Double proton transfer in the isolated and DNA-embedded guanine-cytosine base pair.

Détails

ID Serval
serval:BIB_11BB153D72A3
Type
Article: article d'un périodique ou d'un magazine.
Collection
Publications
Titre
Double proton transfer in the isolated and DNA-embedded guanine-cytosine base pair.
Périodique
The Journal of chemical physics
Auteur⸱e⸱s
Zoete V., Meuwly M.
ISSN
0021-9606 (Print)
ISSN-L
0021-9606
Statut éditorial
Publié
Date de publication
01/09/2004
Peer-reviewed
Oui
Volume
121
Numéro
9
Pages
4377-4388
Langue
anglais
Notes
Publication types: Journal Article ; Research Support, Non-U.S. Gov't
Publication Status: ppublish
Résumé
The energetics and dynamics of double proton transfer (DPT) is investigated theoretically for the Watson-Crick conformation of the guanine-cytosine (GC) base pair. Using semiempirical density functional theory the isolated and DNA-embedded GC pair is considered. Differences in the energetics and dynamics of DPT thus addresses the question of how relevant studies of isolated base pairs are for the understanding of processes occurring in DNA. Two-dimensional potential energy surfaces involving the transferring hydrogen atoms and the proton donors and acceptors are presented for both systems. The DPT reaction is accompanied by a contraction of the distance between the two bases with virtually identical energetic barriers being 18.8 and 18.7 kcal/mol for the isolated and DNA-embedded system, respectively. However, the transition state for DPT in the DNA-embedded GC pair is offset by 0.1 A to larger N-H separation compared to the isolated GC pair. Using activated ab initio molecular dynamics, DPT is readily observed for the isolated base pair with a minimal amount of 21.4 kcal/mol of initial average kinetic energy along the DPT normal mode vector. On a time scale of approximately 100 fs DPT has occurred and the excess energy is redistributed. For the DNA-embedded GC pair considerably more kinetic energy is required (30.0 kcal/mol) for DPT and the process is completed within one hydrogen vibration. The relevance of studies of isolated base pairs and base pair analogs in regard of reactions or properties involving DNA is discussed.

Mots-clé
Base Pairing, Biological Transport, Cytosine/chemistry, DNA/chemistry, Guanine/chemistry, Protons
Pubmed
Web of science
Création de la notice
05/02/2018 16:02
Dernière modification de la notice
21/08/2019 6:37
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