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/z433,391,371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/z353碎片离子进行三级碎裂,其主要特征是消除CH2C O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.
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 - CH2= CHCH3 + 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 pro- tecting 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 ramidates shows the same fragmentation pattern including the loss of and is not effected by the other position configuration. of acetyl protecting glycosyl-1-phospho- molecules of CH2 = C = O and AcOH
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
2006年第6期1070-1074,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金(批准号:20172033
20542004)
教育部博士学科点基金资助