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Thermodynamics of 5-bromouracil tautomerisation from first-principles molecular dynamics simulations
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dc.contributor.author | Holroyd, Leo F. | |
dc.contributor.author | Buehl, Michael | |
dc.contributor.author | Gaigeot, Marie-Pierre | |
dc.contributor.author | van Mourik, Tanja | |
dc.contributor.editor | Jenkins, Samantha | |
dc.contributor.editor | Kirk, Steven | |
dc.contributor.editor | Maruani, Jean | |
dc.contributor.editor | Brandas, Erkki | |
dc.date.accessioned | 2019-01-14T17:30:10Z | |
dc.date.available | 2019-01-14T17:30:10Z | |
dc.date.issued | 2019-01-01 | |
dc.identifier | 252912294 | |
dc.identifier | 969e090c-3330-4043-8786-e43fcda9bd65 | |
dc.identifier | 85048708983 | |
dc.identifier | 000500361700007 | |
dc.identifier.citation | Holroyd , L F , Buehl , M , Gaigeot , M-P & van Mourik , T 2019 , Thermodynamics of 5-bromouracil tautomerisation from first-principles molecular dynamics simulations . in S Jenkins , S Kirk , J Maruani & E Brandas (eds) , Quantum Systems in Physics, Chemistry and Biology - Theory, Interpretation, and Results . Advances of Quantum Chemistry , vol. 78 , Academic Press/Elsevier , pp. 109-128 . https://doi.org/10.1016/bs.aiq.2018.05.001 | en |
dc.identifier.isbn | 9780128160848 | |
dc.identifier.issn | 0065-3276 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/52888695 | |
dc.identifier.other | ORCID: /0000-0001-7683-3293/work/57088476 | |
dc.identifier.uri | https://hdl.handle.net/10023/16860 | |
dc.description | The authors acknowledge support from the Engineering and Physical Sciences Research Council (EPSRC) UK National Service for Computational Chemistry Software (NSCCS); from GENCI (Grand équipement national de calcul intensif); and from CINES (Centre informatique national de l’enseignement supérieur). LFH and TvM gratefully acknowledge support from the HPC-EUROPA2 project with the support of the European Commission - Capacities Area - Research Infrastructures. LFH is grateful to the EPSRC for studentship support through the Doctoral Training Account scheme (grant code EP/K503162/1). | en |
dc.description.abstract | We modelled the driving force for aqueous keto-to-enol tautomerisation of 5-bromouracil, a mutagenic thymine analogue, by first-principles molecular dynamics simulations with thermodynamic integration. Using interatomic distance constraints to model the water-assisted (de)protonation of 5-bromouracil in a periodic water box, we show that the free energy for its enolisation is lower than that of the parent compound, uracil, by around 3.0 kcal/mol (BLYP-D2 level), enough to significantly alter the relative tautomeric ratios. Assuming the energetic difference also holds in the cell, this finding is evidence for the “rare tautomer” hypothesis of 5-bromouracil mutagenicity (and, possibly, that of other base analogues). | |
dc.format.extent | 741863 | |
dc.language.iso | eng | |
dc.publisher | Academic Press/Elsevier | |
dc.relation.ispartof | Quantum Systems in Physics, Chemistry and Biology - Theory, Interpretation, and Results | en |
dc.relation.ispartofseries | Advances of Quantum Chemistry | en |
dc.subject | Density functional theory | en |
dc.subject | Nucleobases | en |
dc.subject | Solvation effects | en |
dc.subject | Mutagenesis | en |
dc.subject | CPMD | en |
dc.subject | Bromouracil | en |
dc.subject | QD Chemistry | en |
dc.subject.lcc | QD | en |
dc.title | Thermodynamics of 5-bromouracil tautomerisation from first-principles molecular dynamics simulations | en |
dc.type | Book item | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1016/bs.aiq.2018.05.001 | |
dc.identifier.url | https://www.sciencedirect.com/bookseries/advances-in-quantum-chemistry/vol/78/suppl/C | en |
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