Differentiation of the anomeric configuration and ring form of glucosyl-glycolaldehyde anions in the gas phase by mass spectrometry:: isomeric discrimination between m/z 221 anions derived from disaccharides and chemical synthesis of m/z 221 standards
Differentiation of the anomeric configuration and ring form of glucosyl-glycolaldehyde anions in the gas phase by mass spectrometry:: isomeric discrimination between m/z 221 anions derived from disaccharides and chemical synthesis of m/z 221 standards
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DOI：
10.1016/j.carres.2006.11.021
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发表时间：
2007-02-05
影响因子：
3.1
通讯作者：
Bendiak, Brad
中科院分区：
文献类型：
--
作者：
Fang, Tammy T.;Zirrolli, Joseph;Bendiak, Brad
双糖在负离子模式下的质谱分析经常产生m/z 221的阴离子产物。用含葡萄糖的双糖，分离的m/z 221产物离子在保罗阱中解离产生的质谱可以很容易地区分离子的头型结构和环状结构。通过对其标准物的化学合成，证明这些离子是葡萄糖基乙醇醛。通过标记双糖的还原性羰基氧与单糖之间的180比质量差，确定了m/z 221离子仅由完整的非还原糖与从还原糖衍生的二碳糖元组成，而不考虑双糖的连接位置。这使得离子的头型构型和环状结构得以确定，离子位于糖苷键的非还原侧的位置得以确定。对保罗阱中再现性所必需的实验因素的详细研究表明，区分同分异构体m/z 221离子的独特解离模式可以每月获得，并结合内部能量输入校准离子，确保可重复的能量沉积到分离的m/z 221离子中。此外，Paul陷阱中双糖m/z 341阴离子的MS/MS断裂模式使连锁位置能够被分配，正如之前报道的其他类型的质谱仪一样。(c) 2006 Elsevier Ltd.版权所有。
Mass spectrometry of disaccharides in the negative-ion mode frequently generates product anions of m/z 221. With glucose-containing disaccharides, dissociation of isolated m/z 221 product ions in a Paul trap yielded mass spectra that easily differentiated between both anomeric configurations and ring forms of the ions. These ions were shown to be glucosyl-glycolaldehydes through chemical synthesis of their standards. By labeling the reducing carbonyl oxygen of disaccharides with 180 to mass discriminate between monosaccharides, it was established that the m/z 221 ions are comprised solely of an intact nonreducing sugar with a two-carbon aglycon derived from the reducing sugar, regardless of the disaccharide linkage position. This enabled the anomeric configuration and ring form of the ion to be assigned and the location of the ion to the nonreducing side of a glycosidic linkage to be ascertained. Detailed studies of experimental factors necessary for reproducibility in a Paul trap demonstrated that the unique dissociation patterns that discriminate between the isomeric m/z 221 ions could be obtained from month-to-month in conjunction with an internal energy-input calibrant ion that ensures reproducible energy deposition into isolated m/z 221 ions. In addition, MS/MS fragmentation patterns of disaccharide m/z 341 anions in a Paul trap enabled linkage positions to be assigned, as has been previously reported with other types of mass spectrometers. (c) 2006 Elsevier Ltd. All rights reserved.