基质固相分散萃取和固相萃取-高效液相色谱-三重四极杆-复合线性离子阱质谱同时测定奶制品中6种雌激素

采用了基质固相分散萃取（MSPD）和固相萃取（SPE）技术分别对奶制品（奶粉和牛奶）中6种雌激素进行提取和净化。结果显示，MSPD适用于固体奶粉的处理，而SPE则适用于液体牛奶的处理。基于优化结果，利用高效液相色谱-三重四极杆-复合线性离子阱质谱（HPLC-Q-TRAP-MS）建立了在不同奶制品中同时测定6种雌激素含量的方法。方法学考察结果显示，建立的分析方法符合含量测定要求，在0.1~200 mg/L（雌三醇为0.1~20 mg/L）范围内线性关系良好（相关系数（R²）>0.99）；检出限（LOD，S/N=3）和定量限（LOQ，S/N=10）分别为0.01~0.05 mg/L和0.05~0.10 mg/L。在添加水平分别为1.0、5.0和10 mg/kg时，固态奶粉经MSPD处理后，6种雌激素的平均回收率为71.8%~106.0%（RSD为1.6%~9.2%，n=3）；液态牛奶经SPE处理后，6种雌激素的平均回收率为70.3%~108.4%（RSD为2.0%~11.0%，n=3）。该方法灵敏度和重复性高，适于分析复杂基质中雌激素的痕量残留。

Simultaneous determination of six estrogens in dairy products by high performance liquid chromatography-triple quadrupole-ion trap mass spectrometry coupled with matrix solid-phase dispersion and solid phase extraction

Matrix solid-phase dispersion (MSPD) and solid-phase extraction (SPE) were respectively developed for the pretreatment six estrogens in milk powder and liquid milk. It was implied that MSPD was suitable for the treatment of milk powder, while SPE was suitable for liquid milk treatment. Based on the optimized pretreatment procedures, the method for the simultaneous determination of the six estrogens in different dairy products was established by high performance liquid chromatography-triple quadrupole-ion trap mass spectrometry (HPLC-Q-TRAP-MS). The proposed method provided low limits of detection (LODs, 0.01-0.05 mg/L) and limits of quantification (LOQs, 0.05-0.10 mg/L), wide linearity range of 0.1-200 mg/L (except for estriol of 0.1-20 mg/L) with excellent correlation coefficients (R²)> 0.99. The average recoveries of the six estrogens in milk powder pretreated by MSPD ranged from 71.8% to 106.0% with RSD of 1.6%-9.2% (n=3), while the corresponding average recoveries in liquid milk pretreated by SPE ranged from 70.3% to 108.4% with RSD of 2.0% and 11.0% (n=3) with spiking levels of 1.0, 5.0, and 10 mg/kg, respectively. This sensitive and reliable method meets the demand for the analysis of trace estrogen residues in complex matrices.