have obtained, or be about to obtain, at least an upper second class honours degree (or equivalent) in a relevant subject.

Funding Notes

This project is to be funded under the BBSRC Doctoral Training Partnership. If you are interested in this project, please make direct contact with the Principal Supervisor to arrange to discuss the project further as soon as possible. You MUST also submit an online application form - full details on how to apply can be found on the BBSRC DTP website View Website

As an equal opportunities institution we welcome applicants from all sections of the community regardless of gender, ethnicity, disability, sexual orientation and transgender status. All appointments are made on merit.

References

1. Determination of the Complete Spin Density Distribution in C-13-Labeled Protein-Bound Radical Intermediates Using Advanced 2D Electron Paramagnetic Resonance Spectroscopy and Density Functional Theory, Taguchi, Alexander T.; O'Malley, Patrick J.; Wraight, Colin A. Journal of Physical Chemistry B, 121, 44, 10256-10268, 2017
2. A Comparison of Experimental and Broken Symmetry Density Functional Theory (BS-DFT) Calculated Electron Paramagnetic Resonance (EPR) Parameters for Intermediates Involved in the S-2 to S-3 State Transition of Nature's Oxygen Evolving Complex, Beal, Nathan J.; Corry, Thomas A.; O'Malley, Patrick J. Journal of Physical Chemistry B, 122, 1394-1407 , 2018
3. Comparison between Experimental and Broken Symmetry Density Functional Theory (BS-DFT) Calculated Electron Paramagnetic Resonance (EPR) Parameters of the S-2 State of the Oxygen-Evolving Complex of Photosystem II in Its Native (Calcium) and Strontium-Substituted Form, Beal, Nathan J.; Corry, Thomas A.; O'Malley, Patrick J. Journal of Physical Chemistry B , 121, 50, 11273-11283, 2017
4. Manganese Oxidation State Assignment for Manganese Catalase, Beal, Nathan J.; O'Malley, Patrick J. Journal of the American Chemical Society, 138, 14, 4358-4361, 2018
5. A Comparison of Experimental and Broken Symmetry Density Functional Theory (BS-DFT) Calculated Electron Paramagnetic Resonance (EPR) Parameters for the Manganese Catalase Active Site in the Superoxidised Mn(III)/Mn(IV) State, Beal, Nathan J.; Corry, Thomas A.; O'Malley, Patrick J. Journal of Physical Chemistry B, 124, 1394-1407, 2018

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