ArticleJournal of the American Society for Mass Spectrometry2018
Collision Induced Dissociation of Benzylpyridinium-Substituted Porphyrins: Towards a Thermometer Scale for Multiply Charged Ions?
Article in Journal of the American Society for Mass Spectrometry, 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 5 papers.
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Who cites it
5 citing papers in PubMed.
- Redox Chemistry and Photophysics of theInorganic chemistry · 2026Article
- Thermally Activated and Nonactivated Excited State Decay of [Cr(dgpy)Inorganic chemistry · 2025Article
- Advancing Inorganic Coordination Chemistry by Spectroscopy of Isolated Molecules: Methods and Applications.Chemistry (Weinheim an der Bergstrasse, Germany) · 2021Review
- Internal Energy Deposition in Infrared Matrix-Assisted Laser Desorption Electrospray Ionization With and Without the Use of Ice as a Matrix.Journal of the American Society for Mass Spectrometry · 2019Article
- Thermometer Ions, Internal Energies, and In-Source Fragmentation in Ambient Ionization.Mass spectrometry reviewsReview
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Authors and funding
7 authors.
Funding
Abstract
We have determined breakdown curves for a range of multiply charged benzylpyridinium-substituted porphyrin cations by collision induced dissociation measurements (CID) as mediated by resonant pulsed radio-frequency (rf) excitation in a helium-filled linear ion trap. Measurements were compared with the predictions of DFT calculations. We find a linear correlation between experimental fragmentation thresholds (in instrumental units of "normalized collision energy") and theoretical dissociation energies, suggesting that these species can be used as calibrants to gauge the fragmentation energetics of closely related systems. We have confirmed this by also studying the fragmentation thresholds of metalloporphyrin-based ions - including multiply negatively charged metalloporphyrin oligomers. Unfortunately, the slope of the linear correlation obtained for benzylpyridinium-substituted porphyrin multications differs significantly from that obtained by us for a set of smaller, singly charged substituted benzylpyridines put forward as "thermometer" ions in previous work. Multiplying the threshold energies in an ad hoc fashion by the ion charge basically reconciles both calibration curves. We conclude that one should use caution when applying small, singly charged benzylpyridines as calibrants to gauge the CID of large, multiply charged ions in ion-trap mass spectrometers. Graphical Abstract.
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