固相萃取–气相色谱–质谱法测定血清邻苯二甲酸酯类化合物含量  

Determination of phthalate acid esters in serum by solid-phase extraction coupled with gas chromatography-mass spectrometry

作　　者：徐海娥[1] 徐吉巧[2] 戴雪璐 刘运明[3] XU Hai-E;XU Ji-Qiao;DAI Xue-Lu;LIU Yun-Ming(Department of Clinical Nutrition,the Second Affiliated Hospital of Nanjing Medical University,Nanjing 210011,China;Department Endocrinological Surgery,the Second Affiliated Hospital of Nanjing Medical University,Nanjing 210011,China;Physical and Chemical Inspection Institute,Jiangsu Provincial Center for Disease Control and Prevention,Nanjing 210009,China)

机构地区：[1]南京医科大学第二附属医院临床营养科,南京210011 [2]南京医科大学第二附属医院外科,南京210011 [3]江苏省疾病预防控制中心理化检验所,南京210009

出　　处：《实验室检测》2024年第11期29-32,共4页Laboratory Testing

摘　　要：目的建立固相萃取(solid phase extraction,SPE)–气相色谱(gas chromatography,GC)–串联四级杆质谱(mass spectrometry,MS)测定血清4种常见的邻苯二甲酸酯类化合物:邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二丁酯及邻苯二甲酸二(2–乙基)己酯的检测方法。方法样本前处理采用SPE(正相键合模式)玻璃小柱对血清中PAEs萃取富集。色谱柱升温程序:初温60℃,保持1 min,以20℃/min升温至220℃,再以5℃/min升温至290℃保持2 min,290℃后运行2 min。质谱条件为:电子轰击源(EI)能量:70 eV;离子源温度:240℃;四级杆温度:150℃;选择离子模式(selected ion monitoring,SIM)检测。以目标化合物保留时间及目标化合物质荷比(m/z)来定性,内标法定量分析。同时对方法的精密度及加标回收率进行测定。结果DMP、DEP、DBP、DEHP的标准曲线回归方程均具有良好的线性关系(相关系数均大于0.997)。4种物质的最低检出限(limit of detection,LOD)为2~3μg/L;精密度分别为2.60%、4.73%、5.50%及5.70%;空白加标中平均回收率为94.5%。甲状腺乳头癌志愿者血清中DMP检出率为31.6%;DEP检出率为73.4%;DBP及DEHP的检出率达100%。结论该方法使用的有机试剂量少,样本萃取耗时短,回收率和重现性良好,检测限较低,可适用于人体血清中多种PAEs类物质的同时检测。Objective To develop a gas chromatography-mass spectrometry solid-phase extractionfor detectingphthalic acid esters(PAEs)in the serum of patients with thyroid cancer.Four PAEs,namely,dimethyl phthalate(DMP),diethyl phthalate(DEP),dibutyl phthalate(DBP),and di(2-ethyl)hexyl phthalate(DEHP),were used in experiments.Methods Samples of PAEs were extracted and enhanced using a solid-phase extraction glass column.The column temperature parameters were as follows:the initial temperature was 60℃.The temperature was maintained at 60℃for 1 min and then increased by 20℃/min to 220℃.The temperature was then increased by 5℃/min to 290℃and maintained at 290℃for 2 min.The mass spectrometry conditions were as follows:the ionization mode was electron impact,the source energy was 70 eV,the ion source temperature was 240℃,the quadrupole temperature was 150℃,and the scanning mode was selective ion monitoring(SIM).These parameters were qualitatively based on the target compound’s retention time and the mass-to-charge ratio(m/z).Quantitative analysis was conductedusing the standard internal method.Results The standard curve regression equations of DMP,DEP,DBP,and DEHP all had excellent linear relationships with correlation coefficients greater than 0.997.The precision of DMP,DEP,DBP,and DEHP was 2.60%,4.73%,5.50%and 5.70%,respectively.The average recoveries were in the average range of 94.5%.The detection rate of DBP,DMP,DEP and DEHP were 100%,31.6%,73.46%,and 100%,respectively.Conclusion The method is suitable for simultaneous detection of PAEs in human serum,with low organic dose,short extraction time,good recovery and reproducibility,and low detection limit.

关 键 词：固相萃取 气相色谱–质谱联用 邻苯二甲酸酯类化合物 血清 

分 类 号：R446.11[医药卫生—诊断学] O657.63[医药卫生—临床医学]