Reichenbach-Klinke, Roland and Kruppa, Michael and Koenig, Burkhard (2002) NADH model systems functionalized with Zn(II)-cyclen as flavin binding site-structure dependence of the redox reaction within reversible aggregates. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 124 (44). pp. 12999-13007. ISSN 0002-7863
Full text not available from this repository. (Request a copy)Abstract
The relative positions and conformations of the prosthetic group FAD and the cofactor NADH have been remarkably conserved within the structurally diverse group of flavin enzymes. To provide a chemical rational for such an obviously optimal relative disposition of the redox partners for efficient reaction we have synthesized NADH models with Zn(II)-cyclen substituents for reversible flavin binding in water. Altogether, four of these model systems with systematically varying spacer length between the recognition site and the redox active dihydronicotinamide were prepared. The binding of these model systems to riboflavin tetraacetate was confirmed by potentiometric pH titration in water and their reaction with flavin was followed by UV-vis spectroscopy in aqueous media under physiological conditions. The measurements reveal a significant rate enhancement of up to 175 times that of an intermolecular reaction. Moreover, a strong dependence of the reaction rate on the spacer length was observed, which clearly shows that within the dynamic reversible assembly only the optimal relative disposition of the redox partners ensures an efficient redox reaction.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | DOUBLE-STRANDED POLYNUCLEOTIDES; MACROCYCLIC ZINC(II) COMPLEXES; PARA-BENZOQUINONE DERIVATIVES; HYDRIDE-TRANSFER REACTIONS; FLAVOENZYME ACTIVITY; GLUTATHIONE-REDUCTASE; SELECTIVE RECOGNITION; ESCHERICHIA-COLI; ELECTRON-TRANSFER; MOLECULAR RECOGNITION; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 26 Aug 2021 12:38 |
| Last Modified: | 26 Aug 2021 12:38 |
| URI: | https://pred.uni-regensburg.de/id/eprint/39678 |
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