Structural and energetic characterization of the emissive RNA alphabet based on the isothiazolo[4,3-: D] pyrimidine heterocycle core
dc.contributor.author
dc.date.accessioned
2016-11-18T07:52:00Z
dc.date.available
2016-11-18T07:52:00Z
dc.date.issued
2016-01-01
dc.identifier.issn
1463-9076
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dc.description.abstract
We present theoretical characterization of fluorescent non-natural nucleobases, tzA, tzG, tzC, and tzU, derived from the isothiazolo[4,3-d]pyrimidine heterocycle. Consistent with the experimental evidence, our calculations show that the non-natural bases have minimal impact on the geometry and stability of the classical Watson-Crick base pairs, allowing them to accurately mimic natural bases in a RNA duplex, in terms of H-bonding. In contrast, our calculations indicate that H-bonded base pairs involving the Hoogsteen edge are destabilized relative to their natural counterparts. Analysis of the photophysical properties of the non-natural bases allowed us to correlate their absorption/emission peaks to the strong impact of the modification on the energy of the lowest unoccupied molecular orbital, LUMO, which is stabilized by roughly 1.0-1.2 eV relative to the natural analogues, while the highest occupied molecular orbital, HOMO, is not substantially affected. As a result, the HOMO-LUMO gap is reduced from 5.3-5.5 eV in the natural bases to 4.0-4.4 eV in the modified ones, with a consequent bathochromic shift in the absorption and emission spectra
dc.description.sponsorship
The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia, project K1017. A. P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c6cp03268k
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© Physical Chemistry Chemical Physics, 2016, vol. 18, núm. 27, p. 18045-18053
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
Structural and energetic characterization of the emissive RNA alphabet based on the isothiazolo[4,3-: D] pyrimidine heterocycle core
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
025570
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1463-9084