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Article(id=1241023852365541659, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241023847537897695, articleNumber=null, orderNo=null, doi=10.20043/j.cnki.MPM.202410288, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1729440000000, receivedDateStr=2024-10-21, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773812743512, onlineDateStr=2026-03-18, pubDate=1737734400000, pubDateStr=2025-01-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773812743512, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773812743512, creator=13701087609, updateTime=1773812743512, updator=13701087609, issue=Issue{id=1241023847537897695, tenantId=1146029695717560320, journalId=1227665162245664772, year='2025', volume='52', issue='2', pageStart='193', pageEnd='384', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773812742361, creator=13701087609, updateTime=1773812823817, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241024189247845056, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241023847537897695, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241024189247845057, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241023847537897695, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=328, endPage=335, ext={EN=ArticleExt(id=1241023852692697390, articleId=1241023852365541659, tenantId=1146029695717560320, journalId=1227665162245664772, language=EN, title=Determination of 18 phthalate esters metabolites in urine by solid-phase supported liquid-liquid extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry, columnId=1228016572065837304, journalTitle=Modern Preventive Medicine, columnName=Experimental Technology and Applications, runingTitle=null, highlight=null, articleAbstract=
Objective

To establish a method for the determination of 18 phthalates (PAEs) metabolites in urine by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) based on solid-phase support liquid-liquid extraction (SLE) technology.

Methods

Urine sample spiked with internal standards was first hydrolyzed by enzyme, then purified on a SLE column. The separation was performed on a BEH C18 column. The detection was performed in multi-reaction monitoring scan under negative mode. Internal standard method was applied for quantitative analysis.

Results

The 18 PAEs metabolites showed good linear relationships in the range of 0.10-80 ng/ml (r>0.999). The average recoveries of 18 PAEs metabolites ranged from 84.0%-113.0% with relative standard deviations between 1.1% and 9.5%. The limits of detection and quantitation of the method were 0.001-0.07ng/ml and 0.002-0.2 ng/ml, respectively. The intra-day and the inter-day precisions were 1.3%-7.0% and 1.0%-8.1%, respectively. 160 urine samples were analyzed with this method. Except for 3 PAEs metabolites that were not detected, the detection rates of the remaining 15 PAEs metabolites ranged from 1.9% to 100%, and the detection rates of 8 PAEs metabolites were 100%. Among them, mono-n-butyl phthalate had the highest concentrations with a median concentration of 126 ng/ml.

Conclusion

This method is simple, sensitive, and accurate, and it is suitable for the determination of 18 PAEs metabolites in large batchs of urine samples.

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目的

基于固相支撑液液萃取(SLE）技术，采用超高效液相色谱-串联质谱法（UPLC-MS/MS）建立尿液中18种邻苯二甲酸酯（PAEs）代谢物的测定方法。

方法

尿样中加入内标，经过酶解、SLE小柱净化后，采用BEH C18色谱柱色谱分离，在负离子多反应监测模式下检测，内标法定量。

结果

18种PAEs代谢物在0.10~80 ng/ml范围内线性关系良好，相关系数均大于0.999。18种PAEs代谢物的平均回收率为84.0%~113.0%，相对标准偏差范围为1.1%~9.5%，方法检出限为0.001~0.07ng/ml，定量限为0.002~0.2 ng/ml，日内和日间的精密度分别为1.3%~7.0%和1.0%~8.1%。应用该方法对160份尿样进行检测，除3种PAEs代谢物未检出外，其余15种PAEs代谢物的检出率在1.9%~100%之间，8种PAEs代谢物的检出率为100%，其中邻苯二甲酸单丁酯的浓度最高，中位值为126 ng/ml。

结论

该方法简便、灵敏、准确，适用于批量尿样中18种PAEs代谢物的检测。

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张艳，E-mail：
, copyrightStatement=本刊刊出的所有文章不代表中华预防医学会和本刊编委会的观点，除非特别声明。, copyrightOwner=中华预防医学会和四川大学华西公共卫生学院, extLink=null, articleAbsUrl=null, sourceXml=ASH/m/RitxOaAHSn6C2eiA==, magXml=ccj4lNXTJd2xLDGqdQ0fQQ==, pdfUrl=null, pdf=JflLl2eZEfTFsbPezQIHyA==, pdfFileSize=1388194, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=OpYRsA1wPWu59uGhuZ6cSA==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=OiABmYw6Hy1jIGjklB9K8w==, mapNumber=null, authorCompany=null, fund=null, authors=

张艳（1982—），女，博士，主任技师，研究方向：理化检验

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张艳（1982—），女，博士，主任技师，研究方向：理化检验

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张艳（1982—），女，博士，主任技师，研究方向：理化检验

