Oxidation potentials of guanine species

Kód výsledku v IS VaVaI

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Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Oxidation potentials of guanine species

Popis výsledku v původním jazyce

Guanine (G) belongs to the most easily oxidizable nucleobases which is well known from various experimental and theoretical studies. Our contribution is directed towards studies, in which we compare theoretical oxidation potentials with their experimentally measured values for guanine (G), guanosine (Guo), deoxyguanosine (dGuo), guanosine -5´- monophosphate (GMP) and 2´- deoxyguanosine -5´- monophosphate (dGMP). For determination of experimental oxidation potentials of all G species linear sweep voltammetry was applied using polymer pencil graphite electrodes (pPeGEs). It was found that the oxidation process for all studied derivatives is irreversible and strongly pH dependent. Anodic peak potentials increase in the order G &lt;&lt; dGMP &lt; GMP &lt; dGuo &lt; Guo and correlate well with the calculated thermodynamic redox potentials. For the determination of theoretical oxidation potentials the structures of G and its derivatives were optimized and the identities of minima were verified by vibration frequency calculations. Redox equilibria were modeled in terms of corresponding thermochemical cycles. The changes in free energy were calculated at DFT level using two different functionals: (a) general purpose B3LYP functional, and (b) a more specific omegaB97X-D functional, both based on a 6-31+G(d) set. Conformity of theoretical and experimental data for radicals (cationic or neutral, respectively) indicates that the deprotonation process of G differs from its analogues whereas the oxidation process of all species takes place on the imidazole ring.

Název v anglickém jazyce

Oxidation potentials of guanine species

Popis výsledku anglicky

Guanine (G) belongs to the most easily oxidizable nucleobases which is well known from various experimental and theoretical studies. Our contribution is directed towards studies, in which we compare theoretical oxidation potentials with their experimentally measured values for guanine (G), guanosine (Guo), deoxyguanosine (dGuo), guanosine -5´- monophosphate (GMP) and 2´- deoxyguanosine -5´- monophosphate (dGMP). For determination of experimental oxidation potentials of all G species linear sweep voltammetry was applied using polymer pencil graphite electrodes (pPeGEs). It was found that the oxidation process for all studied derivatives is irreversible and strongly pH dependent. Anodic peak potentials increase in the order G &lt;&lt; dGMP &lt; GMP &lt; dGuo &lt; Guo and correlate well with the calculated thermodynamic redox potentials. For the determination of theoretical oxidation potentials the structures of G and its derivatives were optimized and the identities of minima were verified by vibration frequency calculations. Redox equilibria were modeled in terms of corresponding thermochemical cycles. The changes in free energy were calculated at DFT level using two different functionals: (a) general purpose B3LYP functional, and (b) a more specific omegaB97X-D functional, both based on a 6-31+G(d) set. Conformity of theoretical and experimental data for radicals (cationic or neutral, respectively) indicates that the deprotonation process of G differs from its analogues whereas the oxidation process of all species takes place on the imidazole ring.

Druh

D - Stať ve sborníku

CEP obor

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OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

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Návaznosti

S - Specificky vyzkum na vysokych skolach

Rok uplatnění

2019

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název statě ve sborníku

XIX. Workshop of Biophysical Chemists and Electrochemists

ISBN

9788021093096

ISSN

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e-ISSN

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Počet stran výsledku

2

Strana od-do

59-60

Název nakladatele

Masarykova univerzita

Místo vydání

Brno

Místo konání akce

Brno

Datum konání akce

14. 6. 2019

Typ akce podle státní příslušnosti

EUR - Evropská akce

Kód UT WoS článku

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