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2020-08-13Zeitschriftenartikel DOI: 10.18452/21931
Enhancing Tris(pyrazolyl)borate-Based Models of Cysteine/ Cysteamine Dioxygenases through Steric Effects
dc.contributor.authorMüller, Lars
dc.contributor.authorHoof, Santina
dc.contributor.authorKeck, Matthias
dc.contributor.authorHerwig, Christian
dc.contributor.authorLimberg, Christian
dc.date.accessioned2020-09-17T12:07:11Z
dc.date.available2020-09-17T12:07:11Z
dc.date.issued2020-08-13none
dc.identifier.other10.1002/chem.202001818
dc.identifier.urihttp://edoc.hu-berlin.de/18452/22632
dc.description.abstractThe design of biomimetic model complexes for the cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO) is reported, where the 3‐His coordination of the iron ion is simulated by three pyrazole donors of a trispyrazolyl borate ligand (Tp) and protected cysteine and cysteamine represent substrate ligands. It is found that the replacement of phenyl groups—attached at the 3‐positions of the pyrazole units in a previous model—by mesityl residues has massive consequences, as the latter arrange to a more spacious reaction pocket. Thus, the reaction with O2 proceeds much faster and afterwards the first structural characterization of an iron(II) η2‐O,O‐sulfinate product became possible. If one of the three Tp‐mesityl groups is placed in the 5‐position, an even larger reaction pocket results, which leads to yet faster rates and accumulation of a reaction intermediate at low temperatures, as shown by UV/Vis and Mössbauer spectroscopy. After comparison with the results of investigations on the cobalt analogues this intermediate is tentatively assigned to an iron(III) superoxide species.eng
dc.language.isoengnone
dc.publisherHumboldt-Universität zu Berlin
dc.rights(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 Internationalger
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectdioxygenaseseng
dc.subjectenzyme modelseng
dc.subjectnonheme ironeng
dc.subjectreaction intermediateseng
dc.subjectspectroscopyeng
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftennone
dc.subject.ddc660 Chemische Verfahrenstechnik und verwandte Technologiennone
dc.titleEnhancing Tris(pyrazolyl)borate-Based Models of Cysteine/ Cysteamine Dioxygenases through Steric Effectsnone
dc.typearticle
dc.subtitleIncreased Reactivities, Full Product Characterization and Hints to Initial Superoxide Formationnone
dc.identifier.urnurn:nbn:de:kobv:11-110-18452/22632-4
dc.identifier.doihttp://dx.doi.org/10.18452/21931
dc.type.versionpublishedVersionnone
local.edoc.container-titleChemistry - A European Journalnone
local.edoc.pages11none
local.edoc.type-nameZeitschriftenartikel
local.edoc.institutionMathematisch-Naturwissenschaftliche Fakultätnone
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
local.edoc.container-publisher-placeWiley-VCHnone
local.edoc.container-eventWeinheimnone
local.edoc.container-volume26none
local.edoc.container-issue51none
local.edoc.container-firstpage11851none
local.edoc.container-lastpage11861none
dc.description.versionPeer Reviewednone
dc.identifier.eissn1521-3765

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