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(In Chinese), articleTitle=SLE-HPLC-MS/MS determining f-ketamine and f-norketamine in blood or urine, refAbstract=null)], funds=[Fund(id=1241023864843596772, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, awardId=2220004000115, language=CN, fundingSource=珠海市社会发展领域科技计划项目(2220004000115), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241023857243517423, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, xref=null, ext=[AuthorCompanyExt(id=1241023857268683248, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, companyId=1241023857243517423, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Department of Physical and chemical Test, Zhuhai Center for Disease Control and Prevention, Zhuhai, Guangdong 519060, China), AuthorCompanyExt(id=1241023857285460465, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, companyId=1241023857243517423, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=珠海市疾病预防控制中心理化检验所，广东　珠海　519060)])], figs=[ArticleFig(id=1241023861593010981, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, language=EN, label=Fig.1, caption=Chromatograms of 18 PAEs metabolites spiked at a concentration of 10.0 ng/ml, figureFileSmall=evXWuYLe4AHvk2LrOt+Cig==, figureFileBig=OpYRsA1wPWu59uGhuZ6cSA==, tableContent=null), ArticleFig(id=1241023863128126262, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, language=CN, label=图1, caption=加标浓度10.0 ng/ml的18种PAEs代谢物色谱图

注：图(A)-(M)为MRM谱图，(N)为总离子流图。

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注：图(A)-(L)为检出目标组分的MRM谱图，(M)为总离子流图。

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Mass spectrometric parameters of 18 PAEs metabolites and internal standards

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物名称
(缩写)		保留时间
（min）		母离子
（m/z）		子离子
（m/z）		DP
（V）		CE
（eV）
邻苯二甲酸单甲酯（MMP）3.56179.077.0a,106.94022,15
邻苯二甲酸单乙酯（MEP）5.03193.077.0a,121.05022,15
邻苯二甲酸单异丙酯（MiPrP）6.71207.177.0a,57.04528,17
邻苯二甲酸单异丁酯（MiBP）9.07221.177.0a,71.05025,17
邻苯二甲酸单(2-乙基-5-氧己基)酯(MEOHP)9.10291.177.0a,141.07040,22
邻苯二甲酸单正丁酯（MnBP）9.30221.177.0a,133.95025,18
邻苯二甲酸单正苄酯（MBzP）9.55255.177.0a,105.15030,20
邻苯二甲酸单(2-乙基-5-羧基戊基)酯（MECPP）9.75307.0159.1a,113.04016,38
邻苯二甲酸单(2-乙基-5-羟基己基)酯(MEHHP)10.08293.1145.0a,120.86519,24
邻苯二甲酸单-(2-羧基甲基己基）酯(MCMHP)10.73307.2158.9a,113.04018,42
邻苯二甲酸单环己酯（MCHP）10.96247.097.1a,77.05719,33
邻苯二甲酸单正戊酯（MnPeP）11.38235.077.0a,85.15527,17
邻苯二甲酸单（2-乙基己基）酯（MEHP）15.52277.1134.0a,127.06021,21
邻苯二甲酸单正辛酯（MOP）15.95277.177.0a,127.06033,21
邻苯二甲酸单异壬酯（MiNP）15.96291.177.0a,141.07032,22
邻苯二甲酸单正壬酯（MNP）16.63291.1141.0a,77.07022,32
邻苯二甲酸单异癸酯（MiDP）16.85305.077.0a,155.08039,23
邻苯二甲酸单正癸酯（MDP）17.14305.1155.0a,77.06023,29
邻苯二甲酸单甲酯-13C43.54182.979.0a4023
邻苯二甲酸单乙酯-13C45.03197.079.0a4022
邻苯二甲酸单正丁酯-13C49.30225.079.0a4025
邻苯二甲酸单苄酯-13C49.54259.079.0a4027
邻苯二甲酸单环己酯-13C410.97251.079.0a5725
), ArticleFig(id=1241023864231228334, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, language=CN, label=表1, caption=

