Abstract
In this study, we evaluated, by electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation tandem mass spectrometry (CID-MS/MS) using a quadrupole orthogonal time-of-flight (QqToF)-MS/MS hybrid instrument, the gas-phase fragmentations of some commercially available biotinyl reagents. The biotin reagents used were: psoralen-BPE 1, p-diazobenzoyl biocytin (DBB) 2, photoreactive biotin 3, biotinyl-hexaethyleneglycol dimer 4, and the sulfo-SBED 5. The results showed that, during ESI-MS and CID-MS/MS analyses, the biotin reagents followed a similar gas-phase fragmentation pattern and the cleavages usually occurred at either end of the spacer arm of the biotin reagents. In general we have observed that the CID-MS/MS fragmentation routes of the five precursor protonated molecules obtained from the biotin linkers 1-5 afforded a series of product ions formed essentially by similar routes. The genesis and the structural identities of all the product ions obtained from the biotin linkers 7-5 have been assigned. All the exact mass assignments of the protonated molecules and the product ions were verified by conducting separate CID-MS/MS analysis of the deuterium-labelled precursor ions. Copyright (C) 2009 John Wiley & Sons, Ltd.