Fragmentation Pathways in Peptide Mass Spectrometry
Karl K. Irikura Research Opportunity Number 50.63.21.B6251
Tandem mass spectrometry is a crucial technology in proteomics. Despite rapid technological advances, the underlying chemical reaction mechanisms remain poorly understood. The practical consequence is that about half the ion signal typically cannot be interpreted and is discarded. We are using quantum chemistry to explain known trends in peptide fragmentation patterns and to predict detailed reaction mechanisms. The goal is to understand the chemistry of peptide ions well enough to provide new rules that will be technologically useful. Our work benefits from the availability of major computing hardware, specialized reactivity-searching software, and the experimental and data resources of the NIST Mass Spectrometry Data Center.