18种PAEs代谢物及内标的质谱参数

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物名称
(缩写)		保留时间
（min）		母离子
（m/z）		子离子
（m/z）		DP
（V）		CE
（eV）
邻苯二甲酸单甲酯（MMP）3.56179.077.0a,106.94022,15
邻苯二甲酸单乙酯（MEP）5.03193.077.0a,121.05022,15
邻苯二甲酸单异丙酯（MiPrP）6.71207.177.0a,57.04528,17
邻苯二甲酸单异丁酯（MiBP）9.07221.177.0a,71.05025,17
邻苯二甲酸单(2-乙基-5-氧己基)酯(MEOHP)9.10291.177.0a,141.07040,22
邻苯二甲酸单正丁酯（MnBP）9.30221.177.0a,133.95025,18
邻苯二甲酸单正苄酯（MBzP）9.55255.177.0a,105.15030,20
邻苯二甲酸单(2-乙基-5-羧基戊基)酯（MECPP）9.75307.0159.1a,113.04016,38
邻苯二甲酸单(2-乙基-5-羟基己基)酯(MEHHP)10.08293.1145.0a,120.86519,24
邻苯二甲酸单-(2-羧基甲基己基）酯(MCMHP)10.73307.2158.9a,113.04018,42
邻苯二甲酸单环己酯（MCHP）10.96247.097.1a,77.05719,33
邻苯二甲酸单正戊酯（MnPeP）11.38235.077.0a,85.15527,17
邻苯二甲酸单（2-乙基己基）酯（MEHP）15.52277.1134.0a,127.06021,21
邻苯二甲酸单正辛酯（MOP）15.95277.177.0a,127.06033,21
邻苯二甲酸单异壬酯（MiNP）15.96291.177.0a,141.07032,22
邻苯二甲酸单正壬酯（MNP）16.63291.1141.0a,77.07022,32
邻苯二甲酸单异癸酯（MiDP）16.85305.077.0a,155.08039,23
邻苯二甲酸单正癸酯（MDP）17.14305.1155.0a,77.06023,29
邻苯二甲酸单甲酯-13C43.54182.979.0a4023
邻苯二甲酸单乙酯-13C45.03197.079.0a4022
邻苯二甲酸单正丁酯-13C49.30225.079.0a4025
邻苯二甲酸单苄酯-13C49.54259.079.0a4027
邻苯二甲酸单环己酯-13C410.97251.079.0a5725
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Recoveries and precision of 18 PAEs metabolites (n=6)

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分析物1.00 ng/ml
测定值（ng/ml）		10.0 ng/ml
测定值（ng/ml）		50.0 ng/ml
测定值（ng/ml）		日内精密度
RSD(%)		日间精密度
RSD(%)
MMP1.03±0.0510.4±0.4450.6±1.686.13.6
MEP1.02±0.0511.3±0.3750.8±0.804.64.2
MiPrP1.00±0.0611.0±0.4551.0±1.072.24.3
MiBP0.84±0.0410.4±0.3149.9±1.573.72.7
MEOHP0.97±0.0510.4±0.3450.1±0.803.73.5
MnBP1.03±0.079.57±0.7949.6±2.093.21.0
MBzP1.00±0.0510.6±0.1950.6±1.861.31.9
MECPP1.03±0.0510.6±0.3850.9±0.771.81.2
MEHHP0.98±0.0310.3±0.3250.4±0.802.93.3
MCMHP0.89±0.0210.1±0.6952.4±2.277.08.1
MCHP1.03±0.0310.2±0.5350.2±0.603.02.0
MnPeP0.98±0.0410.0±0.3249.7±1.493.33.0
MEHP1.04±0.1010.4±0.6549.5±2.014.34.2
MOP1.00±0.0310.7±0.1150.0±1.191.93.6
MiNP0.96±0.0410.1±0.1848.5±1.574.13.7
MNP1.05±0.0210.7±0.3250.0±1.182.12.9
MiDP1.01±0.0310.2±0.5149.5±1.582.93.9
MDP0.98±0.059.81±0.3149.0±0.921.61.9
), ArticleFig(id=1241023864407389113, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, language=CN, label=表2, caption=

尿中18种PAEs代谢物的回收率和精密度（n=6）

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分析物1.00 ng/ml
测定值（ng/ml）		10.0 ng/ml
测定值（ng/ml）		50.0 ng/ml
测定值（ng/ml）		日内精密度
RSD(%)		日间精密度
RSD(%)
MMP1.03±0.0510.4±0.4450.6±1.686.13.6
MEP1.02±0.0511.3±0.3750.8±0.804.64.2
MiPrP1.00±0.0611.0±0.4551.0±1.072.24.3
MiBP0.84±0.0410.4±0.3149.9±1.573.72.7
MEOHP0.97±0.0510.4±0.3450.1±0.803.73.5
MnBP1.03±0.079.57±0.7949.6±2.093.21.0
MBzP1.00±0.0510.6±0.1950.6±1.861.31.9
MECPP1.03±0.0510.6±0.3850.9±0.771.81.2
MEHHP0.98±0.0310.3±0.3250.4±0.802.93.3
MCMHP0.89±0.0210.1±0.6952.4±2.277.08.1
MCHP1.03±0.0310.2±0.5350.2±0.603.02.0
MnPeP0.98±0.0410.0±0.3249.7±1.493.33.0
MEHP1.04±0.1010.4±0.6549.5±2.014.34.2
MOP1.00±0.0310.7±0.1150.0±1.191.93.6
MiNP0.96±0.0410.1±0.1848.5±1.574.13.7
MNP1.05±0.0210.7±0.3250.0±1.182.12.9
MiDP1.01±0.0310.2±0.5149.5±1.582.93.9
MDP0.98±0.059.81±0.3149.0±0.921.61.9
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Determination results of the 18 PAEs metabolites in human urines

