000093808 001__ 93808
000093808 005__ 20250731122602.0
000093808 0247_ $$2pmid$$apmid:19182954
000093808 0247_ $$2doi$$a10.1021/bi801957d
000093808 0247_ $$2ISSN$$a1520-4995
000093808 0247_ $$2ISSN$$a0006-2960
000093808 0247_ $$2WOS$$aWOS:000265170200003
000093808 0247_ $$2datacite_doi$$a10.3204/PHPPUBDB-12176
000093808 0247_ $$2openalex$$aopenalex:W2090141453
000093808 037__ $$aPHPPUBDB-12176
000093808 041__ $$aeng
000093808 082__ $$a570
000093808 1001_ $$aBruning, M.
000093808 1101_ $$aDESY$$bMax-Planck-Arbeitsgruppen
000093808 245__ $$aStructural and kinetic studies on native intermediates and an intermediate analogue in benzoylformate decarboxylase reveal a least motion mechanism with an unprecedented short-lived predecarboxylation intermediate
000093808 260__ $$aColumbus, Ohio$$bAmerican Chemical Society$$c2009
000093808 300__ $$a3258-3268
000093808 3367_ $$2DRIVER$$aarticle
000093808 3367_ $$2DataCite$$aOutput Types/Journal article
000093808 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1554215661_4525
000093808 3367_ $$2BibTeX$$aARTICLE
000093808 3367_ $$2ORCID$$aJOURNAL_ARTICLE
000093808 3367_ $$00$$2EndNote$$aJournal Article
000093808 440_0 $$0PERI:(DE-600)1472258-6$$aBiochem.$$v48$$x0006-2960
000093808 500__ $$3Converted on 2013-05-30 14:50$$a(c) American Chemical Society
000093808 500__ $$3Converted on 2013-06-21 19:21
000093808 520__ $$aThe thiamin diphosphate- (ThDP-) dependent enzyme benzoylformate decarboxylase (BFDC) catalyzes the nonoxidative decarboxylation of benzoylformic acid to benzaldehyde and carbon dioxide. To date, no structural information for a cofactor-bound reaction intermediate in BFDC is available. For kinetic analysis, a chromophoric substrate analogue was employed that produces various absorbing intermediates during turnover but is a poor substrate with a 10(4)-fold compromised kcat. Here, we have analyzed the steady-state distribution of native intermediates by a combined chemical quench/1H NMR spectroscopic approach and estimated the net rate constants of elementary catalytic steps. At substrate saturation, carbonyl addition of the substrate to the cofactor (k' approximately 500 s-1 at 30 degrees C) and elimination of benzaldehyde (k' approximately 2.400 s-1) were found to be partially rate-determining for catalysis, whereas decarboxylation of the transient 2-mandelyl-ThDP intermediate is 1 order of magnitude faster with k' approximately 16.000 s-1, the largest rate constant of decarboxylation in any thiamin enzyme characterized so far. The X-ray structure of a predecarboxylation intermediate analogue was determined to 1.6 A after cocrystallization of BFDC from Pseudomonas putida with benzoylphosphonic acid methyl ester. In contrast to the free acid, for which irreversible phosphorylation of active center Ser26 was reported, the methyl ester forms a covalent adduct with ThDP with a similar configuration at C2alpha as observed for other thiamin enzymes. The C2-C2alpha bond of the intermediate analogue is out of plane by 7degrees, indicating strain. The phosphonate part of the adduct forms hydrogen bonds with Ser26 and His281, and the 1-OH group is held in place by interactions with His70 and the 4'-amino group of ThDP. The phenyl ring accommodates in a hydrophobic pocket formed by Phe464, Phe397, Leu109, and Leu403. A comparison with the previously determined structure of BFDC in noncovalent complex with the inhibitor (R)-mandelate suggests a least motion mechanism. Binding of benzoylphosphonic acid methyl ester to BFDC was further characterized by CD spectroscopy and stopped-flow kinetics, indicating a two-step binding mechanism with a 200-fold slower carbonyl addition to ThDP than determined for benzoylformic acid, in line with the observed slight structural reorganization of Phe464 due to steric clashes with the phosphonate moiety.
