Linkage and Anomeric Differentiation in Trisaccharides by Sequential Fragmentation and Variable-Wavelength Infrared Photodissociation
Linkage and Anomeric Differentiation in Trisaccharides by Sequential Fragmentation and Variable-Wavelength Infrared Photodissociation
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DOI：
10.1007/s13361-014-1025-6
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发表时间：
2015-02
影响因子：
3.2
通讯作者：
Yanglan Tan;N. Polfer
中科院分区：
文献类型：
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作者：
Yanglan Tan;N. Polfer
碳水化合物及其衍生物在生物系统中发挥着重要作用，但它们的异构性也对分析技术提出了相当大的挑战。本文采用可调谐co2激光（9.2-10.7 μm）红外多光子解离（IRMPD）逐步表征葡萄糖基三糖的异构体变体。在傅立叶变换离子回旋共振（FTICR）细胞中将去质子化的三糖捕获并分裂成双糖c2片段后，对c2离子进行进一步的变波长红外照射，产生波长相关的解离模式，以热图表示。这些c2片段的光解模式与具有相同糖苷键的双糖的光解模式惊人地相似。相反，不同糖苷键的光解模式表现出相当大的差异。在这些结果的基础上，可以系统地区分和鉴定三糖中双糖单元的糖苷键的连接位置和异构性，为表征低聚异构体的结构提供了一种有前途的方法。
Carbohydrates and their derivatives play important roles in biological systems, but their isomeric heterogeneity also presents a considerable challenge for analytical techniques. Here, a stepwise approach using infrared multiple-photon dissociation (IRMPD) via a tunable CO2laser (9.2–10.7 μm) was employed to characterize isomeric variants of glucose-based trisaccharides. After the deprotonated trisaccharides were trapped and fragmented to disaccharide C2fragments in a Fourier transform ion cyclotron resonance (FTICR) cell, a further variable-wavelength infrared irradiation of the C2ion produced wavelength-dependent dissociation patterns that are represented as heat maps. The photodissociation patterns of these C2fragments are shown to be strikingly similar to the photodissociation patterns of disaccharides with identical glycosidic bonds. Conversely, the photodissociation patterns of different glycosidic linkages exhibit considerable differences. On the basis of these results, the linkage position and anomericity of glycosidic bonds of disaccharide units in trisaccharides can be systematically differentiated and identified, providing a promising approach to characterize the structures of isomeric oligosaccharides.