中德双边会议-潘远江.ppt

YuanjiangPanZhejiangUniversity2014.11.20,StilbenesfromParthenocissuslaetevirens:Isolation,BioactivityandImplicationofChemicalDefenseSysteminPlant,PNAS,1999,96,13620.,diterpene,antifeedantactivityforbeetle,PNAS,2000,97,14406.,MalesofthemothacquirebyfeedingontheexcrescentfluidsofcertainplantsTheyincorporatethealkaloidsystemicallyandasaresultareprotectedagainstspiders.,pyrrolizidinealkaloid,ChemicalDefenseinFlower,IntheflowerofHypericumcalycinum,dearomatizedisoprenylatedphloroglucinols(DIPs)areresponsiblefortheUVdemarcations.DIPsfulfillbothavisualandadefensivefunction.DIPsalsoserveforprotectionoffemalereproductivestructuresinotherplants.,GronquestM.,et.al.,Proc.Natl.Acad.Sci.U.S.A.,2001,98,13745,ChemicalDefenseinCatepillar,Pinoresinol,alignanofwidedistributioninplants,isfoundtooccurasaminorcomponentinthedefensivesecretionproducedbyglandularhairsofcaterpillarsofthecabbagebutterfly,Pierisrapae.,SchroederF.C.,et.al.,Proc.Natl.Acad.Sci.U.S.A.,2006,103,15497,ROS:reactiveoxygenspecies,ROSincludebothradicalsandnon-radicals.Theyaregenerallyverysmallmoleculesandarehighlyreactiveduetothepresenceofunpairedvalenceshellelectrons.ROSsformasnaturalbyproductsofnormalmetabolismofoxygenandplayimportantrolesincellsignaling.,CircuM.L.,et.al.,FreeRadic.Biol.Med.,2010,48,749-762,EndogenousSourcesofROS,ExogenousSourcesofROS,RadiationUVlight,x-rays,-raysChemicalsthatreacttoformperoxidesozone,singletoxygenChemicalsthatpromotesuperoxideformationquinones,nitroaromatics,bipyrimidiuliumherbicidesChemicalsthataremetabolizedtoradicalspolyhalogenatedalkanes,aminophenolsChemicalsthatreleaseironferritin,ROS2%,trans-resveratrol,cis-resveratrol,UnknowncompoundProposedstructure,UVirradiationonethylacetateextract,0min,120min,Cyclizeddimer5,Cyclizedtrimer8,Biologicalimportanceofoligomerizationofstilbenes,+,Whytrimerweresynthesized,thoughtheirantioxidantactivitieswerelower?,SC50=26.28g/ml,SC50=118.10g/ml,SC50=172.1g/ml,SC50=16.40g/ml,Ref.11:AnewclassofphytoalexinsfromgrapevinesExperientia1977,15,151-152.,ResveratrolNon-antifungal,Antifungal,Antifungal,Hypothesis:Isperoxidasecatalysingoligomerizationanantifungalactivitypromotingreaction?,Antifungalactivitiesofstilbenes,+,Non-antifungal,Antifungal,Nottested.,*InhibitionrateofgrowthofBotrytiscinerea(灰葡萄孢菌)at400g/ml.,Non-antifungal,Antifungalactivitiesofstilbenes,+,+,Non-antifungal,Antifungal,Nottested.,Non-antifungal,Antifungalactivitiesofstilbenes,+,Non-antifungal,Non-antifungal,Antifungal,Needmoreevidencetoprovethehypothesisthatoligomerizationpromotesantifungalactivity.,InhibitionrateofgrowthofBotrytiscinerea(灰葡萄孢菌)at400g/ml.Molconcentrationofresveratrolwas3foldhigherthancompound8.,Summary,10stilbeneoligomerswereisolatedfromtheEAextractofParthenocissuslaetevirens.Fiveofthemarenewcompounds.TheirstructurewereelucidatedbyNMRandMSdata.Theirbiogeneticrelationshipwasprovedbyphotochemicaltransformationandenzymecatalysingoligomerization.,Theirantioxidantactivitieswereassayed.TheresultsledtothehypothesisthatUVinducedcyclizationisanantioxidantactivitypromotingreactionandconsequentlystilbeneswereimpliedtoplayaroleintheantioxidativedefensesystemoftheplant.Inaddition,theresultsofantifungalactivitiesrevealthatenzymecatalysingoligomerizationmaybelinkedtotheantifungaldefensesystemoftheplant,J.Org.Chem.2008,ResveratrolHexamerfromVitischunganeniss,J.Org.Chem.2009,Proposedchunganeno