Environmental and Nuclear Quantum Effects on Double Proton Transfer in the Guanine–Cytosine Base Pair
In: ISSN: 1948-7185, 2023
Online
academicJournal
Zugriff:
International audience ; In the present letter, we investigate the double proton transfer (DPT) tautomerization process in guanine−cytosine (GC) DNA base pairs. In particular, we study the influence of the biological environment on the mechanism, the kinetics and thermodynamics of such DPT. To this end, we present a molecular dynamics (MD) study in the tight-binding density functional theory framework, and compare the reactivity of the isolated GC dimer with that of the same dimer embedded in a small DNA structure. The impact of nuclear quantum effects (NQEs) is also evaluated using Path Integral based MD. Results show that in the isolated dimer, the DPT occurs via a concerted mechanism, while in the model biological environment, it turns into a stepwise process going through an intermediate structure. One of the water molecules in the vicinity of the proton transfer sites plays an important role as it changes H-bond pattern during the DPT reaction. The inclusion of NQEs has the effect of speeding up the tautomeric-to-canonical reaction, reflecting the destabilization of both the tautomeric and intermediate forms.
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Environmental and Nuclear Quantum Effects on Double Proton Transfer in the Guanine–Cytosine Base Pair
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Autor/in / Beteiligte Person: | Angiolari, Federica ; Huppert, Simon ; Pietrucci, Fabio ; Spezia, Riccardo ; Laboratoire de chimie théorique (LCT) ; Institut de Chimie - CNRS Chimie (INC-CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) ; Institut des Nanosciences de Paris (INSP) ; Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) ; Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC) ; Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement IRD : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
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Zeitschrift: | ISSN: 1948-7185, 2023 |
Veröffentlichung: | HAL CCSD ; American Chemical Society, 2023 |
Medientyp: | academicJournal |
DOI: | 10.1021/acs.jpclett.3c00747 |
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