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分析物阳性份数阳性率(%)最小值(ng/ml)最大值(ng/ml)平均值(ng/ml)中位值(ng/ml)
MMP15898.81.4488.2013.8010.20
MEP160100.00.94290.0035.6015.50
MiPrP00.0////
MiBP160100.076.10264.00121.00116.00
MEOHP160100.00.50289.0010.705.82
MnBP160100.025.90645.00148.00126.00
MBzP53.10.110.790.510.56
MECPP160100.00.72481.0019.2011.70
MEHHP160100.00.78529.0018.4010.10
MCMHP160100.00.35120.007.424.74
MCHP42.50.100.300.220.25
MnPeP00.0////
MEHP160100.03.6590.509.868.05
MOP31.90.260.380.310.29
MiNP00.0////
MNP15395.60.100.540.210.19
MiDP2012.50.375.302.182.02
MDP42.50.110.440.270.26
), ArticleFig(id=1241023864617104333, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241023852365541659, language=CN, label=表3, caption=

人尿中18种PAEs代谢物的测定结果

, figureFileSmall=null, figureFileBig=null, tableContent=
分析物阳性份数阳性率(%)最小值(ng/ml)最大值(ng/ml)平均值(ng/ml)中位值(ng/ml)
MMP15898.81.4488.2013.8010.20
MEP160100.00.94290.0035.6015.50
MiPrP00.0////
MiBP160100.076.10264.00121.00116.00
MEOHP160100.00.50289.0010.705.82
MnBP160100.025.90645.00148.00126.00
MBzP53.10.110.790.510.56
MECPP160100.00.72481.0019.2011.70
MEHHP160100.00.78529.0018.4010.10
MCMHP160100.00.35120.007.424.74
MCHP42.50.100.300.220.25
MnPeP00.0////
MEHP160100.03.6590.509.868.05
MOP31.90.260.380.310.29
MiNP00.0////
MNP15395.60.100.540.210.19
MiDP2012.50.375.302.182.02
MDP42.50.110.440.270.26
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固相支撑液液萃取结合超高效液相色谱-串联质谱法测定尿中18种邻苯二甲酸酯代谢物
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张艳 , 曲良娇 , 凌莉 , 吴和岩
现代预防医学 | 实验技术及其应用 2025,52(2): 328-335
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现代预防医学 | 实验技术及其应用 2025, 52(2): 328-335
固相支撑液液萃取结合超高效液相色谱-串联质谱法测定尿中18种邻苯二甲酸酯代谢物
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张艳 , 曲良娇, 凌莉, 吴和岩
作者信息
  • 珠海市疾病预防控制中心理化检验所，广东　珠海　519060

    • 张艳（1982—），女，博士，主任技师，研究方向：理化检验

通讯作者:

张艳，E-mail：
Determination of 18 phthalate esters metabolites in urine by solid-phase supported liquid-liquid extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry
Yan ZHANG , Liang-jiao QU, Li LING, He-yan WU
Affiliations
  • Department of Physical and chemical Test, Zhuhai Center for Disease Control and Prevention, Zhuhai, Guangdong 519060, China
出版时间: 2025-01-25 doi: 10.20043/j.cnki.MPM.202410288
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摘要
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目的

基于固相支撑液液萃取(SLE）技术，采用超高效液相色谱-串联质谱法（UPLC-MS/MS）建立尿液中18种邻苯二甲酸酯（PAEs）代谢物的测定方法。

方法

尿样中加入内标，经过酶解、SLE小柱净化后，采用BEH C18色谱柱色谱分离，在负离子多反应监测模式下检测，内标法定量。

结果

18种PAEs代谢物在0.10~80 ng/ml范围内线性关系良好，相关系数均大于0.999。18种PAEs代谢物的平均回收率为84.0%~113.0%，相对标准偏差范围为1.1%~9.5%，方法检出限为0.001~0.07ng/ml，定量限为0.002~0.2 ng/ml，日内和日间的精密度分别为1.3%~7.0%和1.0%~8.1%。应用该方法对160份尿样进行检测，除3种PAEs代谢物未检出外，其余15种PAEs代谢物的检出率在1.9%~100%之间，8种PAEs代谢物的检出率为100%，其中邻苯二甲酸单丁酯的浓度最高，中位值为126 ng/ml。

结论

该方法简便、灵敏、准确，适用于批量尿样中18种PAEs代谢物的检测。

邻苯二甲酸酯代谢物  /  尿  /  固相支撑液液萃取（SLE）  /  UPLC-MS/MS
Objective

To establish a method for the determination of 18 phthalates (PAEs) metabolites in urine by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) based on solid-phase support liquid-liquid extraction (SLE) technology.

Methods

Urine sample spiked with internal standards was first hydrolyzed by enzyme, then purified on a SLE column. The separation was performed on a BEH C18 column. The detection was performed in multi-reaction monitoring scan under negative mode. Internal standard method was applied for quantitative analysis.

