Identification of a neutral loss from precursor ions with nearly Gaussian-shaped isotopic patterns via inverted isotopic patterns of product ions

Rationale Direct atomic composition determination of ions with very broad Gaussian‐shaped isotopic patterns is challenging because no monoisotopic peak is available for high accurate mass determination and no characteristic shapes in isotopic patterns are visible. Methods Isolation and fragmentation of the ions corresponding to one peak (one nominal mass) in the center of the broad Gaussian‐shaped isotopic pattern lead to a mass spectrum with the product ion signal showing the inverted full isotopic profile of the neutral fragment. Results We have introduced a convenient method for the fast and straightforward identification of a neutral loss for molecular ions with broad isotopic patterns. The theoretical considerations underlying this method are explained and its practical limitations are considered. The benefits of this method are exemplified by guiding a reader through the analysis of a complex mixture of bridged carborate clusters, compounds with very broad isotopic patterns. Conclusions The presented method can be efficiently used for the determination of atomic compositions of compounds with broad isotopic patterns by their fragmentation using mass spectrometry. This method should significantly facilitate the mass spectrometric analysis of compounds containing several atoms with broad isotopic distributions, such as Ge, Sn, Mo, Ru and Hg, and, thus, can considerably broaden the use of mass spectrometry as an analytical method in inorganic and organometallic chemistry. Copyright © 2016 John Wiley & Sons, Ltd.