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Pyrroloquinoline Quinone Aza-Crown Ether Complexes as Biomimetics for Lanthanide and Calcium Dependent Alcohol Dehydrogenases**

Vetsova, Violeta A.; Fisher, Katherine R.; Lumpe, Henning; Schäfer, Alexander 1; Schneider, Erik K. 1; Weis, Patrick 1; Daumann, Lena J.
1 Institut für Physikalische Chemie (IPC), Karlsruher Institut für Technologie (KIT)

Abstract:

Understanding the role of metal ions in biology can lead to the development of new catalysts for several industrially important transformations. Lanthanides are the most recent group of metal ions that have been shown to be important in biology, that is, in quinone-dependent methanol dehydrogenases (MDH). Here we evaluate a literature-known pyrroloquinoline quinone (PQQ) and 1-aza-15-crown-5 based ligand platform as scaffold for Ca$^{2+}$, Ba$^{2+}$, La$^{3+}$ and Lu$^{3+}$ biomimetics of MDH and we evaluate the importance of ligand design, charge, size, counterions and base for the alcohol oxidation reaction using NMR spectroscopy. In addition, we report a new straightforward synthetic route (3 steps instead of 11 and 33 % instead of 0.6 % yield) for biomimetic ligands based on PQQ. We show that when studying biomimetics for MDH, larger metal ions and those with lower charge in this case promote the dehydrogenation reaction more effectively and that this is likely an effect of the ligand design which must be considered when studying biomimetics. To gain more information on the structures and impact of counterions of the complexes, we performed collision induced dissociation (CID) experiments and observe that the nitrates are more tightly bound than the triflates. ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000133866
Veröffentlicht am 14.06.2021
Originalveröffentlichung
DOI: 10.1002/chem.202100346
Scopus
Zitationen: 4
Web of Science
Zitationen: 2
Dimensions
Zitationen: 4
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 12.07.2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000133866
Erschienen in Chemistry - A European Journal
Verlag John Wiley and Sons
Band 27
Heft 39
Seiten 10087-10098
Vorab online veröffentlicht am 19.04.2021
Nachgewiesen in Scopus
Web of Science
Dimensions
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