Abstract
For many years, non-covalently bonded complexes of nucleobases have attracted considerable interest. However, there is a lack of information about the nature of hydrogen bonding between nucleobases when the bonding is affected by metal coordination to one of the nucleobases, and how the individual hydrogen bonds and aromaticity of nucleobases respond to the presence of the metal cation. Here we report a DFT computational study of nucleobase pairs interacting with alkali metal cations. The metal cations contribute to the stabilization of the base pairs to varying degrees depending on their position. The energy decomposition analysis revealed that the nature of bonding between nucleobases does not change much upon metal coordination. The effect of the cations on individual hydrogen bonds were described by changes in VDD charges on frontier atoms, H-bond length, bond energy from NBO analysis, and the delocalization index from QTAIM calculations. The aromaticity changes were determined by a HOMA index.
Original language | English |
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Pages (from-to) | 2112-2126 |
Number of pages | 15 |
Journal | ChemPhysChem |
Volume | 21 |
Issue number | 18 |
Early online date | 9 Jul 2020 |
DOIs | |
Publication status | Published - 15 Sept 2020 |
Funding
M. Solà and O.A.S. are grateful to the Ministerio de Economía y Competitividad (MINECO) of Spain (project CTQ2017‐85341‐P and Juan de la Cierva formación contract FJCI‐2017‐32757 to O.A.S.) and the Generalitat de Catalunya (project 2017SGR39). H.S. and T.M.K. thank the National Science Centre of Poland for supporting this work under the grant no. UMO‐2016/23/B/ST4/00082. M. Swart acknowledges MICINN/MINECO (projects CTQ2014‐59212‐P, CTQ2015‐70851‐ERC, CTQ2017‐87392‐P), GenCat (2014SGR1202, 2017SGR1434 and XRQTC network) and European Fund for Regional Development (FEDER, UNGI104E801). C.F.G. thanks the Netherlands Organization for Scientific Research (NWO) for financial support.
Funders | Funder number |
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MICINN/MINECO | 2014SGR1202, 2017SGR1434 |
National Science Centre of Poland | UMO‐2016/23/B/ST4/00082 |
Netherlands Organization for Scientific Research | |
Generalitat de Catalunya | 2017SGR39 |
Nederlandse Organisatie voor Wetenschappelijk Onderzoek | |
Ministerio de Economía y Competitividad | FJCI‐2017‐32757 |
European Regional Development Fund | UNGI104E801 |
Keywords
- alkali metals
- aromaticity
- density functional calculations
- hydrogen bonds
- nucleobases