Results

The 18 PAEs metabolites showed good linear relationships in the range of 0.10-80 ng/ml (r>0.999). The average recoveries of 18 PAEs metabolites ranged from 84.0%-113.0% with relative standard deviations between 1.1% and 9.5%. The limits of detection and quantitation of the method were 0.001-0.07ng/ml and 0.002-0.2 ng/ml, respectively. The intra-day and the inter-day precisions were 1.3%-7.0% and 1.0%-8.1%, respectively. 160 urine samples were analyzed with this method. Except for 3 PAEs metabolites that were not detected, the detection rates of the remaining 15 PAEs metabolites ranged from 1.9% to 100%, and the detection rates of 8 PAEs metabolites were 100%. Among them, mono-n-butyl phthalate had the highest concentrations with a median concentration of 126 ng/ml.

Conclusion

This method is simple, sensitive, and accurate, and it is suitable for the determination of 18 PAEs metabolites in large batchs of urine samples.

Phthalate esters metabolites  /  Urine  /  Solid-phase supported liquid-liquid extraction(SLE)  /  UPLC-MS/MS
张艳, 曲良娇, 凌莉, 吴和岩. 固相支撑液液萃取结合超高效液相色谱-串联质谱法测定尿中18种邻苯二甲酸酯代谢物. 现代预防医学, 2025 , 52 (2) : 328 -335 . DOI: 10.20043/j.cnki.MPM.202410288
Yan ZHANG, Liang-jiao QU, Li LING, He-yan WU. Determination of 18 phthalate esters metabolites in urine by solid-phase supported liquid-liquid extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Modern Preventive Medicine, 2025 , 52 (2) : 328 -335 . DOI: 10.20043/j.cnki.MPM.202410288
正文
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邻苯二甲酸酯(PAEs)为人工合成化合物，主要用作聚氯乙烯材料的增塑剂，以提高塑料产品可塑性、柔韧性和强度，被广泛应用于玩具、食品包装材料、个人护理产品、医疗器械等产品中。由于PAEs和塑料分子之间通常以分子间相互作用力结合，极易释放到环境中。据报道，在水、食物、室内空气、沉积物、生物样品等各种环境介质中均可检测到PAEs[1-7]。PAEs是潜在的内分泌干扰物和生殖毒物，研究表明，人类接触或摄入PAEs会对其生殖、发育和免疫力产生不利影响[8-10]。PAEs的毒性作用正日益引起公众的关注。PAEs进入人体后，很快代谢为PAEs的单酯、羟基化或氧化产物，以及葡萄糖醛酸结合型代谢产物，进一步从尿液中排出。由于尿液检测结果可以反映多种暴露途径的综合影响，一般以测定尿中PAEs代谢物含量的方式来评估PAEs在人体内的负荷水平。然而，目前尚无尿液中PAEs代谢物检测的国标方法，涉及人体PAEs暴露的研究也不多。
目前，对于PAEs代谢物的研究主要集中在检测方法和前处理技术两方面。其检测技术主要有气相色谱质谱联用法[11-12]和液相色谱质谱联用法[13-17]。前者通常需要衍生化，步骤繁琐，且衍生试剂毒性大，不适于大批量样品的检测。而后者因其具有分离能力强，灵敏度高、特异性强等优点，是目前生物监测中应用最广泛的检测技术。对于尿液样品中PAEs代谢物的提取净化，最常用的方法是固相萃取(SPE)法[12-14]，此外，石飞云等人[15]提出了将尿液酶解后直接用乙腈定容，冷冻除杂后过膜测定的方法，Alves rocha等人[16]提出了基于空气辅助液-液微萃取的尿样制备程序。
