The Analytical Methodology Development And Application Of Bisphenol Analogues In Biological Matrix

Bisphenol compounds(BPs)have been proved to be environmental endocrine disruptors(EEDCs),and been concerned due to its estrogen effects and other toxicities.In this paper,24 kinds of BPs were selects as the research object to establish analytical methods for different biological matrices(breast milk,urine and serum),as well as the exposure of BPs in breast milk samples from 7 provinces were detected and evaluated.The main research contents are as follows:In section one,the derivatization methods of 24 bisphenol compounds were established:pyridine-3-carbonyl chloride was used as a derivatizing agent,the solvent was acetone,and the concentration was 5 mg/mL,the pH of sodium bicarbonate buffer was 10.5.Then the target compounds were incubated at 60 ℃ for 5 min,cooled and extracted with N-hexane for analysis.In section two,a pretreatment method of 24 BPs in breast milk samples was established by detection method of ultra performance liquid chromatography tandem mass spectrometry.The samples were incubated overnight and extracted with acetonitrile,degreased and purified by the EMR-Lipid dispersive solid phase extraction filler,then derivatived with pyridine-3-carbonyl chloride and extracted by N-hexane,and analyzed by UPLC-MS/MS in positive ion mode.The recoveries at three spiked levels in breast milk matrix were 86.11%～119.05%,respectively,with relative standard deviations(RSD)no more than 19.50%(n=6)and intra-day precision less than 11.34%.The limits of quantification and the limit of detection of the method were 0.001～0.200 μg/L for 24 target compounds.This method was applied for the analysis of 20 breast milk samples collected from Hunan Province.In section three,a method of 24 target compounds were established in urine.After incubation overnight,the samples were extracted with ethyl acetate by liquid-liquid extraction.Then the samples were derivatived with PS-C1 and extracted by N-hexane,and analyzed by UPLC-MS/MS.The recoveries for all target compounds in urine were 82.91%～122.49%with RSD less than 12.34%(n=6),and the LOQs and LODs of the method were 0.006～0.250 μg/L and 0.003～0.100 μg/L.This method can be applied for analyzing target compounds in urine collected from Beijing.In section four,a analytical method based on UPLC-MS/MS was established to detect target compounds in serum.Serum samples were incubated overnight and then extracted with acetonitrile,purified by a PRiME HLB cartridge and derived with PS-C1.Recoveries for all BPs at three fortification levels in serum were 58.41%～118.34%and RSD was no more than 13.83%(n=6).The LOQs and LODs of the method were 0.001～0.200 μg/L and 0.0003～0.067 μg/L,respectively.This method was used to analyze real serum samples from Beijing.In section four,102 breast milk samples collected from seven provinces(Heilongjiang,Hebei,Inner Mongolia,Guangxi,Sichuan,Jiangsu and Jiangxi)were analyzed by the above method of breast milk.The results indicated that BPA、BPB、BPE、BPS、BPF、BPZ、BPAF、TBBPA、MCBPA were detected,the concentration range of ND～20.861 μg/L.