分析化学2024，Vol.52Issue(9)：1346-1354,中插29-中插35,16.DOI:10.19756/j.issn.0253-3820.241070
超高效液相色谱-串联质谱法测定血清和尿液中有机磷酸酯及其代谢物
Determination of Organophosphate Esters and Metabolites in Serum and Urine by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry
摘要
Abstract
A new method was developed for simultaneous detection of total 19 kinds of organophosphate esters(OPEs)and their diester metabolites(di-OPEs)in human serum(1.0 mL)and urine(1.5 mL)with low volume of samples.The target compounds were determined using ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)after acetonitrile liquid-liquid extraction combined with purification using an ENVI-18 solid-phase extraction(SPE)column.OPEs and di-OPEs were separated using a Shim-pack GIST C18 column(100 mm×2.1 mm,2 μm)with a Shim-pack GIST-HP(G)C18 guard column.An electrospray ionization source(ESI)was employed in mass spectrometry analysis,with positive/negative ion mode using the multiple reaction monitoring(MRM).All target compounds were separated within 15 min,and exhibited good linear relationships in the concentration range of 2-100 ng/mL,with correlation coefficients(R2)above 0.994.The method detection limits(MDL)in serum ranged from 0.001 to 0.178 ng/mL and the MDL in urine ranged from 0.001 to 0.119 ng/mL.The recoveries of the analytes spiked in serum and urine matrices at two concentration levels were 30.5%-126.8%,with the relative standard deviations(RSDs)ranged from 1%to 23%.In addition,paired serum and urine samples from 11 patients were analyzed.For all samples tested,the internal standards of OPEs exhibited recoveries between 61%and 114%,whereas the internal standards for di-OPEs had recoveries ranging from 43%to 103%.OPEs and di-OPEs exhibited high detection frequencies in 22 serum and urine samples.Triethyl phosphate(TEP),tributyl phosphate(TBP),tris(2-ethylhexyl)phosphate(TEHP),tris(2-butoxyethyl)phosphate(TBEP),tris(1-chloro-2-propyl)phosphate(TCIPP),triphenyl phosphate(TPHP),tri-m-tolyl-phosphate(TMTP)and 2-ethylhexyl diphenyl phosphate(EHDPP)were universally detected in all serum samples.TCIPP was identified at the highest concentrations(median 0.548 ng/mL)in serum samples.In urine samples,the detection frequency for 12 kinds of target compounds reached 100%.Notably,TBP emerged as the predominant OPE in urine,demonstrating a median concentration of 0.506 ng/mL.Regarding di-OPEs,bis(2-chloroethyl)phosphate(BCEP)and bis(2-butoxyethyl)hydrogen phosphate(BBOEP)were the most abundant in urine,with median concentrations of 6.404 and 2.136 ng/mL,respectively.The total concentrations of OPEs and di-OPEs in serum and urine were 1.580-3.843 ng/mL and 5.149-17.537 ng/mL,respectively.These results not only confirmed the effectiveness of the method in detection of OPEs and di-OPEs in biological matrices,but also revealed the widespread presence of OPE compounds in human body and pointed to potential exposure risks.关键词
超高效液相色谱-串联质谱/有机磷酸酯/代谢产物/血清/尿液Key words
Ultra-high performance liquid chromatography-tandem mass spectrometry/Organophosphate esters/Metabolites/Serum/Urine引用本文复制引用
吴文琪,陈春赐,王晓霞,刘文彬,高丽荣,于洋,贾天琪,石喆元,何蕴琛,邓静霖..超高效液相色谱-串联质谱法测定血清和尿液中有机磷酸酯及其代谢物[J].分析化学,2024,52(9):1346-1354,中插29-中插35,16.基金项目
浙江省重点研发计划项目(No.2021C03176)、国家重点研发计划项目(No.2022YFC3902302)和国家自然科学基金项目(No.22076207)资助. Supported by the Key Research and Development Plan of Zhejiang Province(No.2021C03176),the National Key Research and Development Program of China(No.2022YFC3902302)and the National Natural Science Foundation of China(No.22076207). （No.2021C03176）