固相支撑液液萃取(SLE）基于传统液液萃取（LLE）的工作原理，利用特殊处理过的多孔吸附剂如硅藻土作为填料，水性样本吸附于填料微孔中形成表面积很大的液膜，当与水不混溶溶剂流经填料空隙时，溶剂与样本之间形成连续的浓度差，使目标物被高效萃取到溶剂中，实现对目标物的富集与净化。相较于SPE，SLE省去了活化和淋洗步骤，操作更简便，处理样品时，只需上样、静置和洗脱三个步骤即可完成目标分析物的提取和净化。该法消除了LLE中常见的相分离不完全和乳化问题。总体而言，SLE操作简便，易于自动化，是实现实验室高通量、高质量样本处理的有力工具，近年来在生物分析领域得到了广泛的关注和应用[17-19]。
本文采用SLE技术，通过优化萃取、洗脱流程及参数，开发了一种适用于尿液样本的前处理方法，结合UPLC-MS/MS，建立了尿液中18种PAEs代谢物的测定方法。该方法操作简单高效，重复性好，准确度高，实现了多种同分异构体的有效分离，适用于大批量尿样中PAEs代谢物的生物监测。
1　材料与方法
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1.1　仪器与试剂
Acquity UPLC-I-Class-Plus型超高效液相色谱仪(Waters，美国)；Triple Quad 6500+三重四级杆串联质谱仪（AB SCIEX，美国）；Extrahera全自动样品前处理系统（Biotage，瑞典）；TurboVap多功能全自动样品浓缩仪（Biotage，瑞典）；Acquity UPLC BEH 色谱柱，2.1 mm× 100 mm，1.7 μm（Waters，美国)；ISOLUTE SLE 1 mL柱（北京绿棉科技有限公司）；电热恒温水浴锅（美墨尔特，德国）；Milli-Q Advantage A10纯水机（Millipore，美国）；涡漩振荡器（IKA，德国）；电子天平（Sartorus，德国）；0.22 μm滤膜（ANPEL，中国）。
PAEs代谢物和内标的名称及其缩写见表1，邻苯二甲酸单正癸酯（MDP）和邻苯二甲酸单正壬酯（MNP）的标准品为固体，购自加拿大多伦多TRC公司，其余PAEs代谢物和内标均为液体，浓度为100 μg/ml，其中邻苯二甲酸单异癸酯（MiDP）和邻苯二甲酸单正戊酯（MnPeP）购自美国Accustandard公司，其余购自美国剑桥同位素公司。甲醇（MS级）、乙酸乙酯和乙酸铵（HPLC级）购自德国Merck公司。β-葡萄糖醛酸酶（>100 000 U/ml）和乙酸（分析纯）购自上海安谱实验科技有限公司。人工尿样来自北京汇智泰康医药技术有限公司。
1.2　方法
1.2.1　标准溶液配制
称取MDP和MNP标准各5 mg，分别用甲醇配制成100 μg/ml的单标溶液。分别吸取18种PAEs代谢物单标溶液各0.50 ml，用甲醇配制成5.0 μg/ml的PAEs混合标准储备液。取各PAEs代谢物的内标0.50 ml，甲醇稀释定容至10ml，配制成5.0 μg/ml的内标混标储备液。取适量PAEs代谢物的混合标准储备液，用甲醇-水溶液（1:1，v/v）配制成浓度分别为0.10、0.50、2.0、5.0、10、20、40、80 ng/ml的标准系列，其中内标的添加浓度为10 ng/ml。
1.2.2　样品前处理
采集的尿样于-80 ℃冰箱保存，使用时先将尿样置于4℃冰箱中解冻过夜，然后取出放至室温，涡旋混匀。取0.50 ml尿液于玻璃管中，依次加入20 μl内标混标（250 ng/ml）、0.30 ml乙酸铵缓冲溶液（1 mol/L，pH4.5）、20 μl β-葡萄糖醛酸酶，涡旋混匀，置于37℃水浴中避光酶解2 h，然后加入0.80 ml异丙醇-乙酸乙酯溶液（1：3，v/v），充分混匀，待净化。将待净化液加载至SLE柱上，静置5 min，同时收集流出液，加入5 ml乙酸乙酯进行洗脱，合并收集到的流出液和洗脱液，氮吹浓缩至近干，用0.50 ml甲醇-水（1：1，v/v）溶液复溶，涡旋振荡，过0.22μm尼龙滤膜，待上机检测。
1.2.3　色谱条件
流动相A：0.05%乙酸溶液，B:甲醇。洗脱程序：0 min，10% B；0~1.5 min，10%~30% B；1.5~14 min，30%~70% B；14~17 min，70%~95% B；17~19 min，95% B，19.1 min回到初始比例。流速0.3 ml/min，柱温40 ℃，进样5 μl。
1.2.4　质谱条件
电喷雾离子源负离子模式；多反应监测模式(MRM)扫描；喷雾电压-4 500 V；离子源温度550 ℃；气帘气35 psi；喷雾气55 psi；加热气55 psi；碰撞气9 psi。其余质谱参数见表1。
2　结果
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2.1　质谱条件优化
通过针泵进样，选择全扫描和产物离子扫描模式，调谐各参数，使目标化合物的母离子、子离子的响应达到最优。18种PAEs代谢物及内标的母离子、定量离子、定性离子、去簇电压（DP）、碰撞电压（CE）等参数信息见表1。
2.2　色谱条件优化
