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Article: Electronic Effect on Bimetallic Catalysts: Cleavage of Phosphodiester Mediated by Fe(III)–Zn(II) Purple Acid Phosphatase Mimics

TitleElectronic Effect on Bimetallic Catalysts: Cleavage of Phosphodiester Mediated by Fe(III)–Zn(II) Purple Acid Phosphatase Mimics
Authors
Issue Date2020
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2020, v. 59 n. 17, p. 12065-12074 How to Cite?
AbstractThe bimetallic system is an important strategy for the catalytic hydrolysis of phosphodiester. The purple acid phosphatase (PAPs) enzyme is a typical bimetallic catalyst in this field. Mechanistic details for the hydrolysis cleavage of the DNA dinucleotide analogue BNPP– (BNPP– = bis(p-nitrophenyl) phosphate) by hetero-binuclear [FeIII(μ-OH)ZnIIL]2+ complexes (L = 2-[N-bis(2-pyridylmethyl)-aminomethyl]-4-methyl-6-[N′-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl] phenol) were investigated using density functional theory calculations. The catalysts with single-bridged hydroxyl and double-bridged hydroxyl groups were compared. The calculation results show that the doubly hydroxide-bridged complex could better bind to substrates. For the BNPP– hydrolysis, the doubly hydroxide-bridged reactant isomerizes into a single hydroxide-bridged complex, and then the attack is initiated by the hydroxyl group on the iron center. In addition, the catalyst with the electron-donating group (Me) was determined to take precedence over electron-withdrawing groups (Br and NO2 groups) in the hydrolysis reaction. This is because the substituents affect the high-lying occupied molecular orbitals, tuning the Lewis acidity of iron and pKa values of the metal-bonded water. These factors influence the hydroxyl nucleophilicity, leading to changes in catalytic activity. To further examine substituent effects, the occupied orbital energies were calculated with several different substituent groups (-CF3, -OMe, -OH, -NH2, and -N(Me)2). It was found that the HOMO or HOMO-1 energy decreases with the increase of the σp value. Further, the catalyst activity of the [FeIII(μ-OH)ZnIIL]2+ complexes was found to be mainly affected by the phenolate ligand (B) coordinated to the iron and zinc centers. These fundamental aspects of the hydrolysis reactions of BNPP– catalyzed by [FeIII(μ-OH)ZnIIL]2+ complexes should contribute to improved understanding of the mechanism and to catalyst design involving hetero-binuclear metals complexes.
Persistent Identifierhttp://hdl.handle.net/10722/300771
ISSN
2020 Impact Factor: 5.165
2020 SCImago Journal Rankings: 1.348

 

DC FieldValueLanguage
dc.contributor.authorZhou, X-
dc.contributor.authorZhang, XP-
dc.contributor.authorLi, W-
dc.contributor.authorPhillips, DL-
dc.contributor.authorKe, Z-
dc.contributor.authorZhao, C-
dc.date.accessioned2021-07-06T03:10:01Z-
dc.date.available2021-07-06T03:10:01Z-
dc.date.issued2020-
dc.identifier.citationInorganic Chemistry, 2020, v. 59 n. 17, p. 12065-12074-
dc.identifier.issn0020-1669-
dc.identifier.urihttp://hdl.handle.net/10722/300771-
dc.description.abstractThe bimetallic system is an important strategy for the catalytic hydrolysis of phosphodiester. The purple acid phosphatase (PAPs) enzyme is a typical bimetallic catalyst in this field. Mechanistic details for the hydrolysis cleavage of the DNA dinucleotide analogue BNPP– (BNPP– = bis(p-nitrophenyl) phosphate) by hetero-binuclear [FeIII(μ-OH)ZnIIL]2+ complexes (L = 2-[N-bis(2-pyridylmethyl)-aminomethyl]-4-methyl-6-[N′-(2-pyridylmethyl)(2-hydroxybenzyl) aminomethyl] phenol) were investigated using density functional theory calculations. The catalysts with single-bridged hydroxyl and double-bridged hydroxyl groups were compared. The calculation results show that the doubly hydroxide-bridged complex could better bind to substrates. For the BNPP– hydrolysis, the doubly hydroxide-bridged reactant isomerizes into a single hydroxide-bridged complex, and then the attack is initiated by the hydroxyl group on the iron center. In addition, the catalyst with the electron-donating group (Me) was determined to take precedence over electron-withdrawing groups (Br and NO2 groups) in the hydrolysis reaction. This is because the substituents affect the high-lying occupied molecular orbitals, tuning the Lewis acidity of iron and pKa values of the metal-bonded water. These factors influence the hydroxyl nucleophilicity, leading to changes in catalytic activity. To further examine substituent effects, the occupied orbital energies were calculated with several different substituent groups (-CF3, -OMe, -OH, -NH2, and -N(Me)2). It was found that the HOMO or HOMO-1 energy decreases with the increase of the σp value. Further, the catalyst activity of the [FeIII(μ-OH)ZnIIL]2+ complexes was found to be mainly affected by the phenolate ligand (B) coordinated to the iron and zinc centers. These fundamental aspects of the hydrolysis reactions of BNPP– catalyzed by [FeIII(μ-OH)ZnIIL]2+ complexes should contribute to improved understanding of the mechanism and to catalyst design involving hetero-binuclear metals complexes.-
dc.languageeng-
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic-
dc.relation.ispartofInorganic Chemistry-
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in [JournalTitle], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [insert ACS Articles on Request author-directed link to Published Work, see http://pubs.acs.org/page/policy/articlesonrequest/index.html].-
dc.titleElectronic Effect on Bimetallic Catalysts: Cleavage of Phosphodiester Mediated by Fe(III)–Zn(II) Purple Acid Phosphatase Mimics-
dc.typeArticle-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/acs.inorgchem.0c01011-
dc.identifier.pmid32805999-
dc.identifier.scopuseid_2-s2.0-85089979554-
dc.identifier.hkuros323192-
dc.identifier.volume59-
dc.identifier.issue17-
dc.identifier.spage12065-
dc.identifier.epage12074-
dc.publisher.placeUnited States-

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