Use of N ‐(4‐aminophenyl)piperidine derivatization to improve organic acid detection with supercritical fluid chromatography‐mass spectrometry
Use of N ‐(4‐aminophenyl)piperidine derivatization to improve organic acid detection with supercritical fluid chromatography‐mass spectrometry
复制标题
利用 N-(4-氨基苯基)哌啶衍生化改进超临界流体色谱-质谱法的有机酸检测
DOI：
10.1002/jssc.202300343
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发表时间：
2023
影响因子：
3.1
通讯作者：
Grinias, James P.
中科院分区：
文献类型：
--
作者：
Saw, Yih Ling;Boughton, John R.;Wroniuk, Faith L.;Mostafa, Mahmoud Elhusseiny;Pellegrinelli, Peter J.;Calvez, Samantha A.;Kaplitz, Alexander S.;Perez, Lark J.;Edwards, James L.;Grinias, James P.
通过LC-MS分析复杂混合物中的有机酸通常具有挑战性，特别是由于检测这些化合物的天然（即，未衍生或未标记的）形式。这些化合物也很难使用超临界流体色谱（SFC）-MS进行测量，这是一种对代谢组学分析越来越重要的技术，具有基于负离子化的类似限制。在这份报告中，使用高质子亲和力N-（4-氨基苯基）哌啶衍生化标签进行了探索，以改善有机酸检测的SFC-MS。用N-（4-aminophenyl）piperidine衍生了四种具有不同数量羧酸根的有机酸（乳酸、琥珀酸、苹果酸和柠檬酸），使检测限降至0.5 ppb，检测限总体提高了25 - 2100倍。还描述了衍生基团对灵敏度的影响，对于以其天然形式可检测的化合物，灵敏度增加至少200倍，以及质谱检测。对这些衍生化合物分离的初步研究确定了多种固定相，可用于通过SFC完全分离所有四种化合物。这种衍生技术为SFC-MS分析有机酸提供了一种改进的方法，特别是对于那些在其天然形式下无法检测到的有机酸。
The analysis of organic acids in complex mixtures by LC‐MS can often prove challenging, especially due to the poor sensitivity of negative ionization mode required for detection of these compounds in their native (i.e., underivatized or untagged) form. These compounds have also been difficult to measure using supercritical fluid chromatography (SFC)‐MS, a technique of growing importance for metabolomic analysis, with similar limitations based on negative ionization. In this report, the use of a high proton affinityN‐(4‐aminophenyl)piperidine derivatization tag is explored for the improvement of organic acid detection by SFC‐MS. Four organic acids (lactic, succinic, malic, and citric acids) with varying numbers of carboxylate groups were derivatized withN‐(4‐aminophenyl)piperidine to achieve detection limits down to 0.5 ppb, with overall improvements in detection limit ranging from 25‐to‐2100‐fold. The effect of the derivatization group on sensitivity, which increased by at least 200‐fold for compounds that were detectable in their native form, and mass spectrometric detection are also described. Preliminary investigations into the separation of these derivatized compounds identified multiple stationary phases that could be used for complete separation of all four compounds by SFC. This derivatization technique provides an improved approach for the analysis of organic acids by SFC‐MS, especially for those that are undetectable in their native form.