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### 电喷雾质谱在寡糖序列分析中的应用

1. 中国海洋大学医药学院, 海洋药物教育部重点实验室, 山东省糖科学与糖工程重点实验室, 青岛 266003
• 收稿日期:2014-07-07 修回日期:2014-12-23 出版日期:2015-01-10 发布日期:2014-12-23
• 作者简介:赵峡, 男, 博士, 教授, 博士生导师, 主要从事海洋糖类药物研究. E-mail: zhaoxia@ouc.edu.cn
• 基金资助:
国家“十二五冶科技支撑计划(批准号: 2013BAB01B02)、青岛市自主创新重大专项(批准号: 13-7-1-zdzx1-hy)和国家海洋局公益性行业专项项目(批准号: 201005024)资助.

### Application of Electrospray Tandem Mass Spectrometry in Sequence Analysis of Oligosaccharides†

CHEN Huanhuan, ZHAO Xia*(), LUAN Xiaohong, YU Guangli

1. Key Laboratory of Glycoscience and Glycotechnology of Shandong Province, Key Laboratory of Marine Drugs, Ministry of Education, School of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, China
• Received:2014-07-07 Revised:2014-12-23 Online:2015-01-10 Published:2014-12-23
• Contact: ZHAO Xia E-mail:zhaoxia@ouc.edu.cn
• Supported by:
Supported by the National Science &Technology Support Program of China(No. 2013BAB01B02), the Qingdao Independent Innovation Project of China(No. 13-7-1-zdzx1-hy) and the Special Fund for Marine Scientific Research in the Public Interest of China(No. 201005024).

Abstract:

Analysis of oligosaccharide structure and sequence plays a significant role in unravelling the biolo-gical function of glycoconjugates. Electrospray ionization mass spectrometry(ESI-MS) is an important tool for the qualitative and quantitative analysis of oligosaccharides with high sensitivity, high precision and high speed. Some oligosaccharides with different structural characteristics, such as N-glycans, chondroitin sulfate oligosaccharides, human milk oligosaccharides, chitooligosaccharide, alginate oligosaccharides, carrageenan oligosaccharides and sulfated fucan oligosaccharides are discussed in this paper. The application techniques of ESI-MS and fragmentation rule of oligosaccharides in the sequence analysis of the main chain, branch sites, substitution positions of sulfate groups, as well as the monosaccharide composition and the degree of polymerization are summarized. The types of monosaccharide composition can be obtained primarily based on the adjacent m/z difference of B/C fragment ions. The resolution and ionization efficiency of oligosaccharides can be improved by combination with chromatography separation techniques or derivatization methods, and then the molecular weight and degree of polymerization of oligosaccharides can be measured. The information of redu-cing residue and partial sequence of oligosaccharides can be obtained by means of tandem mass spectrometry and characterized derivatization of the reducing end. The types and particular locations of residues can be determined according to their specific fragment ions and abundance. In addition, the branches of oligosaccharide usually occur glycoside bond breakage as a unit or produce D ions, which can be used to determine the branch points. The sulfate groups in different sites can be obtained by their specific cross-ring fragments. The summarization of fragmentation rule of oligosaccharides in ESI-MS provides a guidance to the structure and sequence analysis of unknown oligosaccharides.