使用离子运动质谱法 (IM-MS) 改进了衍生类固醇激素异构体的分析
Shon P Neal1, Walker N Hodges2, Diana C Velosa1
1Chemistry Program, Department of Biomedical and Chemical Engineering and Sciences, Florida Institute of Technology, Melbourne, FL, 32901, USA.
Analytical and bioanalytical chemistry
|September 23, 2023
概括
使用吉拉德试剂和CDI的化学导化显著增强了离子流动性质谱学 (IM-MS) 中的同位素分离. 这种方法提高了类固醇激素异构体的分辨率,使复杂的生物样本能够进行更准确的分析.
科学领域:
- 分析化学 分析化学
- 生物化学 生物化学
- 分离科学 分离科学
背景情况:
- 离子移动性质谱 (IM-MS) 已取得显著的进步,但其分辨能力往往不足以分离构造性和立体化学同体.
- 现有的IM-MS平台通常提供适度的分辨能力 (40-60),限制了复杂异构混合物的常规分析.
- 仪器仪表的改进增加了分辨能力,但化学衍生提供了一个补充的策略,以提高现有硬件的分离能力.
研究的目的:
- 为了研究化学衍生反应的实用性,特别是使用吉拉德试剂和1,1-碳基胺 (CDI),以改善类固醇激素异构体的离子移动性分离.
- 评估这些衍生方法的速度,简单性和成本效益.
- 展示这些方法在复杂的生物矩阵中分析类固醇异构体的应用.
主要方法:
- 使用吉拉德试剂 (向碳基组) 和CDI (向基组) 来衍生类固醇激素异构体.
- 用标准实验室设备在温和条件下 (≤30分钟) 进行衍生反应.
- 通过离子流动性质谱法 (IM-MS) 实现了衍生异构体的分离,分辨率由峰值到峰值分辨率 (Rpp) 量化.
- 碰撞横截面 (CCS) 测量被用于化合物识别.
- 从尿样中提取的类固醇进行了衍生和分析.
- 应用了基于软件的高分辨率解复合方法,以进一步提高分辨率.
主要成果:
- 使用CDI的衍生物显著改善了氧异构体 (Rpp = 1.10),脱氧皮异构体 (Rpp = 1.47) 和脱氧美异构体 (Rpp = 1.98) 的分辨率.
- 吉拉德的试剂和CDI反应是快速的,简单的,经济的,针对类固醇中的关键功能组.
- 特征性的碰撞截面 (CCS) 测量有助于自信地识别衍生类固醇.
- 在提取的尿样中对衍生类固醇的分析产生了可比的分辨率改善.
- 衍生和高分辨率解复软件的结合方法将分辨率提高到>150.
结论:
- 有针对性的化学衍生,特别是CDI和吉拉德试剂,是一种强大的策略,可以通过现有的IM-MS仪器来增强挑战性类固醇激素异构体的分离.
- 这些方法提供了一种实用,具有成本效益和高效的手段,可以放大微妙的结构差异,从而提高分辨率和更准确的识别.
- 在尿液等复杂的生物矩阵中成功应用表明了这种综合类固醇分析方法的临床和研究潜力.
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