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dc.contributor.authorChawla, Mohit
dc.contributor.authorPoater, Albert
dc.contributor.authorBesalu-Sala, Pau
dc.contributor.authorKalra, Kanav
dc.contributor.authorOliva, Romina
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2018-02-27T09:00:13Z
dc.date.available2018-02-27T09:00:13Z
dc.date.issued2018-02-23
dc.identifier.citationChawla M, Poater A, Besalu-Sala P, Kalra K, Oliva R, et al. (2018) Theoretical Characterization of Sulfur-to-Selenium Substitution in an Emissive RNA Alphabet: Impact on H-bonding Potential and Photophysical Properties. Physical Chemistry Chemical Physics. Available: http://dx.doi.org/10.1039/c7cp07656h.
dc.identifier.issn1463-9076
dc.identifier.issn1463-9084
dc.identifier.pmid29497733
dc.identifier.doi10.1039/c7cp07656h
dc.identifier.urihttp://hdl.handle.net/10754/627208
dc.description.abstractWe employ density functional theory (DFT) and time-dependent DFT (TDDFT) calculations to investigate the structural, energetic and optical properties of a new computationally designed RNA alphabet, where the nucleobases,tsA, tsG, tsC, and tsU (ts-bases), have been derived by replacing sulfur with selenium in the previously reported tz-bases, based on the isothiazolo[4.3-d]pyrimidine heterocycle core. We find out that the modeled non-natural bases have minimal impact on the geometry and energetics of the classical Watson-Crick base pairs, thus potentially mimicking the 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 of purines are destabilized as compared to their natural counterparts. We also focus on the photophysical properties of the non-natural bases and correlate their absorption/emission peaks to the strong impact of the modification on the energy of the lowest unoccupied molecular orbital. It is indeed stabilized by roughly 1.1-1.6 eV as compared to the natural analogues, resulting in a reduction of the gap between the highest occupied and the lowest unoccupied molecular orbital from 5.3-5.5 eV in the natural bases to 3.9-4.2 eV in the modified ones, with a consequent bathochromic shift in the absorption and emission spectra. Overall, our analysis clearly indicates that the newly modelled ts-bases are expected to exhibit better fluorescent properties as compared to the previously reported tz-bases, while retaining similar H-bonding properties. In addition, we show that a new RNA alphabet based on size-extended benzo-homologated ts-bases can also form stable Watson-Crick base pairs with the natural complementary nucleobases.
dc.description.sponsorshipThe 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. A.P. thanks the Spanish MINECO for a project CTQ2014-59832-JIN. We thank Professor Yitzhak Tor for helpful comments.
dc.publisherRoyal Society of Chemistry (RSC)
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2018/CP/C7CP07656H#!divAbstract
dc.rightsArchived with thanks to Physical Chemistry Chemical Physics
dc.titleTheoretical Characterization of Sulfur-to-Selenium Substitution in an Emissive RNA Alphabet: Impact on H-bonding Potential and Photophysical Properties
dc.typeArticle
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.identifier.journalPhysical Chemistry Chemical Physics
dc.eprint.versionPost-print
dc.contributor.institutionInstitut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona, Mª Aurèlia Campmany, 17003 Girona, Catalonia, Spain.
dc.contributor.institutionDepartment of Sciences and Technologies, University Parthenope of Naples, Centro Direzionale Isola C4, I-80143, Naples, Italy.
kaust.personChawla, Mohit
kaust.personPoater, Albert
kaust.personKalra, Kanav
kaust.personCavallo, Luigi


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