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采用超高效液相色谱-串联质谱法同时测定人尿液中的雄激素和前列腺素。

Simultaneous determination of androgens and prostaglandins in human urine using ultra-high-performance liquid chromatography-tandem mass spectrometry.

机构信息

Molecular Recognition Research Center, Korea Institute of Science and Technology (KIST), Seoul 02792, Republic of Korea; Department of Chemistry, Yonsei University, Wonju 26493, Republic of Korea.

Department of Dermatology, Kyung Hee University Hospital at Gangdong, Kyung Hee University School of Medicine, 05278, Republic of Korea.

出版信息

J Chromatogr B Analyt Technol Biomed Life Sci. 2019 Mar 1;1109:45-53. doi: 10.1016/j.jchromb.2019.01.022. Epub 2019 Jan 28.

DOI:10.1016/j.jchromb.2019.01.022
PMID:30716600
Abstract

A simultaneous quantitative profiling method for androgens and prostaglandins using ultra-high-performance liquid chromatography-tandem mass spectrometry was developed and validated to evaluate urinary androgen and prostaglandin levels. Solid-phase extraction and liquid-liquid extraction steps were combined during the sample preparation. β-Glucuronidase/arylsulfatase was also used in the enzyme hydrolysis step. Chemical derivatization was performed using 2-hydrazinopyridine for simultaneous determination of androgen and prostaglandin in the same ionization mode. The analytes were all separated and measured using multiple reaction monitoring in the positive ion mode within a run time of 22 min. The method was validated, achieving overall recoveries ranging from 81.0 to 102.9% with limits of quantification ranging from 0.01 to 2 ng/mL. The intra-day accuracy and precision ranged from 6.5 to 14.3% and from 77.1 to 106.8%, respectively. The inter-day accuracy and precision ranged from 8.9 to 18.2% and 89.9 to 101.4%, respectively. The linearity was expressed using the correlation coefficient, which was >0.99. The method developed herein was used to investigate the effects of a one-year finasteride treatment through differences in urinary androgen and prostaglandin levels between treated male pattern baldness patients and normal controls. The urinary androgen and prostaglandin levels were not significantly different between the two groups because of the administration of finasteride. The results confirmed that finasteride affects androgens and PGs related to hair regrowth and growth length, and a one-year finasteride treatment is effective for MPB. The mass spectrometry-based quantitative profiling method used herein for the investigation of male pattern baldness also holds great potential for the evaluation of androgens and prostaglandins associated with the metabolism of various inflammatory diseases.

摘要

建立并验证了一种同时测定雄激素和前列腺素的超高效液相色谱-串联质谱法,用于评估尿液中雄激素和前列腺素水平。在样品制备过程中结合了固相萃取和液-液萃取步骤。在酶水解步骤中也使用了β-葡萄糖醛酸酶/芳基硫酸酯酶。化学衍生化使用 2-肼吡啶进行,以相同的电离模式同时测定雄激素和前列腺素。所有分析物均在正离子模式下以多反应监测进行分离和测定,运行时间为 22 分钟。该方法经过验证,总回收率在 81.0%至 102.9%之间,定量下限在 0.01 至 2ng/mL 之间。日内准确度和精密度分别为 6.5%至 14.3%和 77.1%至 106.8%。日间准确度和精密度分别为 8.9%至 18.2%和 89.9%至 101.4%。线性关系用相关系数表示,大于 0.99。本文所建立的方法用于研究非那雄胺治疗一年对男性型脱发患者和正常对照组尿液中雄激素和前列腺素水平的影响。由于非那雄胺的给药,两组患者的尿液雄激素和前列腺素水平无显著差异。结果证实,非那雄胺影响与头发生长和生长长度相关的雄激素和 PGs,非那雄胺治疗一年对男性型秃发有效。本文用于研究男性型脱发的基于质谱的定量分析方法也为评估与各种炎症性疾病代谢相关的雄激素和前列腺素具有很大的潜力。

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