Theoretical study of mono- and disaccharides collision-induced-dissociation.
Nguan Hock-Seng1*, Chi-Kung Ni1
1Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan
* Presenter:Nguan Hock-Seng,
Carbohydrates structure determination is a bottleneck in understanding many biological processes that involve carbohydrate molecules. Mass spectroscopy with the collision-induced-dissociation (CID) fragmentation method is widely used in analyzing carbohydrates. However, due to the complexity of the carbohydrate molecular structures, the fragmentations patterns of the carbohydrate molecules are poorly understood. In this work, by extensive molecular structures searching and quantum chemistry calculations, we show how the fragmentation pattern of the monosaccharides and disaccharides can be understood [1-4]. The transition states for the reactions that cause the fragmentation were searched through a heuristic approach and also through the nudge elastic band method [5]. Transition states theory was also applied to calculate the reaction rate constants of each dissociation channel. Furthermore, we show that the CID fragmentation pattern across different monosaccharides can be explained by considering the distribution of oxygen atoms on the plane of the cyclic monosaccharides. The physical insights from the computational studies are useful for the development of methods of carbohydrates structures determinations.


1. Chen, J.-L.; Nguan, H. S.; Hsu, P.-J.; Tsai, S.-T.; Liew, C. Y.; Kuo, J.-L.; Hu, W.-P.; Ni, C.-K., Collision-Induced Dissociation of Sodiated Glucose and Identification of Anomeric Configuration. Phys. Chem. Chem. Phys. 2017, 19, 15454-15462.
2. Huynh, H. T.; Phan, H. T.; Hsu, P.-J.; Chen, J.-L.; Nguan, H. S.; Tsai, S.-T.; Roongcharoen, T.; Liew, C. Y.; Ni, C.-K.; Kuo, J.-L., Collision-Induced Dissociation of Sodiated Glucose, Galactose, and Mannose, and the Identification of Anomeric Configurations. Phys. Chem. Chem. Phys. 2018, 20, 19614-19624.
3. Nguan, H.-S.; Tsai, S.-T.; Chen, J.-L.; Hsu, P.-J.; Kuo, J.-L.; Ni, C.-K., Collision-Induced Dissociation of Xylose and Its Applications in Linkage and Anomericity Identification. Phys. Chem. Chem. Phys. 2021.
4. Tsai, S.-T.; Nguan, H.-S.; Ni, C.-K., Identification of Anomericity and Linkage of Arabinose and Ribose through Collision-Induced Dissociation. J. Phys. Chem. A 2021, 125, 6109-6121.
5. G. Henkelman, B. P. Uberuaga and H. Jónsson, J. Chem. Phys., 2000, 113, 9901-9904.

Keywords: Collision-induced-dissociation, Carbohydrate molecules, Quantum chemistry computation, Mass spectroscopy