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Studies on the catalytic mechanism of lactate oxidase : formation of enantiometric flavin-N(5)-glycollyl adducts via carbanion intermediates

Studies on the catalytic mechanism of lactate oxidase : formation of enantiometric flavin-N(5)-glycollyl adducts via carbanion intermediates

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GHISLA, Sandro, Vincent MASSEY, 1980. Studies on the catalytic mechanism of lactate oxidase : formation of enantiometric flavin-N(5)-glycollyl adducts via carbanion intermediates. In: Journal of Biological Chemistry. 255(12), pp. 5688-5696

@article{Ghisla1980Studi-8159, title={Studies on the catalytic mechanism of lactate oxidase : formation of enantiometric flavin-N(5)-glycollyl adducts via carbanion intermediates}, year={1980}, number={12}, volume={255}, journal={Journal of Biological Chemistry}, pages={5688--5696}, author={Ghisla, Sandro and Massey, Vincent} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/8159"> <dc:rights>deposit-license</dc:rights> <dcterms:title>Studies on the catalytic mechanism of lactate oxidase : formation of enantiometric flavin-N(5)-glycollyl adducts via carbanion intermediates</dcterms:title> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T17:41:03Z</dcterms:available> <dc:format>application/pdf</dc:format> <dc:creator>Ghisla, Sandro</dc:creator> <dc:contributor>Ghisla, Sandro</dc:contributor> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:creator>Massey, Vincent</dc:creator> <dcterms:abstract xml:lang="eng">L-Lactate oxidase from Mycobacterium smegmatis reacts with the prochiral subsgtlryactoel late and forms a labile, catalytically competent glycollyl adduct in addition to a similar, but comparatively stable adduct (Massey, V., Ghisla, S., and Kieschke, K. (1980) J. Bid. Chem 255,2796-2806). The latter was isolated by Sephadex G-25 chromatography at 0-4°C and was also obtained from lactate oxidase, in which FMN had been replaced by the analogue 2-thio-FMN. The stable adduct is identical with the product obtained from illumination of the lactate oxidase●tartronate complex (Ghisla, S., Massey, V., and Choong, Y. S. (1979) J. Biol. Chem 254, 10662-10669) and thus has the structure of a glycollyl adduct to position N(5) of the reduced enzyme flavin. The stable adduct decays directly to oxidized enzyme and glycollate, with a t1/2 of 20 min at 25°C; the Arrhenius activation energy 21.4 kcal/mol. When the adduct is formed from reaction with [2,S- 2H] or with α-dideuteroglycollate, the decay reaction shows an isotope effect of 1.5. In contrast, no isotope effect is observed when the adduct is obtained from [2,R-2H]glycollate. Using [2,R-3H]- and [2,S-3H]glycollate, it is shown that the enzyme oxidizes catalytically the Re-hydrogen of this substrate, which is stereochemically equivalent to the α-hydrogen of L-lactate. On decay of the adduct, the Si-hydrogen bond of glycollate is (re)formed. This is demonstrated by the stereochemistry of glycollate obtained from decay of adduct formed photochemically from enzyme and [2-3H]- tartronate. The direct formation of a covalent glycollyl adduct at position N(5) of reduced FMN is interpreted as being equivalent to addition of a transient carbanion, which is formed by abstraction of a proton from the glycollate α position.</dcterms:abstract> <dc:contributor>Massey, Vincent</dc:contributor> <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/8159/1/Studies_on_the_catalytic_mechanism_of_lactate_oxidase.pdf"/> <dc:language>eng</dc:language> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dcterms:issued>1980</dcterms:issued> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/8159"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T17:41:03Z</dc:date> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/28"/> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/28"/> <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/8159/1/Studies_on_the_catalytic_mechanism_of_lactate_oxidase.pdf"/> <dcterms:bibliographicCitation>First publ. in: Journal of Biological Chemistry 255 (1980), 12, pp. 5688-5696</dcterms:bibliographicCitation> <dcterms:rights rdf:resource="https://creativecommons.org/licenses/by-nc-nd/2.0/legalcode"/> </rdf:Description> </rdf:RDF>

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