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Protonated nucleobases are not fully ionized in their chloride salt crystals and form metastable base pairs further stabilized by the surrounding anions

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cris.lastimport.scopus2024-02-12T19:32:30Z
dc.abstract.enhis paper presents experimental charge-density studies of cytosinium chloride, adeninium chloride hemihydrate and guaninium dichloride crystals based on ultra-high-resolution X-ray diffraction data and extensive theoretical calculations. The results confirm that the cohesive energies of the studied systems are dominated by contributions from intermolecular electrostatic interactions, as expected for ionic crystals. Electrostatic interaction energies (E es) usually constitute 95% of the total interaction energy. The E es energies in this study were several times larger in absolute value when compared, for example, with dimers of neutral nucleobases. However, they were not as large as some theoretical calculations have predicted. This was because the molecules appeared not to be fully ionized in the studied crystals. Apart from charge transfer from chlorine to the protonated nucleobases, small but visible charge redistribution within the nucleobase cations was observed. Some dimers of singly protonated bases in the studied crystals, namely a cytosinium-cytosinium trans sugar/sugar edge pair and an adeninium-adeninium trans Hoogsteen/Hoogsteen edge pair, exhibited attractive interactions (negative values of E es) or unusually low repulsion despite identical molecular charges. The pairs are metastable as a result of strong hydrogen bonding between bases which overcompensates the overall cation-cation repulsion, the latter being weakened due to charge transfer and molecular charge-density polarization.
dc.affiliationUniwersytet Warszawski
dc.contributor.authorCabaj, Małgorzata Katarzyna
dc.contributor.authorKumar, Prashant
dc.contributor.authorDominiak, Paulina
dc.contributor.authorPazio, Aleksandra
dc.date.accessioned2024-01-25T18:20:57Z
dc.date.available2024-01-25T18:20:57Z
dc.date.issued2018
dc.description.financeNie dotyczy
dc.description.numberPart 4
dc.description.volume5
dc.identifier.doi10.1107/S2052252518006346
dc.identifier.urihttps://repozytorium.uw.edu.pl//handle/item/117315
dc.languageeng
dc.pbn.affiliationchemical sciences
dc.relation.ispartofIUCrJ
dc.relation.pages449-469
dc.rightsClosedAccess
dc.sciencecloudnosend
dc.subject.encharge density
dc.subject.enmultipole refinement
dc.subject.enquantum crystallography
dc.subject.enelectrostatic potential
dc.subject.enelectrostatic interaction energy
dc.subject.enlike-charged ions
dc.subject.ennucleobases
dc.subject.encytosine
dc.subject.enadenine
dc.subject.enguanine
dc.subject.enbase pairs
dc.subject.enintermolecular interactions
dc.subject.enspin density
dc.subject.enmomentum density
dc.subject.enhydrogen bonding
dc.subject.enpharmaceutical solids
dc.subject.ennucleic acid structures
dc.titleProtonated nucleobases are not fully ionized in their chloride salt crystals and form metastable base pairs further stabilized by the surrounding anions
dc.typeJournalArticle
dspace.entity.typePublication