识别三唑类农药的片段印迹聚合物的合成及在固相萃取中的应用

Vo.l30高等学校化学学报No.11200911CHEMICALJOURNALOFCHINESEUNIVERSITIES2159~2164彭畅,刘维娟,张春涛,张玲,张智超(,,300071),7().,(M1)7.,:,4,,.(MSPD)M1(MISPE),.3,75%~102%,3%~9%(n=5),(3)09~15g/kg.MSPDMISPE.;;;;O656A02510790(2009)11215906:20090417.:(:20375018).:,,,,.Emai:[e-mail],,,.Emai:[e-mail].1Structuresoftriazoles(1)..,7.(MIP),.,[1].:[2~4];.[5~10].7,,,,.(M1)7.(MSPD)(MISPE).MSPD,,[11,12],,MSPD[13,14];MISPE.MSPDMISPE[13].MSPDM1MISPE,,,.11.14(4VP)(EDMA,,AlfaAesar),;(AIBN)(,),;(Triadimefon)(Diniconazole)(Paclobutrazol)(Uniconazole)(Tebuconazole)(Triadimenol)(Bitertanol)(95%,),;2,463,42,62,4(99%,);(,);(60~90)(,),;(,);(,);(,)(165~245m,),5003h,.1.2Agilent6890N,.HP5,30m032mm025m;(99999%),1160mL/min;,1!10,10L;235310;:150,10/min230,4min,30/min275,5min..1.305mmol20mmol4VP180mL(15cm13mm.id.),,41h.10mmolEDMA400mgAIBN,5min,4min,,6024h.,,38~165m./(4!1).1.(NIP),.Table1TemplatesusedforthepreparationofpolymersPolymerTemplatePolymerTemplateM12NitrophenolM74ChlorophenolM22,4Dimethyl6nitrophenolM83NitrophenolM33,4Dimethyl2,6dinitrophenolM94NitrophenolM42,4DinitrophenolM10PhenolM5NitrobenzeneM11TolueneM62ChlorophenolM12Triadimefon1.4200mg,200mL7(00200mmol/L),5h,,,(GC).3..,.2160高等学校化学学报Vo.l30,.1.5MSPDMISPE200g,100mL7,(20mL),,,.160g80mL,.,50g,,.300mL.,,50mL,MISPE.MISPE(500mgM1)/(4!1)50mL.MSPD,200mL/(50!1).80mL,,,100mL,GC.22.1(2),(M1~M11),(M1).Table2AdsorptioncapacityofMIPsandNIPtotriazoles*PolymerAdsorptioncapacity(%)TriadimefonDiniconazolePaclobutrazolUniconazoleTebuconazoleTriadimenolBitertanolM160747581848689M254686977818385M348606372767982M441475261647071M534353648575862M628303245545660M720222332434349M822182835335040M918142327294335M1017142327294335M1180801417182825M1231243541445748NIP50606070801090*Relativestandarddeviationswereallbetween1%and5%(n=3).,(M12).2,M12:.,4VP,M12.,,M12,.MIP,MIP,[15].M12.M1,M1:∀.,M1.,,,;,,,,,,;,,2,.,M1.,2161No.11彭畅等:识别三唑类农药的片段印迹聚合物的合成及在固相萃取中的应用M1,,4VP,.,M12.,M1,4VP,,.(2),,4VP,(60%)(NIP)(5%),.Fig.2Conceptoftherecognitionmechanismofthefragmentimprintedpolymerfortriazoles.,.,.,(M1,M2,M3,M4)(M12)(2).,,,,.2.2MISPE2.2.1上样条件的优化500mL(60~90)(500g/mL),80mL.,,#98%,M1.,50mL,MISPE,.2.2.2淋洗条件的优化MIP[16].,.,.500mL(500g/mL,),500mL200mL/(50!1),80mL.3.,NIP67%~30%,M176%~97%.,NIP,M1.500mL,,,200mL/(50!1).Fig.3Recoveriesfortriazolesintheelutionfractions,afterthepercolationofastandardsolutioncontaining250gofeachcompoundin500mLofpetroleumetherthroughM1andNIPcolumnsWashingstep:(A)500mLofpetroleumether;(B)200mLofapetroleumetherdichloromethane(50!1,volumeratio)mixture.Elutionstep:80mLofethylacetate.a.Triadimefon;b.diniconazole;c.paclobutrazo;ld.uniconazole;e.tebuconazole;.ftriadimeno;lg.bitertano.l2.2.3洗脱条件的优化.500mL2162高等学校化学学报Vo.l30(500g/mL,),80mL,,90%,#98%,80mL.2.3MSPD100mLGC,,[4(A)(B)].3102%~172%(3).,MSPD,MSPD.M1MISPEMSPD,GC[4(C)(D)],375%~102%(3).