高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

甘露糖磷酰氨基酸缀合物的ESI-MS研究

孙麒1, 马强1, 何立1, 巨勇1,2, 赵玉芬1   

  1. 1. 清华大学化学系生命有机磷化学及化学生物学教育部重点实验室, 北京 100084;
    2. 兰州大学应用有机化学国家重点实验室, 兰州 730000
  • 收稿日期:1900-01-01 修回日期:1900-01-01 出版日期:2006-06-10 发布日期:2006-06-10
  • 通讯作者: 巨勇

Studies on ESI-MS of Mannosyl-1-phosphoramidates

SUN Qi1, MA Qiang1, HE Li1, JU Yong 1,2* , ZHAO Yu-Fen 1

  

  1. 1. The Key Laboratory of Bioorganic Phosphorus Chemistry, Ministry of Education,
    Department of Chemistry, Tsinghua University, Beijing 100084, China;
    2. National Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China
  • Received:1900-01-01 Revised:1900-01-01 Online:2006-06-10 Published:2006-06-10
  • Contact: JU Yong

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摘要： 一系列全乙酰保护甘露糖-1-磷酰氨基酸酯缀合物的α构型和β构型异构体的ESI-MSn裂解规律研究表明, β构型异构体会出现一系列特征的m/z 433, 391, 371的碎片离子, 且［M-CH2CHCH3+Na］+碎片丰度较大. ［M-糖基+Na］+和［糖基+Na］+碎片相对丰度较小. α构型分子反之. 同时对全乙酰保护的［糖基+Na］+ m/z 353碎片离子进行三级碎裂, 其主要特征是消除CH2CO和AcOH中性分子的碎片离子, 而且其它位羟基构型的差异对质谱中碎裂方式影响不大.

关键词: 甘露糖磷酰胺缀合物, 电喷雾质谱, 裂解规律

Abstract: Phosphoglycoproteins are a kind of compounds that have many important biological functions. In order to study the relationship between the structure and the biological functions of these compounds, some core structures(glycosyl-1-phosphoramides) of these compounds were synthesized. Electrospray ionization mass spectrometry(ESI-MS) was used to study the fragmentation characteristics of various types of acetyl protecting mannosyl-1-phosphoramidates. The results show that there are very different characteristics between α- and β- anomeric isomers. The ESI-MS2 spectra of the quasi\|molecular ion ［M+Na］+ of β-anomeric isomers show characteristic fragment ions at m/z 433, 391 and 371; and the relative abundance of fragment ion ［M-CH2CHCH3+Na］+ peak is much higher than that of αanomeric isomers. That this characteristic fragmentation should be due to the interaction of the phosphoramide group at the anomeric carbon and the acetyl protecting groups of the hydroxyl groups, especially the acetyl protecting group at C2. Meanwhile, the ESI-MS3 spectrum of fragment ion ［sugar+Na］+ m/z 353 of different isomers of acetyl protecting glycosyl-1-phosphoramidates shows the same fragmentation pattern including the loss of molecules of CH2=C=O and AcOH and is not effected by the other position configuration.

Key words: Mannosyl-1-phosphoramidate, ESI-MS, Fragmentation pattern

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