Shin Hyun Du, Suh Joon Hyuk, Kim Junghyun, Cho Hyun-Deok, Lee Su Duk, Han Kwan Seok, Wang Yu, Han Sang Beom
Department of Pharmaceutical Analysis, College of Pharmacy, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 06974, Republic of Korea; Racing Laboratory, Korea Racing Authority, Republic of Korea.
Department of Food Science and Human Nutrition, Citrus Research and Education Center, University of Florida, 700 Experiment Station Rd, Lake Alfred, FL 33850, USA.
J Pharm Biomed Anal. 2017 Oct 25;145:46-51. doi: 10.1016/j.jpba.2017.06.036. Epub 2017 Jun 19.
A high throughput method for simultaneous screening of anabolic steroids and their metabolites (4-esterendione, trenbolone, boldenone, oxandrolone, nandrolone, methandrostenolone, testosterone, 1-androstendione, ethisterone, normethandrolone, methyltestosterone, 16β-Hydroxystanozolol, epitestosterone, bolasterone, norethandrolone, danazol, stanozolol and androstadienone) in equine urine by online turbulent flow extraction coupled with liquid chromatography-tandem mass spectrometry was developed. The use of turbulent flow chromatography could simplify pretreatment of horse urine, which has complex matrices as well as high viscosity. The urine was extracted by mixed-mode cation exchange solid phase extraction, and hydrolyzed using β-glucuronidase/arylsulfatase. Then, the sample was automatically loaded on the TurboFlow Cyclone extraction column for removal of further matrix, followed by separation on a fused core C18 column before MS/MS detection. Optimization and validation of the method were discussed in detail. All analytes were rapidly detected within 10min with high sensitivity (picogram to nanogram per milliliter level), and no interference was observed. The linearity range was from 0.1-10ng/mL for nine steroids and 1.0-50ng/mL for the others, with correlation of coefficient values over 0.995. Precision and accuracy ranged from 0.1 to 14.5% and 1.7 to 12.4%, respectively. The developed method was successfully applied to the analysis of anabolic steroids in horse urine after administration of a model drug.
建立了一种在线湍流萃取结合液相色谱 - 串联质谱法同时筛选马尿中合成代谢类固醇及其代谢物(4 - 酯二酮、群勃龙、勃地酮、氧雄龙、诺龙、甲基雄烯醇酮、睾酮、1 - 雄烯二酮、炔孕酮、诺美睾酮、甲基睾酮、16β - 羟基司坦唑醇、表睾酮、勃拉睾酮、诺乙雄龙、达那唑、司坦唑醇和雄甾二烯酮)的高通量方法。湍流色谱的使用可简化马尿的预处理,马尿基质复杂且粘度高。尿液通过混合模式阳离子交换固相萃取进行萃取,并用β - 葡萄糖醛酸酶/芳基硫酸酯酶水解。然后,将样品自动加载到TurboFlow Cyclone萃取柱上以进一步去除基质,随后在熔融核C18柱上进行分离,然后进行MS/MS检测。详细讨论了该方法的优化和验证。所有分析物在10分钟内快速检测到,灵敏度高(皮克到纳克每毫升水平),且未观察到干扰。九种类固醇的线性范围为0.1 - 10ng/mL,其他类固醇为1.0 - 50ng/mL,相关系数值超过0.995。精密度和准确度分别为0.1%至14.5%和1.7%至12.4%。所建立的方法成功应用于模型药物给药后马尿中合成代谢类固醇的分析。