(001~006mg/kg),MSPD,121%~172%;MISPE,,92%~102%.,MISPEMSPD,.Table3RecoveriesofMSPDextractswithoutandwithadditionalcleanupbyMISPEfromsoilsamplesspikedatdifferentlevels*TriazoleRecoveries(%)[spikinglevel/(mg∃kg-1)]MSPDMSPDMISPEMSPDMSPDMISPEMSPDMSPDMISPETriadimefon132(001)92(001)110(01)85(01)102(05)75(05)Diniconazole125(001)95(001)109(01)90(01)102(05)81(05)Paclobutrazol172(005)96(005)147(01)88(01)129(05)80(05)Uniconazole153(002)102(002)131(01)97(01)108(05)90(05)Tebuconazole134(006)98(006)127(01)98(01)110(05)95(05)Triadimenol164(005)102(005)143(01)97(01)110(05)90(05)Bitertanol121(005)98(005)109(01)97(01)102(05)94(05)*Relativestandarddeviationswereallbetween3%and9%(n=5).Fig.4GCchromatogramsofMSPDextractfromtheblanksoilsample(A),MSPDextractfromthespikedsoilsample(B),MSPDMISPEextractfromtheblanksoilsample(C)andMSPDMISPEextractfromthespikedsoilsample(D)Spikingleve:l1.triadimefon10g/kg;2.triadimenol50g/kg;3.paclobutrazol50g/kg;4.uniconazole20g/kg;5.diniconazole10g/kg;6.tebuconazole60g/kg;7.bitertanol50g/kg.6,S/N=3:10g/kg;80g/kg;10g/kg;20g/kg;090g/kg;20g/kg;15g/kg.MSPDMISPE,,,,,.2163No.11彭畅等:识别三唑类农药的片段印迹聚合物的合成及在固相萃取中的应用[1]AndrssonL.I.,PapricaA.,ArvidssonT..Chromatographia[J],1997,46:57%62[2]TheodoridisG.,KantifesA.,ManesiotisP.,etal..J.Chromatogr.A[J],2003,987:103%109[3]JodlbauerJ.,MaiernM.,LindnerW..J.Chromatogr.A[J],2002,945:45%63[4]WANGJinCheng(),XUQing(),XUEXingYa(),etal..Chem.J.ChineseUniversities()[J],2006,27(7):1227%1231[5]HosoyaK.,YoshizakoK.,SasakiH.,etal..J.Chromatogr.A[J],1998,828:91%94[6]KuboT.,HosoyaK.,WatabeY.,etal..J.Chromatogr.A[J],2003,987:389%394[7]KuboT.,HosoyaK.,WatabeY.,etal..J.Chromatogr.A[J],2004,1029:37%41[8]KuboT.,HosoyaK.,WatabeY.,etal..J.Sep.Sc.i[J],2004,27:316%324[9]KuboT.,NomachiM.,NemotoK.,etal..Ana.lChim.Acta[J],2006,577:1%7[10]MohamedR.,MottierP.,TreguierL.,etal..J.Agric.FoodChem.[J],2008,56:3500%3508[11]KristensonE.M.,RamosL.,BrinkmanU.A.Th..TrendsAna.lChem.[J],2006,25:96%111[12]GarcaLpezM.,CanosaP.,RodrguezI..Ana.lBioana.lChem.[J],2008,391:963%974[13]CrescenziC.,BayoudhS.,CormackP.A.G.,etal..Ana.lChem.[J],2001,73:2171%2177[14]YanH.,QiaoF.,RowH.R..Ana.lChem.[J],2007,79:8242%8248[15]CaroE.,MarR.M.,CrmackP.A.G.,etal..J.Chromatogr.A[J],2003,99