14 有机污染物生物富集因子定量预测模型的建立与评价

2009年第54卷第1期:27~32有机污染物生物富集因子定量预测模型的建立与评价,*,,,,,,,116024,E-mail:[e-mail]2008-09-02,2008-11-20(:2006CB403302)QinH,ChenJW,WangY,etal.Developmentandassessmentofquantitativestructure-activityrelationshipmodelsforbioconcentrationfactorsoforganicpollutants.ChineseScienceBulletin,2009,54(4):628—634,doi:10.1007/s11434-009-0053-2(BCF).(OECD)-(QSAR),(LSER),(PLS)8BCFQSAR.,Connolly(CMA)(α)(MW)BCF,,.(R2Y=0.868,RMSE=0.553)(Q2CUM=0.860)(Q2EXT=0.755,RMSE=0.647).Williams(AD).,BCF,.(BCF)[1],(POPs)1),(PBT)2),BCF[2].BCF3,4),BCF,,.BCF.-(QSAR)BCF,[3~12].,QSAR()[13].QSAR,,[13].2004(OECD)QSAR,,5QSAR5),[14~16]:(1);(2);(3);(4);(5).BCFQSAR,/(KOW),logKOW6;logKOW6[12,17].1)UNEP(UnitedNationsEnvironmentProgram).FinalactoftheconferenceofplenipotentiariesontheStockholmconventiononpersistentor-ganicpollutants.UNEP/POPS/CONF/4,20012)EnvironmentalCanada.Toxicsubstancesmanagementpolicy,persistenceandbioaccumulationcriteria.EN40-499/2-1995E,19963)OECD(OrganisationforEconomicCo-OperationandDevelopment).OECDguidelinesfortestingofchemicals,proposalforupdatingguide-lines305,bioconcentration:Flow-throughfishtest.OECD305,19964)U.S.EPA(EnvironmentalProtectionAgency).Ecologicaleffectstestguidelines,OPPTS8501730,FishBCF.EPA712-C-96-129,19965)OECD(OrganisationforEconomicCo-OperationandDevelopment).Guidelinedocumentonthevalidationof(quantitative)structure-activityrelationships[(Q)SAR]models.ENV/JM/MONO(2007)2,20072009年1月第54卷第1期28,,[3,5,18~22][3][23][7~9,24].OECD,,8BCFQSAR,.11.1122logBCF[9],.70logBCF[5,17],.,POPs,,BCF.1.2,,(LSER)[25],()()().16.,(MW)(α)(TE)(ΔHf)Connolly(CAA)Connolly(CMA)Connolly(CSEV)(Ov)[26],.(μ)μ2,.(ELUMO)(EHOMO)(q−C)(q+H)(q+Cl)(q+max),.MOPAC2000(CSChemOffice2004),PM3;CSChem3DUltra(ChemOffice2004).1.3Simca6.0(PLS).:,PLS,(VIP),,,PLS(Q2CUM).Q2CUM,VIP,VIP.,.P0.001,Q2CUMPLS.1.4(R2X,R2Y)(RMSE).R2XR2YPLSXY.,70%30%,10,Q2CUM.,(R2),RMSE(Q2EXT).222(fit)11()()nniiiiRyyyy===−−∑∑,(1)RMSE21ˆ(),niiiyyn==−∑(2)Q2EXTextext22ext11ˆ1.0()(),nniiiiiyyyy===−−−∑∑(3),yi(fit)ilogBCF,ylogBCF,yiˆiyilogBCF,extylogBCF,n,next.Williams[27](AD).(δ*)(−2.5,+2.5),Y;Hat(hi)[27](h*=3p′/n),.δ*,hih*:δ*21ˆˆ()()(1)niiiiiyyyynA==−−−−∑,(4)hi=xTi(XTX)−1xi,(5)h*=3(m+1)/n,(6),xii,xTixi,X,XTX,(XTX)−1XTX,m,29APLS.22.1:logBCF=−7.043×10−1+9.937×10−3CMA+1.212×10−2α+5.017×10−3MW+1.817q−C,(7)n=122,R2X=0.729,R2Y=0.868,Q2CUM=0.864,A=1,RMSE=0.553,P0.001,R2XR2Y0.7290.868,.R2YQ2CUM0.3,[13].1.1logBCF70%,PLS,30%.10,:Q2CUM=0.860,RMSE=0.545(70%),R2=0.867(70%),RMSE=0.577(30%),R2=0.869(30%).,.2.21PLS,4(1).PLSCMA,α,MW,.CMA,αMW(VIP),logBCF,(W*),,CMA,αMWlogBCF.