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https://hdl.handle.net/1959.11/56016
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DC Field | Value | Language |
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dc.contributor.author | O'Reilly, Robert J | en |
dc.contributor.author | Karton, Amir | en |
dc.date.accessioned | 2023-09-12T00:46:31Z | - |
dc.date.available | 2023-09-12T00:46:31Z | - |
dc.date.issued | 2023-06 | - |
dc.identifier.citation | Electronic Structure, 5(2), p. 1-12 | en |
dc.identifier.issn | 2516-1075 | en |
dc.identifier.uri | https://hdl.handle.net/1959.11/56016 | - |
dc.description.abstract | <p>The relative free energies of the isomers formed upon <i>N</i>-chlorination of each nitrogen atom within the DNA nucleobases (adenine, guanine, and thymine) have been obtained using the high-level G4(MP2) composite <i>ab initio</i> method (the free energies of the <i>N</i>-chlorinated isomers of cytosine have been reported at the same level of theory previously). Having identified the lowest energy <i>N</i>-chlorinated derivatives for each nucleobase, we have computed the free energies associated with chlorine transfer from <i>N</i>-chlorinated nucleobases to other unsubstituted bases. Our results provide quantitative support pertaining to the results of previous experimental studies, which demonstrated that rapid chlorine transfer occurs from <i>N</i>-chlorothymidine to cytidine or adenosine. The results of our calculations in the gas-phase reveal that chlorine transfer from <i>N</i>-chlorothymine to either cytosine, adenine, or guanine proceed via exergonic processes with ∆G<sup>o</sup> values of −50.3 (cytosine), −28.0 (guanine), and −6.7 (adenine) kJ mol<sup>–1</sup>. Additionally, we consider the effect of aqueous solvation by augmenting our gas-phase G4(MP2) energies with solvation corrections obtained using the conductor-like polarizable continuum model. In aqueous solution, we obtain the following G4(MP2) free energies associated with chlorine transfer from <i>N</i>-chlorothymine to the three other nucleobases: −58.4 (cytosine), −26.4 (adenine), and −18.7 (guanine) kJ mol<sup>–1</sup>. Therefore, our calculations, whether in the gas phase or in aqueous solution, clearly indicate that chlorine transfer from any of the <i>N</i>-chlorinated nucleobases to cytosine provides a thermodynamic sink for the active chlorine. This thermodynamic preference for chlorine transfer to cytidine may be particularly deleterious since previous experimental studies have shown that nitrogen-centered radical formation (via N–Cl bond homolysis) is more easily achieved in <i>N</i>-chlorinated cytidine than in other <i>N</i>-chlorinated nucleosides. </p> | en |
dc.language | en | en |
dc.publisher | Institute of Physics Publishing Ltd | en |
dc.relation.ispartof | Electronic Structure | en |
dc.title | A high-level quantum chemical study of the thermodynamics associated with chlorine transfer between N-chlorinated nucleobases | en |
dc.type | Journal Article | en |
dc.identifier.doi | 10.1088/2516-1075/acd234 | en |
local.contributor.firstname | Robert J | en |
local.contributor.firstname | Amir | en |
local.profile.school | School of Science & Technology | en |
local.profile.school | School of Science and Technology | en |
local.profile.email | roreill6@une.edu.au | en |
local.profile.email | akarton@une.edu.au | en |
local.output.category | C1 | en |
local.record.place | au | en |
local.record.institution | University of New England | en |
local.publisher.place | United Kingdom | en |
local.identifier.runningnumber | 024005 | en |
local.format.startpage | 1 | en |
local.format.endpage | 12 | en |
local.peerreviewed | Yes | en |
local.identifier.volume | 5 | en |
local.identifier.issue | 2 | en |
local.contributor.lastname | O'Reilly | en |
local.contributor.lastname | Karton | en |
dc.identifier.staff | une-id:roreill6 | en |
dc.identifier.staff | une-id:akarton | en |
local.profile.orcid | 0000-0002-5000-1920 | en |
local.profile.orcid | 0000-0002-7981-508X | en |
local.profile.role | author | en |
local.profile.role | author | en |
local.identifier.unepublicationid | une:1959.11/56016 | en |
local.date.onlineversion | 2023-05-12 | - |
dc.identifier.academiclevel | Academic | en |
dc.identifier.academiclevel | Academic | en |
local.title.maintitle | A high-level quantum chemical study of the thermodynamics associated with chlorine transfer between N-chlorinated nucleobases | en |
local.output.categorydescription | C1 Refereed Article in a Scholarly Journal | en |
local.search.author | O'Reilly, Robert J | en |
local.search.author | Karton, Amir | en |
local.open.fileurl | https://rune.une.edu.au/web/retrieve/002b807c-a01e-44c5-b002-aa53cec82db7 | en |
local.uneassociation | Yes | en |
local.atsiresearch | No | en |
local.sensitive.cultural | No | en |
local.year.available | 2023 | - |
local.year.published | 2023 | - |
local.fileurl.open | https://rune.une.edu.au/web/retrieve/002b807c-a01e-44c5-b002-aa53cec82db7 | en |
local.fileurl.closedpublished | https://rune.une.edu.au/web/retrieve/002b807c-a01e-44c5-b002-aa53cec82db7 | en |
local.subject.for2020 | 340701 Computational chemistry | en |
local.subject.seo2020 | 280120 Expanding knowledge in the physical sciences | en |
local.profile.affiliationtype | UNE Affiliation | en |
local.profile.affiliationtype | UNE Affiliation | en |
Appears in Collections: | Journal Article School of Science and Technology |
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