Targeted LC-MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA.

Targeted LC-MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA.
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DOI:
10.1007/s00216-010-3575-1
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发表时间:
2010-05
影响因子:
4.3
通讯作者:
Irth, Hubertus
Irth, Hubertus
中科院分区:
化学2区
文献类型:
--
作者:
Eggink, Mark;Wijtmans, Maikel;Kretschmer, Ansgar;Kool, Jeroen;Lingeman, Henk;de Esch, Iwan J. P.;Niessen, Wilfried M. A.;Irth, Hubertus

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以醛类衍生试剂4-(2-(三甲铵基)乙氧基)二溴化苯铵(4-APC)为模板,设计了一种新的衍生试剂,并将其用于脂质过氧化反应生物标志物的分析和筛选。新的衍生试剂4-(2-((4-溴苯乙基)二甲基铵基)乙氧基)苯铵二溴化物(4-APEBA)含有溴苯乙基基团,以将同位素特征结合到衍生物中,并添加额外的片段化标识符,共同增强检测和筛选未知醛的能力。衍生化可以在温和条件下实现(pH 5.7,10 °C)。通过改变辅助试剂(1-乙基-3-(3-二甲氨基丙基)碳二亚胺代替氰基硼氢化钠),4-APEBA也适用于羧酸的选择性衍生。合成的新标签,探索衍生化条件,表征的MS/MS中的醛和羧酸衍生物的碎片,并初步应用标记策略分析尿液和血浆中的醛。辛酸衍生的4-APEBA试剂的结构和MS/MS裂解谱本文的在线版本(doi:10. 1007/s 00216 -010-3575-1)包含补充材料,可供授权用户使用。
Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add additional fragmentation identifiers, collectively enhancing the abilities for detection and screening of unknown aldehydes. Derivatization can be achieved under mild conditions (pH 5.7, 10 °C). By changing the secondary reagent (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide instead of sodium cyanoborohydride), 4-APEBA is also applicable to the selective derivatization of carboxylic acids. Synthesis of the new label, exploration of the derivatization conditions, characterization of the fragmentation of the aldehyde and carboxylic acid derivatives in MS/MS, and preliminary applications of the labeling strategy for the analysis of aldehydes in urine and plasma are described. Structure and MS/MS fragmentation spectrum of 4-APEBA reagents derivatized with octanoic acid The online version of this article (doi:10.1007/s00216-010-3575-1) contains supplementary material, which is available to authorized users.
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