分别比较了Acquity UPLC BEH C18、Acquity UPLC HSS T3以及Acquity UPLC CSH C18三种常用色谱柱对18种PAEs代谢物的分离效果。相同流动相条件下，BEH C18柱对各组分的色谱分离表现最优，其次为HSS T3，CSH C18较差。各组分在BEH C18和HSS T3上的质谱响应差异不大，但对于MnBP和MiBP等同分异构体的分离，BEH C18柱的表现明显优于HSS T3，因此选用BEH C18作为分离柱。
比较了乙腈和甲醇两种有机相，水、0.05%甲酸水溶液、0.05%乙酸水溶液、5 mmol/L乙酸铵作为水相条件下，18种PAEs代谢物的色谱分离效果。结果表明，18种PAEs代谢物在甲醇和乙腈下的质谱响应差异不大，各组分在甲醇下的保留时间稍长于乙腈下的保留时间，但对于MnBP和MiBP等同分异构体的分离，甲醇的表现要明显优于乙腈。当水相为水时，目标组分的色谱峰拖尾严重，加入酸或者铵盐，峰型得到明显改善，各组分在0.05%乙酸水溶液的质谱响应和色谱峰型最优，其次为0.05%甲酸水溶液和5 mmol/L乙酸铵。还考察了0.025%乙酸水溶液、0.05%乙酸水溶液和0.1%乙酸水溶液三种浓度的水溶液对各组分色谱分离的影响，结果显示，0.05%乙酸水溶液对各组分的质谱响应和同分异构体的分离效果最优，其次为0.025%乙酸水溶液和0.1%乙酸水溶液。在优化的色谱条件下，加标浓度10.0 ng/ml的18种PAEs代谢物的UPLC-MS/MS色谱图见图1。
2.3　前处理优化
对于SLE，主要通过改变洗脱溶剂的种类和样液pH值来优化提取条件。选取环己烷、三氯甲烷、二氯甲烷、乙酸乙酯作为洗脱溶剂，考察其对18种PAEs代谢物的洗脱效果，采用目标组分的回收率进行评价，洗脱溶剂的用量均参照SLE小柱的推荐值5 ml进行操作。如图2所示，对于加标浓度为10 ng/ml的尿样，18种PAEs代谢物在环己烷、三氯甲烷、二氯甲烷、乙酸乙酯作为洗脱剂的回收率分别为38.8%~110.4%、58.2%~117.2%、74.4%~107.5%和82.4%~110.8%。因此选用乙酸乙酯作为洗脱溶剂。此外，试验还对乙酸乙酯的用量进行了优化，比较了3 ml、5 ml、8 ml不同体积洗脱的效果。当使用3 ml乙酸乙酯洗脱时，部分组分的回收率低于70%，洗脱不完全；而当采用5 ml和8 ml乙酸乙酯进行洗脱时，18种PAEs代谢物的回收率相当，均在80%以上。因此最终采用5 ml乙酸乙酯进行洗脱。
为获得最佳回收率，本试验对pH为4.5、6.5及9.0的乙酸铵缓冲液进行了测试。图3为不同pH的缓冲溶液下，18种PAEs代谢物的回收率结果。显然，当采用pH4.5的乙酸铵缓冲液时，所有目标组分经乙酸乙酯洗脱后，均获得了满意的回收率；当采用pH6.5的乙酸铵缓冲液时，MMP、MEP、MiPrP、MECPP和MCMHP的回收率低于50%；而当pH为9.0时，多达10种PAEs代谢物的回收率低于50%。因此样品处理时采用pH为4.5的乙酸铵缓冲液。
根据文献报道[14-15]，2.0 ml尿液在20 μl β-葡萄糖醛酸酶（大于85 000 U/ml）下酶解2 h，即可实现完全酶解。本实验的尿液样品量为0.50 ml，使用的β-葡萄糖醛酸酶浓度大于100 000 U/ml，因此选用酶解液用量20 μl、时间2 h作为酶解条件。通过对比实际尿样在20 μl酶解液2 h和30 μl酶解液12 h两种条件下的测定浓度，结果显示两者无显著差异。
2.4　复溶溶剂优化
样品净化液氮吹至近干后，比较了甲醇-水（1：9，v/v）、甲醇-水（1：1，v/v）及纯甲醇三种溶剂对18种PAEs代谢物的复溶效果。结果表明，以甲醇-水（1：9，v/v）为溶剂时，目标组分的信号强度明显低于用其他两种溶剂时的信号，而甲醇-水（1：1，v/v）和纯甲醇为溶剂时的信号强度相当；目标组分在纯甲醇中拖尾严重，而在其余两种溶剂中均可获得对称尖锐的峰型。因此复溶时选用甲醇-水（1：1，v/v）作为溶剂。
2.5　样品基质效应
取空白尿样按本法处理，对提取后的空白基质加入10 ng/ml混合标准溶液，同时以甲醇-水（1：1，v/v）为溶剂配制同浓度的工作液，通过比较该两种工作液在质谱中的信号强度，计算基质效应，结果显示，除MnBP的基质效应为1.40，表现为中等基质增强效应外，其余组分的基质效应在0.99~1.13之间，均表现为弱基质效应。基于此，本方法采用内标法进行定量，以降低基质效应的影响。
2.6　方法的线性范围、检出限及定量限
在最优分析参数下，测定标准系列溶液，以保留时间和离子丰度比定性，以目标组分与内标的定量离子峰面积比与其相应的质量浓度比作图，得到标准曲线。18种PAEs代谢物在0.10~80 ng/ml之间呈现了良好的线性，相关系数均大于0.999。取空白尿样进行提取净化，然后添加标准，以产生信噪比为3的响应时对应的浓度为检出限，信噪比为10对应的浓度为定量限，18种PAEs代谢物的检出限为0.001~0.07ng/ml，定量限为0.002~0.2 ng/ml。
2.7　加标回收率与精密度
