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! 39 "! # 2020 $ % &'()*+ FENXICESHIXUEBAO JournalofInstrumentalAnalysis Vol39No6 715~721 !"#$2020-02-08 %&#$2020-02-19 '()*-YZ3ê452017YFC1600300 +,-.ì 99:3<=3<>?BAåæL&'E-mail shaobingch@sinacom doi 103969/jissn1004-4957202006003 0123456 96: ¡b¢3X £¤H 23 ¥¦§J¨©> NOP ( Q RST UVW 5 X Y Z 1.Oë^_X:8c,g BL,³;¸+¹ºOëYZ[\]Oë 100013 2.,-f\f© /*3<0<$f(,gOë 100123 3.H=/¹k* BAjxETL¹º*0H= 300457 C DD§æ1l>?@¿Æ§Tù~ CUPLC-MS/MS f(Aù½ù, 23 ©ø#$LBPs z>ÒAXA|}ÂÈ»Þe½ùXA|}¼ÞeG PRiMEHLB B#ÞeG>?@¿Æ§Tø«Â¼ù 01 »ÈܼâþU|} ACQUITYUPLCBEH 18 21mm×100mm 17 μ &Cr+â,-.,+rf(23 5V LQ 0005~100μ g/L 45µ¤°Ãâ 0002~0030μ g/L ¯DÃâ 0005~0100 μ g/L «¼®â 766 ~122 pVo½^RSD â 060 ~14 }D§z>Ò&yp 20 ÑAù 20 ѽ ùXAæf(Ñ>ÒXA}Dw¯°yÓ«./Aù½ùXA, 23 BPs zA©(¯ó3EFG©ø#$LA½ù>?@¿Æ~ CUPLC-MS/MS HI7JKO65763 O6577  LMNOPA  LQRK1004-4957 2020 06-0715-07 SimultaneousDeterminationof23BisphenolAnalogsandTheirHalogenated DerivativesinUrineandSerumbyUltrahighPerformance LiquidChromatography-TandemMassSpectrometry NIUYumin WANGBin YANGRunhui DUANHejun ZHANGJing SHAOBing 1.BeijingKeyLaboratoryofDiagnosticandTraceabilityTechnologiesforFoodPoisoning BeijingCenterforDisease PreventionandControl Beijing 100013 China 2.ChineseAcademyofInspectionandQuarantine ComprehensiveTestCenter Beijing 100123 China 3.CollegeofFoodEngineeringand Biotechnology TianjinUniversityofScience&Technology Tianjin 300457 China Abstract Anultrahighperformanceliquidchromatography-tandemmassspectrometric UPLC- MS/MS methodwasdevelopedforthesimultaneousdeterminationof23bisphenolanalogsandtheir halogenatedderivatives BPs inurineandserumbasedonderivatizationofpyridine3sulfonylchlo ride.Urinesampleswereextractedbyliquid-liquidextractionwithethylacetate whileserumsam pleswereextractedwithacetonitrileandfollowedbyPRiMEHLBcartridgepurification.Afterderivat izationwithpyridine3sulfonylchloride theextractswereseparatedonanACQUITYUPLCBEHC 18 21mm×100mm 17μ columnwithacetonitrileandwatercontaining01 formicacidas mobilephases anddeterminedbyUPLC-MS/MSwithelectrosprayionization ESI inpositiveion mode.Thereweregoodlinearrelationshipsfor23BPsinbothurineandserumsamplesintherange of0005-100 μ g/L withtheirlimitsofdetectionbetween0002 μ g/Land0030 μ g/L limitsof quantitationbetween0005 μ g/L and0100 μ g/L.Averagerecoveriesrangedfrom 766 to 122 withrelativestandarddeviations RSD of060 -14 .Themethodwasappliedinthe analysisofBPsin20urinesamplesand20serumsamples.Themethodcouldmeettherequirements forsimultaneousdeterminationof23BPsinurineandserum sampleswithlowsampleconsumption andhighsensitivity. Keywords bisphenolanalogsandtheirhalogenatedderivatives urine serum pyridine3sulfonyl

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Page 1: 0123456 ž 96:€¡šb¢3X

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2020$

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FENXICESHIXUEBAO(JournalofInstrumentalAnalysis)         Vol39No6

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:2020-02-19 

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(2017YFC1600300)+,-.

