Abstract The enantioselective analytical method for trace ketoprofen (KET) in human saliva was developed for the first time using liquid chromatography/electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS) combined with a derivatization using a chiral reagent, (S)‑1‑methyl‑4‑(5‑(3‑aminopyrrolidin‑1‑yl)‑2,4‑dinitro‑phenyl)piperazine (APy‑PPZ). The APy‑PPZ derivatization enabled highly sensitive detection (detection limit, 0.5 fmol on column) and complete separation with high resolution (Rs = 4.3) of KET enantiomers. The calibration curves of both KET enantiomers in saliva were linear in the concentration range of 5–500 nM. The developed method showed good analytical performance with relative standard deviations (RSDs) below 2.6% and good accuracy (100.5–105.9%) through intra- and inter-assay and gave a potential for practical application to the quantitative determination of KET in human saliva.

中文翻译：

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手性衍生化液相色谱/串联质谱法对人唾液中酮洛芬的对映选择性分析

摘要 使用液相色谱/电喷雾电离串联质谱 (LC/ESI-MS/MS) 结合手性试剂衍生化，首次开发了人唾液中痕量酮洛芬 (KET) 的对映选择性分析方法，(S )-1-甲基-4-(5-(3-氨基吡咯烷-1-基)-2,4-二硝基-苯基)哌嗪(APy-PPZ)。APy‑PPZ 衍生化实现了 KET 对映异构体的高灵敏度检测（检测限，柱上 0.5 fmol）和高分辨率 (Rs = 4.3) 的完全分离。唾液中两种 KET 对映异构体的校准曲线在 5–500 nM 的浓度范围内呈线性。开发的方法显示出良好的分析性能，相对标准偏差 (RSD) 低于 2.6%，准确度 (100.5–105)。