3d-Metall-Käfig-Komplexe als Modelle für aktive Zentren von nicht-Häm Proteinen

3d metal cage complexes as models for active centers of non heme proteins

by Sarah Carolin Bete
Doctoral thesis
Date of Examination:2023-11-08
Date of issue:2024-10-22
Advisor:Dr. Matthias Otte
Referee:Dr. Matthias Otte
Referee:Prof. Dr. Franc Meyer
Referee:Prof. Dr. Manuel Alcarazo
Persistent Address: http://dx.doi.org/10.53846/goediss-10770

 

 

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Abstract

English

This thesis presents a broad study on a new ligand system, specially designed for the mimicry of the quasi-chelating coordination by amino acid side chain residues in enzymatic pockets. The ligand system is based on an endo-functionalized organic cage framework and provides a wide-pored cavity with a defined metal coordination site. Complex formation is initially shown for copper in a tris-imidazole environment and the isolated complex is investigated for its resemblance of this recurring motif, as well as for its applicability in oxidation catalysis. Further development of the ligand systems allows for (within a cage cavity unprecedented) pseudo-heteroleptic quasi-chelation. The introduced protocols give rise to a broad range of (L1)2L2-endo-functionalized ligands, (L1 and L2 representing amino acid side chain residues) with great potential for accurate mimicry of the huge variety of non-heme active sites. The presented investigations focus on specially designed mimics of the CuC site of particulate methane monooxygenase, and of the general structure of non-heme iron oxygenases based on the 2his-1-carboxylate facial triad. On those, functional mimicry is shown in the regard of the behavior towards dioxygen as well as in the reactivity in connection with according relevant cofactors. Both are capable of oxidizing CH-bonds of medium strength. The accuracy of the structural mimicry of the overall system is confirmed by the very good reflections of the according enzyme’s spectral features.
Keywords: biomimetic chemistry; enzyme models; active cage compounds
 
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