Enhanced Nuclear Quantum Effects in Radical Cationic Adenine-Thymine Base Pairs
4 affiliations
- 1Gifu University , , Yanagido 1-1 , ,
- 2Institute of Science Tokyo , , 2-12-1 Ookayama , Meguro-ku, ,
- 3Yokohama City University , , 22-2 Seto , Kanazawa-ku, ,
- 4Chulalongkorn University , , 254 Phayathai Road , ,
Abstract
Proton-transfer reactions in DNA base pairs have long been discussed in relation to tautomer formation and mismatch generation during DNA replication. In this study, nuclear quantum effects (NQEs) on neutral and radical cationic adenine–thymine (A–T) base pairs were investigated using classical molecular dynamics (CLMD) and path integral molecular dynamics (PIMD) simulations at the (U)ωB97XD/6–31G** level. For the neutral A–T pair, NQEs mainly affected covalent bond lengths, whereas intermolecular hydrogen-bond distances were only weakly influenced. For the radical cationic A–T+ pair, NQEs instead manifested primarily as a broadening of the proton-transfer distribution and a qualitative reshaping of the free-energy profile. Specifically, the double-well profile obtained with CLMD changed into a broad single-well-like profile in PIMD, accompanied by substantial proton delocalization between adenine and thymine. These results indicate that cationization markedly amplifies NQEs and promotes access to proton-shared and tautomer-like configurations in A–T base pairs.
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BibTeX
@article{udagawa2026enhanced,
title = {{Enhanced Nuclear Quantum Effects in Radical Cationic Adenine-Thymine Base Pairs}},
author = {Taro Udagawa and Takuya Kosugi and Hikaru Tanaka and Kazuaki Kuwahata and Masanori Tachikawa},
journal = {ACS Omega},
year = {2026},
month = oct,
doi = {10.1021/acsomega.6c08290},
url = {https://pubs.acs.org/acsodf/article/11/41/64200/5447776/Enhanced-Nuclear-Quantum-Effects-in-Radical},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Enhanced Nuclear Quantum Effects in Radical Cationic Adenine-Thymine Base Pairs
AU - Taro Udagawa
AU - Takuya Kosugi
AU - Hikaru Tanaka
AU - Kazuaki Kuwahata
AU - Masanori Tachikawa
PY - 2026
DA - 2026/10/09
JO - ACS Omega
DO - 10.1021/acsomega.6c08290
UR - https://pubs.acs.org/acsodf/article/11/41/64200/5447776/Enhanced-Nuclear-Quantum-Effects-in-Radical
AB - Proton-transfer reactions in DNA base pairs have long been discussed in relation to tautomer formation and mismatch generation during DNA replication. In this study, nuclear quantum effects (NQEs) on neutral and radical cationic adenine–thymine (A–T) base pairs were investigated using classical molecular dynamics (CLMD) and path integral molecular dynamics (PIMD) simulations at the (U)ωB97XD/6–31G** level. For the neutral A–T pair, NQEs mainly affected covalent bond lengths, whereas intermolecular hydrogen-bond distances were only weakly influenced. For the radical cationic A–T+ pair, NQEs instead manifested primarily as a broadening of the proton-transfer distribution and a qualitative reshaping of the free-energy profile. Specifically, the double-well profile obtained with CLMD changed into a broad single-well-like profile in PIMD, accompanied by substantial proton delocalization between adenine and thymine. These results indicate that cationization markedly amplifies NQEs and promotes access to proton-shared and tautomer-like configurations in A–T base pairs.
SN - 2470-1343
ER -