MASS SPECTROMETRY OF METAL COORDINATED OLIGOSACCHARIDES

该项目的长期目标包括：1） 绝对立体化学构型的测定 使用由快原子产生的金属-配体络合的寡糖 轰击（FAB）和电喷雾电离（ESI）结合 串联质谱（MS/MS），2）分析方法学的开发 用于使用ESI-测定复杂碳水化合物中的键合位置 金属配位的多电荷离子的MS/MS，3） 多电荷物质的气相解离机制，以及4） 寡糖增敏与结构分析 通过在线LC-MS/MS使用柱后添加金属 氯化物。 预计完整的立体化学分析， 可以使用动能释放测量来获得低聚糖 (KER)金属配体寡糖的解离产物 配合物这包括上的所有官能团的立体化学。 环以及区分α和β端基异构体。 此外，还对多电荷金属配位化合物的ESI-MS/MS进行了研究。 将研究寡糖作为测定序列的方法 和整个碳水化合物的连接位置，如将在线 使用三轴探针的LC-MS/MS。每一个项目都将 补充气相离子研究，以确定的机制， 离解、金属配位位置和电荷效应 本地化

The long term goal of this project includes the following: 1) determination of the absolute stereochemical configuration of oligosaccharides using metal-ligand complexation generated by fast atom bombardment (FAB) and electrospray ionization (ESI) in combination with tandem mass spectrometry (MS/MS), 2) development of analytical methodology for determination of linkage position in complex carbohydrates using ESI- MS/MS of the metal-coordinated multiply charged ions, 3) determination of gas phase dissociation mechanisms of the multiply charged species, and 4) sensitivity enhancement and structural analysis of oligosaccharide mixtures via on-line LC-MS/MS using post column addition of metal chlorides. It is anticipated that complete stereochemical analysis of oligosaccharides can be achieved using kinetic energy release measurements (KER) of the dissociation products of metal-ligand-oligosaccharide complexes. This includes the stereochemistry of all functional groups on the ring as well as differentiating the alpha and beta anomers. Additionally, ESI-MS/MS of the multiply charged metal-coordinated oligosaccharide will be investigated as a method for determining sequence and linkage position throughout the carbohydrate, as will be the on-line LC-MS/MS utilizing a triaxial probe. Each of these projects will be complemented with gas phase ion studies to determine the mechanisms of dissociation, site of metal coordination, and effects of charge localization.