Reactivity of Flavins with Nucleophiles Using a Theoretical
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F24%3A43928498" target="_blank" >RIV/60461373:22310/24:43928498 - isvavai.cz</a>
Nalezeny alternativní kódy
RIV/60461373:22810/24:43928498
Výsledek na webu
<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202300547" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.202300547</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/cplu.202300547" target="_blank" >10.1002/cplu.202300547</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Reactivity of Flavins with Nucleophiles Using a Theoretical
Popis výsledku v původním jazyce
Covalent adducts of flavin cofactors with nucleophiles play an important role in non-canonical function of flavoenzymes as well as in flavin-based catalysis. Herein, the interaction of flavin derivatives including substituted flavins (isoalloxazines), 1,10-ethylene-bridged flavinium salts, and non-substituted alloxazine and deazaflavin with selected nucleophiles was investigated using an experimental and computational approach. Triphenylphosphine or trimethylphosphine, 1-nitroethan-1-ide, and methoxide were selected as representatives of neutral soft, anionic soft, and hard nucleophiles, respectively. The interactions were investigated using UV/Vis and 1H NMR spectroscopy as well as by DFT calculations. The position of nucleophilic attack estimated using the calculated Gibbs free energy values was found to correspond with the experimental data, favouring the addition of phosphine and 1-nitroethan-1-ide into position N(5) and methoxide into position C(10a) of 1,10-ethylene-bridged flavinium salts. The calculated Gibbs free energy values were found to correlate with the experimental redox potentials of the flavin derivatives tested. These findings can be utilized as valuable tools for the design of artificial flavin-based catalytic systems or investigating the mechanism of flavoenzymes.
Název v anglickém jazyce
Reactivity of Flavins with Nucleophiles Using a Theoretical
Popis výsledku anglicky
Covalent adducts of flavin cofactors with nucleophiles play an important role in non-canonical function of flavoenzymes as well as in flavin-based catalysis. Herein, the interaction of flavin derivatives including substituted flavins (isoalloxazines), 1,10-ethylene-bridged flavinium salts, and non-substituted alloxazine and deazaflavin with selected nucleophiles was investigated using an experimental and computational approach. Triphenylphosphine or trimethylphosphine, 1-nitroethan-1-ide, and methoxide were selected as representatives of neutral soft, anionic soft, and hard nucleophiles, respectively. The interactions were investigated using UV/Vis and 1H NMR spectroscopy as well as by DFT calculations. The position of nucleophilic attack estimated using the calculated Gibbs free energy values was found to correspond with the experimental data, favouring the addition of phosphine and 1-nitroethan-1-ide into position N(5) and methoxide into position C(10a) of 1,10-ethylene-bridged flavinium salts. The calculated Gibbs free energy values were found to correlate with the experimental redox potentials of the flavin derivatives tested. These findings can be utilized as valuable tools for the design of artificial flavin-based catalytic systems or investigating the mechanism of flavoenzymes.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
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OECD FORD obor
10401 - Organic chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/GA21-14179S" target="_blank" >GA21-14179S: Nová strategie přepólování s využitím kovalentní organokatalýzy s flaviny</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2024
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
ChemPlusChem
ISSN
2192-6506
e-ISSN
2192-6506
Svazek periodika
89
Číslo periodika v rámci svazku
2024-01-24
Stát vydavatele periodika
DE - Spolková republika Německo
Počet stran výsledku
7
Strana od-do
"e202300547"
Kód UT WoS článku
001140264700001
EID výsledku v databázi Scopus
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