Isotope-coding derivatization for quantitative profiling of reactive α-dicarbonyl species in processed botanicals by liquid chromatography-tandem mass spectrometry
Isotope-coding derivatization for quantitative profiling of reactive α-dicarbonyl species in processed botanicals by liquid chromatography-tandem mass spectrometry
复制标题
通过液相色谱-串联质谱法对加工植物中的活性α-二羰基物质进行同位素编码衍生定量分析
DOI：
10.1021/acs.jafc.1c04122
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发表时间：
2021
影响因子：
6.1
通讯作者：
Xiaoqing Chen
中科院分区：
文献类型：
--
作者：
Meiling Wang;Yaxuan Liu;Bin Guo;Fan Zhang;Fang Chou;Ming Ma;Libin Huang;Ziwei Luo;Bo Chen;Xiaoqing Chen
α-二羰基化合物（α-DCs）是一种结构多样的重要反应性美拉德中间体，广泛存在于食品和生物体内，但对这些潜在有害亲电体的完整分子谱知之甚少。在此，我们报道了一种新的同位素编码衍生化（ICD）策略，用于天然食品中（非）目标α-DC种类的广谱定量分析。它利用差分同位素标记（DIOL）与试剂对邻苯二胺（OPD）/OPD-d4（氘代），以形成稳定的喹喔啉，用于使用液相色谱-混合四极杆线性离子阱质谱（LC-QqLIT）进行类别特异性碎片依赖性采集。简单的一锅定量标记和方便的净化方案的组合通过基质匹配的ICD-内标校准提供了令人满意的灵敏度、线性、准确度（81-116%）和过程回收率（86-109%，RSD < 10%），而没有显著的基质干扰（~ 9 - 5%）、同位素效应（<0.5%）和鸡尾酒效应。一种更通用的基于DIOL的LC-QqLIT算法集成了双前体离子和中性丢失扫描，以触发具有独特同量异位素双重标签（4 Da位移）的增强产物离子，从而能够在单次分析中同时筛选和相对定量非靶向α-DC类似物。本研究拓宽了对传统植物中复杂α-DC谱的认识，揭示了α-DC在这些富含糖的加工产品中广泛存在，但它们的丰度在不同样品中差异很大。
α-Dicarbonyls (α-DCs) are key reactive Maillard intermediates with structural diversity and are widely found in foods and in vivo, but little is known regarding the complete molecular profiles of these potentially harmful electrophiles. Herein, we reported a novel isotope-coding derivatization (ICD) strategy for the broad-spectrum, quantitative profiling of (non)target α-DC species in natural foodstuffs. It utilized differential isotope labeling (DIOL) with a reagent pair o-phenylenediamine (OPD)/OPD-d4 (deuterated) to form stable quinoxalines for class-specific fragmentation-dependent acquisition using liquid chromatography-hybrid quadrupole linear ion trap mass spectrometry (LC-QqLIT). A combination of facile one-pot quantitative labeling and convenient cleanup protocol afforded satisfactory sensitivity, linearity, accuracy (81-116%), and process recovery (86-109% with RSDs < 10%) by matrix-matched ICD-internal standard calibration, without significant matrix interference (-9 to 5%), isotopic effect (<0.5%), and cocktail effect. A more generic DIOL-based LC-QqLIT algorithm integrated double precursor ion and neutral loss scan to trigger enhanced product ions with the unique isobaric doublet tags (4 Da shift), enabling simultaneous screening and relative quantitation of nontarget α-DC analogues in a single analysis. This study has widened the vision on complex α-DC profiles in traditional botanicals, which revealed a wide occurrence of α-DCs in such processed sugar-rich products, yet their abundance varied greatly among different samples.