在空白尿样中加入低、中、高（1.00、10.0、50.0 ng/ml）3个浓度，按本法处理后，每个浓度水平分析6次。结果列于表2，回收率在84.0%~113.0%之间，相对标准偏差（RSD）在1.1%~9.5%之间。通过对同一尿样进行日内精密度和日间精密度考察，结果日内精密度为1.3%~7.0%，日间精密度为1.0%~8.1%。结果表明，该方法回收率和稳定性较好，能满足生物样品检测的要求。
2.8　样品测定
采集160份人群尿液样品，按照本法进行测定，18种PAEs代谢物的测定结果列于表3。结果显示，除MiPrP、MnPeP、MiNP未检出外，其余15种PAEs代谢物的检出率在1.9%至100%之间，其中8种PAEs代谢物的检出率为100%。检出的组分按中位值从小到大排列依次为MNP、MCHP、MDP、MOP、MBzP、MiDP、MCMHP、MEOHP、MEHP、MEHHP、MMP、MECPP、MEP、MiBP、MnBP，其中MiBP和MnBP的中位值分别为116 ng/ml和126 ng/ml。图4为某一典型尿样的色谱图。
3　讨论
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18种PAEs代谢物中既有短链代谢物，又有长链代谢物，极性差异较大，加之多组分互为异构体，色谱分离是难点。选择合适的色谱柱是关键，本实验通过比较选择了通用性极佳的BEH C18色谱柱，该柱填料为杂化硅胶颗粒，耐受性较强，适用于分析非极性和中等极性化合物，18种PAEs代谢物均能获得较好的色谱分离。PAEs代谢物为羧基化合物，在中性或碱性条件下稳定性差，为防止其发生羧酸解离，色谱分离时可使用酸性流动相，促进其在色谱柱上的保留。实验结果也表明，水相中加入0.05%乙酸可以明显改善色谱峰型，增强质谱响应，但随着乙酸浓度的进一步增加，质谱响应呈减弱趋势，且同分异构体的分离也变差，可能是因为高浓度的酸会抑制目标物的离子化效率。
在SLE中，选择合适的吸附剂和洗脱条件对于提高回收率至关重要。目前，市场上SLE的吸附剂以硅藻土居多。根据SLE的工作原理，对于洗脱溶剂的选择，既要考虑是否与水混溶，又要考虑其对目标物的溶解性。本研究中，通过对4种不同溶剂的洗脱结果表明：使用环己烷洗脱时，MMP、MEP、MiPrP、MEOHP及MECPP的回收率较低；三氯甲烷作为洗脱剂时，MCMHP的回收率较低；而采用二氯甲烷和乙酸乙酯作为洗脱剂对所有化合物的回收均获得了满意结果，且乙酸乙酯的结果相对更优。环己烷和三氯甲烷的极性相对较小，而二氯甲烷和乙酸乙酯的极性比前两者要强，因此，用二氯甲烷和乙酸乙酯的回收率相对较高。此外，由于二氯甲烷对健康和环境的危害相对较大，洗脱时最终选用了乙酸乙酯。缓冲溶液的pH值对分析物的回收率起着关键作用。本实验通过比较不同pH值的回收率结果发现，除6个组分MEHP、MOP、MiNP、MNP、MiDP和MDP受pH的影响较小外，其余12种PAEs代谢物的回收率随着pH的升高而降低，在pH为4.5时回收率最优。由于PAEs代谢物呈弱酸性，当溶液pH呈弱酸性时，PAEs代谢物以分子形式存在，萃取效率更高。
对于PAEs代谢物的检测，试验过程尽可能采用玻璃材质的器皿，避免使用可能引入干扰物的试剂和耗材。当样品前处理的空白值高时，可在净化前先采用甲醇多次淋洗SLE柱，以便降低本底干扰。
本文采用SLE结合UPLC-MS/MS，建立了尿液中18种PAEs代谢物的分析方法。该方法操作简便，快速，方法准确性高，稳定性好，灵敏度高，适用于尿液样品中PAEs代谢物的定性定量分析，为人群生物监测快速测定人尿中PAEs代谢物提供了技术参考。应用该方法对160份尿样进行了监测，结果显示当地人群PAEs暴露情况不容乐观。
基金
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  • 珠海市社会发展领域科技计划项目(2220004000115)
文献
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2025年第52卷第2期
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doi: 10.20043/j.cnki.MPM.202410288
  • 接收时间：2024-10-21
  • 首发时间：2026-03-18
  • 出版时间：2025-01-25
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  • 收稿日期：2024-10-21
基金
珠海市社会发展领域科技计划项目(2220004000115)
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    珠海市疾病预防控制中心理化检验所，广东　珠海　519060

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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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