Thiyl Radical-Based Charge Tagging Enables Sterol Quantitation via Mass Spectrometry,Analytical Chemistry

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Thiyl Radical-Based Charge Tagging Enables Sterol Quantitation via Mass Spectrometry
Analytical Chemistry ( IF 6.7 ) Pub Date : 2017-11-22 00:00:00 , DOI: 10.1021/acs.analchem.7b04080
Sarju Adhikari _{1,

2} , Yu Xia _{1,

2}

Affiliation

Inspired by the high reactivity and specificity of thiyl radicals toward alkenes, we have developed a new charge derivatization method to enable fast and quantitative analysis of sterols via electrospray ionization-mass spectrometry (ESI-MS). Thioglycolic acid (TGA), a commercially available compound, has been established as a highly efficient tagging reagent. Initiated from photochemical reactions, the thiyl radical derived from TGA abstracts an allylic hydrogen in the B ring of sterols, forming a radical intermediate which rapidly recombines with a second thiyl radical to produce the final tagged product. Because of the incorporation of a carboxylic acid group, TGA tagging not only improves the limit of detection (sub-nM) for sterols but also facilitates their quantitation via characteristic 44 Da neutral loss scan. This radical based derivatization is fast (1 min) and efficient (>90% yield) when conducted in a flow microreactor. The analytical utility of thiyl radical charge tagging method has been demonstrated by quantifying sterols from human plasma and vegetable oil.

中文翻译：

基于巯基自由基的电荷标记使质谱能够进行甾醇定量

受巯基自由基对烯烃的高反应活性和特异性的启发，我们开发了一种新的电荷衍生化方法，可通过电喷雾电离质谱（ESI-MS）快速，定量地分析固醇。巯基乙酸（TGA），一种可商购的化合物，已经被确立为一种高效的标记试剂。由光化学反应引发，衍生自TGA的噻吩基在甾醇的B环中提取出一个烯丙基氢，形成自由基中间体，该中间体与第二个噻吩基迅速重组以生成最终的标记产物。由于引入了一个羧酸基团，TGA标记不仅可以提高固醇的检出限（sub-nM），而且还可以通过特征性的44 Da中性丢失扫描促进其定量。当在流动微反应器中进行时，这种基于自由基的衍生反应快速（1分钟）且有效（> 90％的产率）。巯基自由基电荷标记方法的分析实用性已通过对人血浆和植物油中的固醇进行定量来证明。

更新日期：2017-11-23

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