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Mimicking the Outer...
Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models : From Extended Ligand Design to Metal-Organic Frameworks
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- Pullen, Sonja (författare)
- Uppsala universitet,Molekylär biomimetik
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- Ott, Sascha (preses)
- Uppsala universitet,Molekylär biomimetik
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- Holland, Patrick L., Professor (opponent)
- Department of Chemistry - Yale University
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(creator_code:org_t)
- ISBN 9789155498788
- Uppsala : Acta Universitatis Upsaliensis, 2017
- Engelska 115 s.
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Serie: Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, 1651-6214 ; 1498
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Abstract
Ämnesord
Stäng
- Biomimetic catalysis is an important research field, as a better understanding of nature´s powerful toolbox for the conversion of molecules can lead to technological progress. [FeFe]-hydrogenases are very efficient catalysts for hydrogen production. These enzymes play a crucial role in the metabolism of green algae and certain cyanobacteria. Their active site consists of a diiron complex that is embedded in an interactive protein matrix.In this thesis, two pathways for mimicking the outer coordination sphere effects resulting from the protein matrix are explored.The first is the construction of model complexes containing phosphine ligands that are coordinated to the iron center as well as covalently linked to the bridging ligand of the complex. The effect of such linkers is an increased energy barrier for the rotation of the Fe(CO2)(PL3)-subunit, which potentially could stabilize a terminal hydride that is an important intermediate in the proton reduction cycle.The second pathway follows the incorporation of [FeFe]-hydrogenase active site model complexes into metal-organic frameworks (MOFs). Resulting MOF-catalysts exhibit increased photocatalytic activity compared to homogenous references due to a stabilizing effect on catalytic intermediates by the surrounding framework. Catalyst accessibility within the MOF and the influence of the framework on chemical reactivity are examined in the work presented. Furthermore, an initial step towards application of MOF-catalysts in a device was made by interfacing them with electrodes.The work of this thesis highlights strategies for the improvement of biomimetic model catalysts and the knowledge gained can be transferred to other systems mimicking the function of enzymes.
Ämnesord
- NATURVETENSKAP -- Kemi -- Oorganisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)
Nyckelord
- [FeFe]-hydrogenases
- outer coordination sphere
- model complexes
- biomimetic catalysis
- artificial photosynthesis
- metal-organic frameworks
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