α,MWCMA,.,,.,2,2′,4,4′-,q−C−0.111,2,2′,4,4′-α(MW),2,2′,4,4′-BCF.q−ClogBCF,q−C,()[28],,,q−C,.,2-3-,MW,2-q−C(),BCF.,,.1VIPPLSVIPW*[1]CMA1.1310.565α1.1280.564MW1.1010.554q−C0.4690.2352.3:next=70,Q2EXT=0.533,R2=0.626,RMSE=0.910.Williamsh*=0.148(2).92()113(2--4,6-)hh*,|δ*|2.5,.BCF.,,,NH2,BCF[29].2--4,6-NO2OH,122,BCF.,32(1,2,4,5-)hh*,,[27].2009年1月第54卷第1期302hWilliams,4(10′,32′,33′,70′)hh*,,10′([a])66′(),70′(2,2′-),,.32′(4-)33′(4-),|δ*|2.5,,.,AD,hh*AD.8|δ*|2.5,,AD.,6:35′()O,37′()OHO,54′()61′()OCONH,58′()59′()SCON.,[30],[31,32].,,,,.2(20′,34′),34′(3,3′-)92(),NH2,|δ*|2.5.20′(2,2′,4,4′,6-)|δ*|2.5,.hh*Y,:Q2EXT=0.755,R2=0.760,RMSE=0.647.2.4KOWBCFQSAR[12],/()/./()/[29],KOWBCF,.,KOWKOW,,(RMSE=0.77,n=238)[7].,,.,BCFQSAR(2).:(1)Wei[23]RMSE=0.13,,n=27,.(2)Lu[5]Gramatica[7],13;(GA),.(3)Sacan[9],,.,;.,AD,.312a)mnR2RMSEFQ2EXTADWei[23]MLR3270.9310.13103NRNRNRLu[5]NLR132390.8100.60NRRNRNRSacan[9]MLR21220.8510.59338RNRNRGramaticaPapa[7]GA-OLS42380.8160.59258RNRRPLS41220.8680.55120R0.755Ra)MLR,;NLR,;OLS,;R,;NR,3OECDQSAR,LSER,PLS8BCFQSAR.,.,Williams(AD).,.QSAR,BCF.1王连生.有机污染化学.北京:高等教育出版社,2005.253—2542ArnotJA,MackayD,BonnellM.Estimatingmetabolicbiotransformationratesinfishfromlaboratorydata.EnvironToxicolChem,2008,27(2):341—3513ConnellDW,SchrmannG.Evaluationofvariousmolecularparametersaspredictorsofbioconcentrationinfish.EcotoxicolEnvironSaf,1988,15(3):324—3354BinteinS,DevillersJ,KarcherW.Nonlineardependenceoffishbioconcentrationonn-octanol/waterpartitioncoefficient.SARQSAREnvironRes,1993,1(1):29—395LuXX,TaoS,HuH,DawsonRW.Estimationofbioconcentrationfactorsofnonionicorganiccompoundsinfishbymolecularconnectivityindicesandpolaritycorrectionfactors.Chemosphere,2000,41(10):1675—16886DimitrovSD,DimitrovaNC,WalkerJD,etal.Predictingbioconcentrationfactorsofhighlyhydrophobicchemicals.Effectsofmo-lecularsize.PureApplChem,2002,74(10):1823—18307GramaticaP,PapaE.QSARmodelingofbioconcentrationfactorbytheoreticalmoleculardescriptors.QSARCombSci,2003,22(3):374—3858DeardenJC,ShinnaweiNM.Improvedpredictionoffishbioconcentrationfactorofhydrophobicchemicals.SARQSAREnvironRes,2004,15(5-6):449—4559SacanMT,ErdemSS,OzpinarGA,etal.QSPRstudyonthebioconcentrationfactorsofnonionicorganiccompoundsinfishbycharacteristicrootindexandsemiempiricalmoleculardescriptors.JChemInfComputSci,2004,44(3):985—99210PapaE,DeardenJC,GramaticaP.LinearQSARregressionmodelsforthepredictionofbioconcentrationfactorsbyphysicochemicalpropertiesandstru