高等学校化学学报
高等學校化學學報
고등학교화학학보
CHEMICAL JOURNAL OF CHINESE UNIVERSITIES
2015年
1期
1-8
,共8页
陈欢欢%赵峡%栾晓红%于广利
陳歡歡%趙峽%欒曉紅%于廣利
진환환%조협%란효홍%우엄리
电喷雾质谱%寡糖%碎片断裂规律%序列分析
電噴霧質譜%寡糖%碎片斷裂規律%序列分析
전분무질보%과당%쇄편단렬규률%서렬분석
Electrospray ionization mass spectrometry%Oligosaccharide%Fragmentation rule%Sequence analysis
选取具有不同结构特征的N-糖链、硫酸软骨素寡糖、人乳寡糖以及海洋来源的壳寡糖、褐藻胶寡糖、卡拉胶寡糖和硫酸岩藻寡糖等,对电喷雾质谱在寡糖的主链序列、分支位点、硫酸基取代位置确定、单糖组成和聚合度分析等方面的应用技术及碎片离子的断裂规律进行了总结。根据相邻同类碎片离子之间的质荷比差值可初步判断寡糖的单糖组成类型;通过与色谱分离技术联用或衍生化方法可提高寡糖的分辨率和离子化效率,并测得寡糖的分子量及聚合度;借助串联质谱及对寡糖还原端的特异性标记,可获得寡糖的还原端残基和部分序列信息;根据寡糖产生的特征碎片离子及其丰度大小可判断残基的特定位置和类型。另外,寡糖的分支通常作为一个整体发生糖苷键断裂或产生D离子,据此可判断分支点的位置;根据硫酸寡糖产生的特异性跨环断裂碎片,可以确定硫酸基的连接位置。这些规律和方法的总结为未知寡糖的结构和序列的分析提供了启发和指导。
選取具有不同結構特徵的N-糖鏈、硫痠軟骨素寡糖、人乳寡糖以及海洋來源的殼寡糖、褐藻膠寡糖、卡拉膠寡糖和硫痠巖藻寡糖等,對電噴霧質譜在寡糖的主鏈序列、分支位點、硫痠基取代位置確定、單糖組成和聚閤度分析等方麵的應用技術及碎片離子的斷裂規律進行瞭總結。根據相鄰同類碎片離子之間的質荷比差值可初步判斷寡糖的單糖組成類型;通過與色譜分離技術聯用或衍生化方法可提高寡糖的分辨率和離子化效率,併測得寡糖的分子量及聚閤度;藉助串聯質譜及對寡糖還原耑的特異性標記,可穫得寡糖的還原耑殘基和部分序列信息;根據寡糖產生的特徵碎片離子及其豐度大小可判斷殘基的特定位置和類型。另外,寡糖的分支通常作為一箇整體髮生糖苷鍵斷裂或產生D離子,據此可判斷分支點的位置;根據硫痠寡糖產生的特異性跨環斷裂碎片,可以確定硫痠基的連接位置。這些規律和方法的總結為未知寡糖的結構和序列的分析提供瞭啟髮和指導。
선취구유불동결구특정적N-당련、류산연골소과당、인유과당이급해양래원적각과당、갈조효과당、잡랍효과당화류산암조과당등,대전분무질보재과당적주련서렬、분지위점、류산기취대위치학정、단당조성화취합도분석등방면적응용기술급쇄편리자적단렬규률진행료총결。근거상린동류쇄편리자지간적질하비차치가초보판단과당적단당조성류형;통과여색보분리기술련용혹연생화방법가제고과당적분변솔화리자화효솔,병측득과당적분자량급취합도;차조천련질보급대과당환원단적특이성표기,가획득과당적환원단잔기화부분서렬신식;근거과당산생적특정쇄편리자급기봉도대소가판단잔기적특정위치화류형。령외,과당적분지통상작위일개정체발생당감건단렬혹산생D리자,거차가판단분지점적위치;근거류산과당산생적특이성과배단렬쇄편,가이학정류산기적련접위치。저사규률화방법적총결위미지과당적결구화서렬적분석제공료계발화지도。
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 polymeri- zation are summarized. The types of monosaccharide composition can be obtained primarily based on the adja- cent 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 de- termined 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 summa- rization of fragmentation rule of oligosaccharides in ESI-MS provides a guidance to the structure and sequence analysis of unknown oligosaccharides.