Radboud University, Institute for Molecules and Materials , Synthetic Organic Chemistry , Heyendaalseweg 135 , 6525 AJ , Nijmegen , The Netherlands.
Radboud University, Institute for Molecules and Materials , FELIX Laboratory , Toernooiveld 7c , 6525 ED , Nijmegen , The Netherlands.
J Am Chem Soc. 2018 May 16;140(19):6034-6038. doi: 10.1021/jacs.8b01236. Epub 2018 May 7.
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.
糖基阳离子是酶促和化学糖基化过程中形成的关键中间体。这些反应中间体具有内在的高反应性和短寿命，因此使用光谱技术对其进行表征具有很大的挑战性。在此，我们报告了使用碰撞诱导解离串联质谱在气相中生成糖基阳离子，然后使用 FELIX 红外自由电子激光进行红外离子光谱学研究。将实验观察到的红外光谱与 DFT 计算光谱进行比较，从而能够详细阐明难以捉摸的糖基氧鎓和二氧杂环戊烯鎓离子的结构。
