Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Jeong, Donghyun | - |
dc.contributor.author | Sun, Seungwon | - |
dc.contributor.author | Moon, Dohyun | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.accessioned | 2021-11-26T08:30:04Z | - |
dc.date.available | 2021-11-26T08:30:04Z | - |
dc.date.created | 2021-11-04 | - |
dc.date.issued | 2022-01 | - |
dc.identifier.issn | 0162-0134 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/15866 | - |
dc.description.abstract | Quercetin 2,4-dioyxgenase (QueD) has been known to catalyze the oxygenative degradation of flavonoids and quercetin. Recent crystallographic study revealed a nickel ion occupies the active site as a co-factor to support O2 activation and catalysis. Herein, we report a nickel(II) flavonolate complex bearing a tridentate macrocyclic ligand, [NiII(Me3-TACN)(Fl)(NO3)](H2O) (1, Me3-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane, Fl = 3-hydroxyflavone) as a functional model for QueD. The flavonolatonickel(II) complex was characterized by using spectrometric analysis including UV–vis spectroscopy, electrospray ionization mass spectrometer (ESI-MS), infrared spectroscopy (FT-IR) and 1H nuclear magnetic resonance spectroscopy (NMR). The single crystal X-ray structure of 1 shows two isomers with respect to the direction of a flavonolate ligand. Two isomers commonly are in the octahedral geometry with a bidentate of flavonolate and a monodentate of nitrate as well as a tridentate binding of Me3-TACN ligand. The spin state of 1 is determined to be a triplet state based on the Evans' method. Interestingly, electronic configuration of 1 from density functional theory (DFT) calculations revealed that the two singly occupied molecular orbitals (SOMOs) lie energetically lower than the highest (doubly) occupied molecular orbital (HOMO), that is so-called the SOMO-HOMO level inversion (SHI). The HOMO shows an electron density localized in the flavonolate ligand, indicating that flavonolate ligand is oxidized first rather than the nickel center. Thermal degradation of 1 resulted in the formation of benzoic acid and salicylic acid, which is attributed to the oxygenation of flavonolate of 1. © 2021 | - |
dc.language | English | - |
dc.publisher | Elsevier | - |
dc.title | A functional model for quercetin 2,4-dioxygenase: Geometric and electronic structures and reactivity of a nickel(II) flavonolate complex | - |
dc.type | Article | - |
dc.identifier.doi | 10.1016/j.jinorgbio.2021.111632 | - |
dc.identifier.wosid | 000711955100003 | - |
dc.identifier.scopusid | 2-s2.0-85117721053 | - |
dc.identifier.bibliographicCitation | Journal of Inorganic Biochemistry, v.226 | - |
dc.description.isOpenAccess | FALSE | - |
dc.subject.keywordAuthor | Quercetin dioyxgenase | - |
dc.subject.keywordAuthor | Functional model complex | - |
dc.subject.keywordAuthor | Nickel(II) complex | - |
dc.subject.keywordAuthor | Flavonol adduct | - |
dc.subject.keywordAuthor | Oxygenation reaction | - |
dc.subject.keywordAuthor | SOMO-HOMO inversion | - |
dc.subject.keywordPlus | ENZYME-SUBSTRATE COMPLEX | - |
dc.subject.keywordPlus | OXYGENATION | - |
dc.subject.keywordPlus | CU | - |
dc.subject.keywordPlus | NI | - |
dc.subject.keywordPlus | CRYSTALLOGRAPHY | - |
dc.subject.keywordPlus | COORDINATION | - |
dc.subject.keywordPlus | CONVERSION | - |
dc.subject.keywordPlus | MANGANESE | - |
dc.subject.keywordPlus | MECHANISM | - |
dc.subject.keywordPlus | ENERGIES | - |
dc.citation.title | Journal of Inorganic Biochemistry | - |
dc.citation.volume | 226 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Biochemistry & Molecular Biology; Chemistry | - |
dc.relation.journalWebOfScienceCategory | Biochemistry & Molecular Biology; Chemistry, Inorganic & Nuclear | - |
dc.type.docType | Article | - |
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