Fragmentation of Multi-charged Derivatized Lysine Using Nanospray CID Tandem Mass Spectrometry
We demonstrate increasing the charge state of small molecules using derivatized lysine as our model system. Lysine is chemically tagged with three tertiary amines which enables efficient production of highly charged analytes. A +3 charge state is obtained from direct infusion nanoelectrospray conditions. Collisional activation of the +3 derivatized lysine yielded structurally informative product ions corresponding to cleavages across the analyte backbone and within the proton affinity tags. This suggests a role for multi-charging of metabolites in both targeted MRM analyses and untargeted analyses to help identify novel metabolites. Density functional calculations aid peak assignment and rationalization of structure-property relationships.
KeywordsSupercharging Nanospray Metabolite ETC CID
This material is based upon work supported by the National Science Foundation under grant no. DBI-0922879 for acquisition of the LTQ-Velos Pro Orbitrap LC-MS/MS. Brad Evans is thanked for his assistance with the ETD experiments.
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