000093808 536__ $$0G:(DE-H253)POF1-DORIS-PETRA-20130405$$aFacility (machine) DORIS/PETRA (POF1-DORIS-PETRA-20130405)$$cPOF1-DORIS-PETRA-20130405$$fPOF I$$x0
000093808 588__ $$aDataset connected to Pubmed
000093808 650_7 $$00$$2NLM Chemicals$$aBacterial Proteins
000093808 650_7 $$0EC 4.1.1.-$$2NLM Chemicals$$aCarboxy-Lyases
000093808 650_7 $$0EC 4.1.1.7$$2NLM Chemicals$$abenzoylformate decarboxylase
000093808 650_2 $$2MeSH$$aBacterial Proteins: chemistry
000093808 650_2 $$2MeSH$$aBacterial Proteins: metabolism
000093808 650_2 $$2MeSH$$aCarboxy-Lyases: chemistry
000093808 650_2 $$2MeSH$$aCarboxy-Lyases: metabolism
000093808 650_2 $$2MeSH$$aCatalysis
000093808 650_2 $$2MeSH$$aCrystallography, X-Ray
000093808 650_2 $$2MeSH$$aDecarboxylation
000093808 650_2 $$2MeSH$$aKinetics
000093808 650_2 $$2MeSH$$aMagnetic Resonance Spectroscopy
000093808 650_2 $$2MeSH$$aPseudomonas putida: enzymology
000093808 650_2 $$2MeSH$$aStructure-Activity Relationship
000093808 650_2 $$2MeSH$$aSubstrate Specificity
000093808 650_2 $$2MeSH$$aThermodynamics
000093808 650_2 $$2MeSH$$aTime Factors
000093808 693__ $$0EXP:(DE-H253)DORISIII(machine)-20150101$$1EXP:(DE-H253)DORISIII-20150101$$5EXP:(DE-H253)DORISIII(machine)-20150101$$aDORIS III$$eFacility (machine) DORIS III$$x0
000093808 7001_ $$aBerheide, M.
000093808 7001_ $$aMeyer, D.
000093808 7001_ $$aGolbik, R.
000093808 7001_ $$aBartunik, H. D.
000093808 7001_ $$aLiese, A.
000093808 7001_ $$aTittmann, K.
000093808 773__ $$0PERI:(DE-600)1472258-6$$a10.1021/bi801957d$$gVol. 48, p. 3258-3268$$p3258-3268$$q48<3258-3268$$tBiochemistry$$v48$$x0006-2960$$y2009
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.pdf$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.pdf$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.pdf$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.gif?subformat=icon$$xicon$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.jpg?subformat=icon-1440$$xicon-1440$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.jpg?subformat=icon-180$$xicon-180$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.jpg?subformat=icon-640$$xicon-640$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/bi802162s.pdf?subformat=pdfa$$xpdfa$$yRestricted$$zStatID:(DE-HGF)0599
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.gif?subformat=icon$$xicon$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.jpg?subformat=icon-1440$$xicon-1440$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.jpg?subformat=icon-180$$xicon-180$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.jpg?subformat=icon-640$$xicon-640$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/BFDC%20manuscript%20Tittmann%20%26%20Liese%202008%20%20revision.pdf?subformat=pdfa$$xpdfa$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.gif?subformat=icon$$xicon$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.jpg?subformat=icon-1440$$xicon-1440$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.jpg?subformat=icon-180$$xicon-180$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.jpg?subformat=icon-640$$xicon-640$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 8564_ $$uhttps://bib-pubdb1.desy.de/record/93808/files/Supplementary%20Information%20Tittmann%20%26%20Liese%202008%20revision.pdf?subformat=pdfa$$xpdfa$$yPublished on 2009-01-30. Available in OpenAccess from 2010-01-30.
000093808 909CO $$ooai:bib-pubdb1.desy.de:93808$$pdnbdelivery$$pdriver$$pVDB$$popen_access$$popenaire
000093808 9101_ $$0I:(DE-HGF)0$$aExternes Institut$$kExtern
000093808 9131_ $$0G:(DE-HGF)POF1-550$$1G:(DE-HGF)POF1-500$$2G:(DE-HGF)POF1$$9G:(DE-H253)POF1-DORIS-PETRA-20130405$$aDE-H253$$bProgrammorientierte Förderung I$$lStruktur der Materie$$vGroßgeräte für die Forschung mit Photonen, Neutronen, Ionen$$x0
000093808 9141_ $$a(c) American Chemical Society. No copyright permission for full text.$$y2009
000093808 915__ $$0StatID:(DE-HGF)0150$$2StatID$$aDBCoverage$$bWeb of Science Core Collection
000093808 915__ $$0StatID:(DE-HGF)0530$$2StatID$$aEmbargoed OpenAccess
000093808 915__ $$0StatID:(DE-HGF)0100$$2StatID$$aJCR
000093808 915__ $$0StatID:(DE-HGF)0010$$2StatID$$aJCR/ISI refereed
000093808 915__ $$0StatID:(DE-HGF)1$$2StatID$$aNo Author Disambiguation
000093808 915__ $$0StatID:(DE-HGF)0300$$2StatID$$aDBCoverage$$bMedline
000093808 915__ $$0StatID:(DE-HGF)0199$$2StatID$$aDBCoverage$$bThomson Reuters Master Journal List
000093808 920__ $$k001
000093808 9201_ $$0I:(DE-H253)HASYLAB_-2012_-20130307$$kHASYLAB(-2012)$$lExperiments with synchrotron radiation$$x0
000093808 9201_ $$0I:(DE-H253)MPG_-2012_-20120307$$kMPG(-2012)$$lMax-Planck-Gesellschaft$$x1
000093808 920_1 $$iExperiments with synchrotron radiation$$kHASYLAB
000093808 980__ $$ajournal
000093808 980__ $$aVDB
000093808 980__ $$aUNRESTRICTED
000093808 980__ $$aI:(DE-H253)HASYLAB_-2012_-20130307
000093808 980__ $$aI:(DE-H253)MPG_-2012_-20120307
000093808 9801_ $$aFullTexts