头发中甲状腺激素和类固醇激素的高效液相色谱串联质谱检测  

Determination of Thyroids and Steroids in Hair by High Performance Liquid Chromatography Tandem Mass Spectrometry

作　　者：袁琳 吴彦 楚刘喜 王为 朱敏惠 张贺 杨瑾[2] 邓慧华 YUAN Lin;WU Yan;CHU Liu-Xi;WANG Wei;ZHU Min-Hui;ZHANG He;YANG Jin;DENG Hui-Hua(Key Laboratory of Child Development and Learning Science,School of Biological Science and Medical Engineering,Southeast University,Nanjing 210096,China;School of Public Health,Southeast University,Nanjing 210096,China)

机构地区：[1]东南大学生物科学与医学工程学院,儿童发展与教育部重点实验室,南京210096 [2]东南大学公共卫生学院,南京210096

出　　处：《应用化学》2022年第11期1703-1715,共13页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(No.81761128004)资助。

摘　　要：基于高效液相色谱-串联质谱(HPLC-MS/MS),开发了一种灵敏、可靠的方法,用于同时测定人类头发中的甲状腺和类固醇激素,包括甲状腺素(T4)、3,3′,5-三碘甲状腺原氨酸(T3)、3,3′,5′-三碘甲状腺原氨酸(rT3)、3,3′-二碘甲状腺原氨酸(3,3′-T2)、L-甲状腺原氨酸(T0)、皮质醇(F)和可的松(E)。头发用量20 mg,使用甲醇/氨水(体积比95∶5)在40℃下孵育24 h。采用电喷雾离子源,在多反应监测模式和正离子模式下进行定量分析。在甲醇/纯水(体积比80∶20,含0.2 mmol/L乙酸铵)的等度洗脱条件下,7种待测物分离良好。该方法检测上述7种激素的检测限在0.3~1.9 pg/mg,定量限在1.1~6.5 pg/mg;日内、日间变异系数均小于10%,回收率在89.4%~109.1%之间;稳定性、残留效应均符合检测标准要求。运用该方法检测140名被试的头发样本,所有被试的T0、F和E均可定量检测,而T4、T3、rT3和3,3′-T2的含量非常低,均在定量限附近,仅在少量被试中可被检出。A sensitive and reliable method based on high performance liquid chromatography-tandem massspectrometry(LC-MS/MS)is developed for the simultaneous determination of thyroids and steroids in humanhair,including thyroxine(T4),3,3′,5-triiodothyronine(T3),3,3′,5′-triiodothyronine(r T3),3,3′-diiodothyronine(3,3′-T2) L-thyronine(T0),cortisol(F) and cortisone(E). The seven endogenouscompounds are extracted from 20 mg hair sample incubated in the mixture solution of methanol and ammonia(volume ratio is 95∶5)for 24 hours at 40 ℃,and then analyzed with an electrospray ionization source inmultiple reaction monitoring mode and positive ion mode. Under the isocratic elution conditions with methanol/pure water(volume ratio is 80∶20,containing 0. 2 mmol/L ammonium acetate)as mobile phase,sevenanalytes are separated and well resolved. The limits of detection for the seven hormones range from 0. 3 to1. 9 pg/mg and the limits of quantification from 1. 1 to 6. 5 pg/mg. The intra-and inter-day coefficients ofvariation are less than 10% and the recoveries range from 89. 4% to 109. 1% for all seven compounds. Thestability and carryover also meet the detection criteria. The population analysis on hair samples from 140participants reveals that T0,F and E could be quantified in all subjects,while T4,T3,r T3 and 3,3′-T2could be detected in a small number of subjects,showing the contents around their limits of quantification.

关 键 词：甲状腺激素 类固醇激素 液相色谱串联质谱法 头发含量 

分 类 号：O657.6[理学—分析化学]