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,E-mail:shaobingch@sinacom

doi:103969/jissn1004-4957202006003

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:1004-4957(2020)06-0715-07

SimultaneousDeterminationof23BisphenolAnalogsandTheirHalogenatedDerivativesinUrineandSerumbyUltrahighPerformanceLiquidChromatography-TandemMassSpectrometry

NIUYumin1,WANGBin2,YANGRunhui3,DUANHejun1,ZHANGJing1,SHAOBing1

(1.BeijingKeyLaboratoryofDiagnosticandTraceabilityTechnologiesforFoodPoisoning,BeijingCenterforDiseasePreventionandControl,Beijing 100013,China;2.ChineseAcademyofInspectionandQuarantine

ComprehensiveTestCenter,Beijing 100123,China;3.CollegeofFoodEngineeringandBiotechnology,TianjinUniversityofScience&Technology,Tianjin 300457,China)

Abstract:Anultrahighperformanceliquidchromatography-tandemmassspectrometric(UPLC-MS/MS)methodwasdevelopedforthesimultaneousdeterminationof23bisphenolanalogsandtheirhalogenatedderivatives(BPs)inurineandserumbasedonderivatizationofpyridine3sulfonylchloride.Urinesampleswereextractedbyliquid-liquidextractionwithethylacetate,whileserumsampleswereextractedwithacetonitrileandfollowedbyPRiMEHLBcartridgepurification.Afterderivatizationwithpyridine3sulfonylchloride,theextractswereseparatedonanACQUITYUPLCBEHC18(21mm×100mm,17μm)columnwithacetonitrileandwatercontaining01% formicacidasmobilephases,anddeterminedbyUPLC-MS/MSwithelectrosprayionization(ESI)inpositiveionmode.Thereweregoodlinearrelationshipsfor23BPsinbothurineandserumsamplesintherangeof0005-100μg/L,withtheirlimitsofdetectionbetween0002μg/Land0030μg/L,limitsofquantitationbetween0005μg/Land0100μg/L.Averagerecoveriesrangedfrom766% to122%,withrelativestandarddeviations(RSD)of060% -14%.ThemethodwasappliedintheanalysisofBPsin20urinesamplesand20serumsamples.Themethodcouldmeettherequirementsforsimultaneousdeterminationof23BPsinurineandserumsampleswithlowsampleconsumptionandhighsensitivity.Keywords:bisphenolanalogsandtheirhalogenatedderivatives;urine;serum;pyridine3sulfonyl

Page 2: 0123456 ž 96:€¡šb¢3X

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Analyte Retentiontime(min) Parention(m/z) Daughterion(m/z) Collisionenergy(eV) Internalstandard

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�©

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Table2 LODs,LOQs,recoveriesandRSDsof23BPs

AnalyteLOD(μg/L) LOQ(μg/L) Recovery(%) IntradayRSD(%) InterdayRSD(%)

Urine Serum Urine Serum Urine Serum Urine Serum Urine SerumBPA 0017 0017 0050 0050 969~103 918~116 060~47 26~42 40 20BPB 0002 0002 0005 0005 962~102 101~106 12~73 61~13 16 73BPC 0002 0008 0005 0025 109~120 776~972 45~73 20~13 62 62BPE 0002 0002 0005 0005 955~103 833~109 14~30 26~67 36 33BPF 0017 0003 0050 0010 914~107 911~106 37~73 24~70 29 38

BPM/BPP 0002 0003 0005 0010 857~988822~933 10~43 48~14 21 12BPS 0007 0008 0020 0025 957~106 991~108 16~95 060~13 57 14BPZ 0003 0008 0010 0025 940~103848~972 19~26 76~87 24 48BPAF 0003 0003 0010 0010 101~104 100~101 25~71 72~80 25 77BPAP 0002 0002 0005 0005 955~100 853~103 20~53 55~68 25 82BPBP 0002 0002 0005 0005 929~102 899~103 20~26 84~13 40 10BPFL 0003 0003 0010 0010 949~982784~928 11~41 49~11 29 84DHDPE 0017 0027 0050 0080 103~104 915~118 11~23 27~99 090 87MCBPA 0010 0017 0030 0050 102~106 776~878 32~75 16~69 10 49DCBPA 0007 0003 0020 0010 107~113 766~876 10~31 59~93 18 67TriCBPA 0008 0008 0025 0025 975~122842~964 24~48 39~98 55 43TCBPA 0017 0008 0050 0025 996~110 945~104 18~92 63~81 10 56TBBPA 0017 0008 0050 0025 930~110 973~104 17~12 58~11 11 84MCBPF 0030 0017 0100 0050 829~104 788~106 10~33 30~52 10 17DCBPF 0030 0008 0100 0025 860~114 943~108 10~41 49~68 41 55TriCBPF 0030 0017 0100 0050 846~108 809~101 090~43 49~80 48 67TCBPF 0030 0030 0100 0100 843~108 103~110 18~59 75~11 45 14

