Direct Experimental Characterization of Glycosyl Cations by Infrared Ion Spectroscopy
Direct Experimental Characterization of Glycosyl Cations by Infrared Ion Spectroscopy
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DOI：
10.1021/jacs.8b01236
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发表时间：
2018-05-16
影响因子：
15
通讯作者：
Boltje, Thomas J.
中科院分区：
文献类型：
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作者：
Elferink, Hidde;Severijnen, Marion E.;Boltje, Thomas J.
糖基阳离子是在酶促和化学糖基化过程中形成的重要中间体。这些反应中间体固有的高反应性和短寿命使得它们很难用光谱技术进行表征。在这里，我们报告了使用碰撞诱导解离串联质谱仪在气相中产生糖基阳离子，然后使用Felix红外自由电子激光进行红外离子光谱分析。将实验观察到的红外光谱与DFT计算的光谱进行了比较，从而能够详细地阐明难以捉摸的糖基氧碳正离子和二氧钚离子的结构。
Glycosyl cations are crucial intermediates formed during enzymatic and chemical glycosylation. The intrinsic high reactivity and short lifetime of these reaction intermediates make them very challenging to characterize using spectroscopic techniques. Herein, we report the use of collision induced dissociation tandem mass spectrometry to generate glycosyl cations in the gas phase followed by infrared ion spectroscopy using the FELIX infrared free electron laser. The experimentally observed IR spectra were compared to DFT calculated spectra enabling the detailed structural elucidation of elusive glycosyl oxocarbenium and dioxolenium ions.