Shining a Spotlight on Methyl Groups : Photochemically Induced Dynamic Nuclear Polarization Spectroscopy of 5-Deazariboflavin and Its Nor Analogs
5-Deazaflavins are analogs of naturally occurring flavin cofactors. They serve as substitutes for natural flavin cofactors to investigate and modify the reaction pathways of flavoproteins. Demethylated 5-deazaflavins are potential candidates for artificial cofactors, allowing us to fine-tune the reaction kinetics and absorption characteristics of flavoproteins. In this contribution, demethylated 5-deazariboflavin radicals are investigated (1) to assess the influence of the methyl groups on the electronic structure of the 5-deazaflavin radical and (2) to explore their photophysical properties with regard to their potential as artificial cofactors. We determined the proton hyperfine structure of demethylated 5-deazariboflavins using photochemically induced dynamic nuclear polarization (photo-CIDNP) spectroscopy, as well as density functional theory (DFT). To provide context, we compare our findings to a study of flavin mononucleotide (FMN) derivatives. We found a significant influence of the methylation pattern on the absorption properties, as well as on the proton hyperfine coupling ratios of the xylene moiety, which appears to be solvent-dependent. This effect is enhanced by the replacement of N5 by C5-H in 5-deazaflavin derivatives compared to their respective flavin counterparts.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:25 |
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| Enthalten in: |
International journal of molecular sciences - 25(2024), 2 vom: 10. Jan. |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Panter, Sabrina [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 24.01.2024 Date Revised 28.01.2024 published: Electronic Citation Status MEDLINE |
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| doi: |
10.3390/ijms25020848 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| 245 | 1 | 0 | |a Shining a Spotlight on Methyl Groups |b Photochemically Induced Dynamic Nuclear Polarization Spectroscopy of 5-Deazariboflavin and Its Nor Analogs |
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| 520 | |a 5-Deazaflavins are analogs of naturally occurring flavin cofactors. They serve as substitutes for natural flavin cofactors to investigate and modify the reaction pathways of flavoproteins. Demethylated 5-deazaflavins are potential candidates for artificial cofactors, allowing us to fine-tune the reaction kinetics and absorption characteristics of flavoproteins. In this contribution, demethylated 5-deazariboflavin radicals are investigated (1) to assess the influence of the methyl groups on the electronic structure of the 5-deazaflavin radical and (2) to explore their photophysical properties with regard to their potential as artificial cofactors. We determined the proton hyperfine structure of demethylated 5-deazariboflavins using photochemically induced dynamic nuclear polarization (photo-CIDNP) spectroscopy, as well as density functional theory (DFT). To provide context, we compare our findings to a study of flavin mononucleotide (FMN) derivatives. We found a significant influence of the methylation pattern on the absorption properties, as well as on the proton hyperfine coupling ratios of the xylene moiety, which appears to be solvent-dependent. This effect is enhanced by the replacement of N5 by C5-H in 5-deazaflavin derivatives compared to their respective flavin counterparts | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a 5-deazaflavin | |
| 650 | 4 | |a hyperfine coupling | |
| 650 | 4 | |a hyperpolarization | |
| 650 | 4 | |a photo-CIDNP | |
| 650 | 4 | |a spin-correlated radical pair | |
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| 700 | 1 | |a Ayekoi, Audrey |e verfasserin |4 aut | |
| 700 | 1 | |a Tesche, Jannis |e verfasserin |4 aut | |
| 700 | 1 | |a Chen, Jing |e verfasserin |4 aut | |
| 700 | 1 | |a Illarionov, Boris |e verfasserin |4 aut | |
| 700 | 1 | |a Bacher, Adelbert |e verfasserin |4 aut | |
| 700 | 1 | |a Fischer, Markus |e verfasserin |4 aut | |
| 700 | 1 | |a Weber, Stefan |e verfasserin |4 aut | |
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