 themethodcannotdistinguishBPMandBPP(2>Ò(Ò¡&

BPMù

BPP)

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BPSzf·®Hâ

100%,C

DPy&yâ

0450~7199μg/L、0046~1483μg/Lù

0176~1836μg/L,ÝH;&yâ

2115、0268、0708μg/L,BPA)9òóz

BPs。Q½ùXA,

,BPAzf·®9�

(â

70%),CDPyâ

0050~0399μg/L;C0Df·

BPF、BPAFù

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3 h

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23�

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[1] JiangDQ,ChenWQ,ZengXL,TangLB.EnvironSciTechnol.,2018,52:3706-3715.[2] Ziv-GalA,FlawsJA.FertilSteril.,2016,106:827-856.[3] ChenD,KannanK,TanHL,ZhengZG,FengYL,WuY,WidelkaM.EnvironSciTechnol.,2016,50:5438-5453.[4] EFSAPanelonFoodContactMaterials,FlavouringsandProcessingAids(CEF).EFSAJ.,2015,13:3978.[5] LiaoCY,LiuF,KannanK.EnvironSciTechnol.,2012,46:6515-6522.[6] CabatonN,DumontC,SeverinI,PerduE,ZalkoD,Cherkaoui-MalkiM,ChagnonMC.Toxicology,2009,255:

15-24.[7] SchoenbergerF,ChromikA,KerresJ.Polymer,2009,50:2010-2024.[8] ChuSG,HaffnerGD,LetcherRJ.JChromatogrA,2005,1097:25-32.[9] ZhengS,ShiJC,HuJY,HuWX,ZhangJ,ShaoB.WaterRes.,2016,107:1-10.[10] HuJY,AizawaT,OokuboS.EnvironSciTechnol.,2002,36:1980-1987.

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[11] KinchCD,IbhazehieboK,JeongJH,HabibiHR,KurraschDM.PNAS,2015,112:1475-1480.[12] AndraSS,CharisiadisP,AroraM,vanVliet-OstaptchoukJV,MakrisKC.EnvironInt.,2015,85:352-379.[13] Molina-MolinaJM,AmayaE,GrimaldiM,SaenzJM,RealM,FernandezMF,BalaguerP,OleaN.ToxicolAppl

Pharm.,2013,272:127-136.[14] LiangXZ,SuiHX,LiD,ZhongHN.JInstrumAnal(

���

,��

,��

,���

.&'()*+

),

2018,37(1):87-91.[15] YueQ,YuZQ,WangDC,ShengGY,FuJM.JInstrumAnal(

�õ

,lqõ

,6Ý~

,�-B

,¦��

.&

'()*+

),2009,28(7):859-862.[16] WangY,LiGL,ZhuQQ,LiaoCY.Talanta,2019,205:120144.[17] VenisseN,CambienG,RobinJ,RouillonS,NadeauC,CharlesT,RabouanS,MigeotV,DupuisA.Talanta,

2019,204:145-152.[18] OwczarekK,KubicaP,KudakB,RutkowskaA,KoniecznaA,RachońD,Namies'nikJ,WasikA.SciTotalEnvi

ron.,2018,628/629:1362-1368.[19] SongSM,DuanYS,ZhangT,ZhangB,ZhaoZ,BaiXY,XieL,HeY,OuyangJP,HuangXF,SunHW.

EcotoxicolEnvironSaf.,2019,169:822-828.[20] NiuYM,WangB,ZhaoYF,ZhangJ,ShaoB.JAgricFoodChem.,2017,65:10452-10463.

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