首页> 外文期刊>Journal of mass spectrometry: JMS >4-Chloro--cyanocinnamic acid is an efficient soft matrix for cyanocobalamin detection in foodstuffs by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS)
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4-Chloro--cyanocinnamic acid is an efficient soft matrix for cyanocobalamin detection in foodstuffs by matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS)

机译:4-氯氰基氨基甲酸是一种通过基质辅助激光解吸/电离质谱(MALDI MS)检测食品中氰钴胺素的有效软基质

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摘要

4-Chloro--cyanocinnamic acid (ClCCA) is a very useful matrix able to give the protonated adduct [M+H](+) of intact cyanocobalamin (CNCbl) as the base peak (m/z 1355.58) in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS). The only fragment observed is [M-CN+H](+center dot) formed through the facile (CN)-C-center dot neutral loss reflecting the fairly low Co-C bond energy. All other investigated proton transfer matrices, including -cyano-4-hydroxycinnamic acid, para-nitroaniline and 2,5-dihydroxybenzoic acid, give rise to a complete decyanation of CNCbl with concomitant formation of [M-CN+H](+center dot), [M-CN+Na](+center dot) and [M-CN+K](+center dot) adducts at m/z 1329.57, 1351.55 and 1367.51, respectively. Depending on the matrix used, a variable degree of fragmentation involving the -side axial ligand was observed. A plausible explanation of the specific behaviour of 4-chloro--cyanocinnamic acid as a soft matrix is discussed. Tandem mass spectra of both [M+H](+) and [M-CN+H](+center dot) ions were obtained and product ions successfully assigned. The possibility of detecting the protonated adduct of intact CNCbl was exploited in foodstuff samples such as cow milk and hen egg yolk by MALDI tandem MS upon sample extraction. We believe that our data provide strong basis for the application of MALDI tandem MS in the qualitative analysis of natural CNCbl, including fish, liver and meat samples. Copyright (c) 2016 John Wiley & Sons, Ltd.
机译:4-氯氰基氨基甲酸(ClCCA)是一种非常有用的基质,能够在基质辅助激光中给出完整氰基钴胺素(CNCbl)的质子化加合物[M + H](+)作为基峰(m / z 1355.58)解吸/电离(MALDI)质谱(MS)。观察到的唯一片段是通过容易的(CN)-C-中心点中性损失形成的[M-CN + H](+中心点),反映出相当低的Co-C键能量。所有其他研究的质子转移基质,包括-氰基-4-羟基肉桂酸,对硝基苯胺和2,5-二羟基苯甲酸,都导致CNCbl完全脱氰,并伴随形成[M-CN + H](+中心点),[M-CN + Na](+中心点)和[M-CN + K](+中心点)加合物分别在m / z 1329.57、1351.55和1367.51处发生。根据所使用的基质,观察到涉及-侧轴向配体的可变程度的断裂。讨论了对4-氯氰基氨基甲酸作为软基质的特定行为的合理解释。获得了[M + H](+)和[M-CN + H](+中心点)离子的串联质谱,并成功分配了产物离子。样品提取后,通过MALDI串联质谱分析法在食品样品(如牛奶和鸡蛋黄)中检测了完整的CNCbl质子化加合物的可能性。我们认为,我们的数据为MALDI串联质谱在天然CNCbl(包括鱼,肝和肉样品)的定性分析中的应用提供了坚实的基础。版权所有(c)2016 John Wiley&Sons,Ltd.

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