人尿中双酚型二缩甘油醚及衍生物的液相色谱串联质谱测定法

Determination of bisphenol type diglycidyl ethers and derivatives in human urine by high-performance liquid chromatography-tandem mass spectrometry

目的建立测定人尿中游离型双酚A型与双酚F型二缩甘油醚（BADGE,BFDGE）及其水解衍生物浓度的同位素内标-液液萃取-高效液相色谱串联质谱（HPLC）测定法。方法采用不同萃取剂和不同规格固相萃取柱进行前处理,以含乙酸铵或甲酸的甲醇和水为流动相,以梯度洗脱方式用C18色谱柱对目标化合物进行分离。以正离子喷雾模式电离,多反应离子监测方式进行定性及定量检测。结果该方法检测BADGE、BFDGE和2种衍生物在0.25~50 ng/ml范围内满足线性要求（r=0.999）。以D6-BADGE作为内标物质,液液萃取法对4种目标化合物3个浓度水平的加标回收率均在80%~120%,最低检出限为0.08~0.15 ng/ml,定量限为0.25~0.50 ng/ml,日内和日间RSD〈10%。结论该方法对人尿中BADGE、BFDGE及其水解代谢产物的测定具有较高的灵敏度和精确性,可满足尿液样本中痕量BFDGE的检测需要;实际样本检测表明双酚型二缩甘油醚类物质可能对我国人群存在较广泛的暴露。

Objective To establish an effective method for the determination of bisphenol A diglycidyl ether （BADGE）, bisphenol F diglycidyl ether （BFDGE） and their hydrolytic derivatives in human urine. Methods Different organic extracts and solid phase extraction （SPE） cartridges were used in the pretreatment process. Methanol and Milli-Q water containing ammonium acetate were applied as the mobile phase under a gradient elution system, while a C18 analytical column was used for analytes seperation. Mass spectrometry under positive electrospray ionization mode and multiple reaction monitoring （MRM） were performed for the qualitative and quantitative analysis. Results The linear range for four analytes was 0.25-50 ng/ml （r=0.999）. Optimized recoveries of all four analytes at three different levels spiked in urine samples corrected by the inter standard （D6-BADGE） were in the range of 80%-120%. The limit of detections and quantifications were 0.08-0.15 ng/ml and 0.25-0.50 ng/ml respectively. The intra- and inter- day RSDs were lower than 10%. Conclusion This method is sensitive, and the selectivity and orecision are high enough for the determination of trace BADGE in human urine soecimens.