气相色谱-微芯片常压光电离质谱法分析选择性雄激素受体调节剂。

Analysis of selective androgen receptor modulators by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry.

机构信息

Laboratory of Analytical Chemistry, Department of Chemistry, University of Helsinki, Helsinki, Finland.

出版信息

J Am Soc Mass Spectrom. 2010 Feb;21(2):310-6. doi: 10.1016/j.jasms.2009.10.019. Epub 2009 Nov 6.

DOI:10.1016/j.jasms.2009.10.019

PMID:20004589

Abstract

A gas chromatography-microchip atmospheric pressure photoionization-mass spectrometric (GC-microAPPI-MS) method was developed and used for the analysis of three 2-quinolinone-derived selective androgen receptor modulators (SARMs). SARMs were analyzed from spiked urine samples, which were hydrolyzed and derivatized with N-methyl-N-(trimethylsilyl)trifluoroacetamide before analysis. Trimethylsilyl derivatives of SARMs formed both radical cations (M(+)) and protonated molecules (M + H) in photoionization. Better signal-to-noise ratios (S/N) were obtained in MS/MS analysis using the M(+) ions as precursor ions than using the M + H ions, and therefore the M(+*) ions were selected for the precursor ions in selected reaction monitoring (SRM) analysis. Limits of detection (LODs) with the method ranged from 0.01 to 1 ng/mL, which correspond to instrumental LODs of 0.2-20 pg. Limits of quantitation ranged from 0.03 to 3 ng/mL. The mass spectrometric response to the analytes was linear (R > or = 0.995) from the LOQ concentration level up to 100 ng/mL concentration, and intra-day repeatabilities were 5%-9%. In addition to the GC-microAPPI-MS study, the proof-of-principle of gas chromatography-microchip atmospheric pressure chemical ionization-Orbitrap MS (GC-microAPCI-Orbitrap MS) was demonstrated.

摘要

建立了一种气相色谱-微芯片常压光电离-质谱联用（GC-microAPPI-MS）方法，并用于分析三种 2-喹啉酮衍生的选择性雄激素受体调节剂（SARMs）。SARMs 从加标尿液样品中进行分析，这些样品在分析前用 N-甲基-N-（三甲基硅基）三氟乙酰胺进行水解和衍生化。在光电离中，SARMs 的三甲基硅衍生物形成自由基阳离子（M(+)) 和质子化分子(M + H)。与使用 M + H 离子作为前体离子相比，使用 M(+) 离子作为前体离子进行 MS/MS 分析可获得更好的信噪比（S/N），因此在选择反应监测（SRM）分析中选择 M(+*) 离子作为前体离子。该方法的检出限（LOD）范围为 0.01-1 ng/mL，相当于仪器检出限为 0.2-20 pg。定量限范围为 0.03-3 ng/mL。分析物的质谱响应从 LOQ 浓度水平到 100 ng/mL 浓度呈线性（R>或=0.995），日内重复性为 5%-9%。除了 GC-microAPPI-MS 研究之外，还证明了气相色谱-微芯片常压化学电离-轨道阱质谱（GC-microAPCI-Orbitrap MS）的原理验证。