Ion fragmentation of small molecules in mass spectrometry.pdfVIP

Ion fragmentation of small molecules in mass spectrometry Jeevan Prasain jprasain@uab.edu 6-2612 J. Prasain 01/19/11 Nomenclature: the main names and acronyms used in mass spectrometry • Molecular ion: Ion formed by addition or the removal of one or several electrons to or from the sample molecules- - +• - Electron Impact (EI-MS). M + e M + 2e • Adduct Ion: Ion formed through interaction of two species and containing all the atoms of one of them plus one or several atoms of them (e.g. alkali, ammonium). J. Prasain 01/19/11 1 Contd.. • Pseudomolecular ion: Ion originating from the analyte molecule by abstraction of a proton [M-H]- or addition of proton [M+H]+ • Tandem mass spectrometry (Cooks, 1976): MS/MS (McLafferty, 1978), tandem in space or time • Precursor ion/parent ion: Ions undergoing fragmentation. • Product ion/daughter ion: Ions resulting from parent/precursor ions. • Neutral loss: Fragments lost as neutral molecules • In positive ionization mode, a trace of formic acid is often added to aid protonation of the sample molecules; in negative ionization mode a trace of ammonia solution or a volatile amine is added to aid deprotonation of the sample molecules. Proteins and peptides are usually analysed under positive ionization conditions and polyphenols and acids under negative ionization conditions. In all cases, the m/z scale must be calibrated. J. Prasain 01/19/11 Terminology.. • Ionspray denotes pneumatically assisted ESI operating at aflow rate of approximately 5 to 50 uL/min. • Turboionspray is ionspr