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时间:2018-07-28
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1、AminoAcidCofactorsSecondaryarticleVictorLDavidson,UniversityofMississippiMedicalCenter,Jackson,Mississippi,USAArticleContents.IntroductionAminoacidcofactorsaretypicallymetalororganicionsthatareessentialforelectrophilic.PyruvoylEnzymescatalysis..DehydroalanylEnzymes.QuinoproteinsIntroduction.OtherCr
2、osslinkedAminoAcidCofactors.AminoAcid-basedFreeRadicalsCertainaminoacidresiduesattheactivesitesofenzymestypicallyplaycriticalrolesincatalysis.Theside-chainsofsomeaminoacidresiduesarechemicallywellsuitedtoPyruvoylEnzymesfunctionaselectrondonorsinnucleophiliccatalysis.Ingeneral,aminoacidsdonotfunctio
3、nwellaselectrophilesPyruvoylenzymescompriseaclassofenzymesthatpossess(i.e.electronacceptors).Instead,metalsandorganicacovalentlyboundpyruvoylprostheticgroup(Figure1).cofactors(e.g.pyridoxalphosphateandflavins)areThiscofactorisderivedfromtheposttranslationaltypicallyrequiredbytheenzymetoserveaselectr
4、onmodificationofaserineresidue,anditdoesnotequilibrateacceptors.Metalsandorganiccofactorsarealsousuallywithexogenouspyruvate(Dowhan,1997).Thisclassofrequiredbyenzymesthatcatalysereactionsthatproceedenzymesincludesbacterialhistidinedecarboxylases,bac-viafree-radicalintermediates.Ithasrecentlybeenob-t
5、erialandeukaryoticS-adenosylmethioninedecarboxy-servedthatcertainenzymeshaveevolvedtocircumventthelases,bacterialandeukaryoticphosphatidylserineneedforexogenouscofactors.Alternatively,endogenousdecarboxylases,bacterialandeukaryotic4’-phosphatecofactorsmaybegeneratedbyposttranslationalmodifica-pantot
6、henoylcysteinedecarboxylases,E.coliaspartatetionofaminoacidresiduesonthepolypeptidechaindecarboxylase,andprolinereductasefromClostridium(Table1).Inmostcasestheseendogenousaminoacid-stricklandii.Asisevidentfromthislist,thisclassofderivedcofactorsfunctionaselectrophilesincatalysisandenzymesplaysanimp
7、ortantroleintheformationofsometimesstabilizefree-radicalintermediates.Inmanybiologicallyimportantaminesfromaminoacidsandcases,thepresenceofaminoacidcofactorswasunrecog-aminoacid-derivedsubstrates.nizeduntil
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