Proton transfer in guanine-cytosine base pair analogues studied by NMR spectroscopy and PIMD simulations

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F18%3A00499337" target="_blank" >RIV/61388963:_____/18:00499337 - isvavai.cz</a>

Alternative codes found

RIV/60461373:22340/18:43916704

Result on the web

<a href="https://pubs.rsc.org/en/content/articlehtml/2018/fd/c8fd00070k" target="_blank" >https://pubs.rsc.org/en/content/articlehtml/2018/fd/c8fd00070k</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c8fd00070k" target="_blank" >10.1039/c8fd00070k</a>

Result language

angličtina

Original language name

Proton transfer in guanine-cytosine base pair analogues studied by NMR spectroscopy and PIMD simulations

Original language description

It has been hypothesised that proton tunnelling between paired nucleobases significantly enhances the formation of rare tautomeric forms and hence leads to errors in DNA replication. Here, we study nuclear quantum effects (NQEs) using deuterium isotope-induced changes of nitrogen NMR chemical shifts in a model base pair consisting of two tautomers of isocytosine, which form hydrogen-bonded dimers in the same way as the guanine-cytosine base pair. Isotope effects in NMR are consequences of NQEs, because ro-vibrational averaging of different isotopologues gives rise to different magnetic shielding of the nuclei. The experimental deuterium-induced chemical shift changes are compared with those calculated by a combination of path integral molecular dynamics (PIMD) simulations with DFT calculations of nuclear shielding. These calculations can directly link the observable isotope-induced shifts with NQEs. A comparison of the deuterium-induced changes of N-15 chemical shifts with those predicted by PIMD simulations shows that inter-base proton transfer reactions do not take place in this system. We demonstrate, however, that NMR isotope shifts provide a unique possibility to study NQEs and to evaluate the accuracy of the computational methods used for modelling quantum effects in molecules. Calculations based on the PBE functional from the general-gradient-approximation family provided significantly worse predictions of deuterium isotope shifts than those with the hybrid B3LYP functional.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA18-11851S" target="_blank" >GA18-11851S: Intermolecular interactions studied by NMR spectroscopy and advanced quantum-chemical calculations</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2018

Confidentiality

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

Name of the periodical

Faraday Discussions

ISSN

1359-6640

e-ISSN

—

Volume of the periodical

212

Issue of the periodical within the volume

Dec 1

Country of publishing house

GB - UNITED KINGDOM

Number of pages

14

Pages from-to

331-344

UT code for WoS article

000455021000016

EID of the result in the Scopus database

2-s2.0-85054544876