Negative nucleotide ions as sensitive probes for energy specificity in collision‐induced fragmentation in mass spectrometry

  • Rationale: The most commonly used fragmentation methods in tandem mass spectrometry (MS/MS) are collision‐induced dissociation (CID) and higher energy collisional dissociation (HCD). While in CID the preselected ions in the trap are resonantly (and m/z exclusively) excited, in HCD the entire m/z range experiences the dissociative acceleration. The different excitation is reflected in different fragment distributions. Methods: As a test‐bed for particularly pronounced fragmentation specificity, here MS/MS experiments on several 4‐mer oligonucleotides were conducted employing both collision methods and the results were thoroughly compared. Oligonucleotides are shown to be sensitive probes to subtle changes, especially in the negative ion mode. A detailed analysis of these differences reveals insight into the dissociation mechanics. Results: Thedifferencesarerepresentedinheat‐maps,whichallowforadirectvisualinspectionRationale: The most commonly used fragmentation methods in tandem mass spectrometry (MS/MS) are collision‐induced dissociation (CID) and higher energy collisional dissociation (HCD). While in CID the preselected ions in the trap are resonantly (and m/z exclusively) excited, in HCD the entire m/z range experiences the dissociative acceleration. The different excitation is reflected in different fragment distributions. Methods: As a test‐bed for particularly pronounced fragmentation specificity, here MS/MS experiments on several 4‐mer oligonucleotides were conducted employing both collision methods and the results were thoroughly compared. Oligonucleotides are shown to be sensitive probes to subtle changes, especially in the negative ion mode. A detailed analysis of these differences reveals insight into the dissociation mechanics. Results: Thedifferencesarerepresentedinheat‐maps,whichallowforadirectvisualinspection oflargeamountsofdata.Inthesefalsecolourrepresentationsthe,sometimessubtle,changesinthe individual dissociation product distributions become distinct. Another advantage of these graphic plots can be found in the formation of systematic patterns. These patterns reflect trends in dissociation specificity which allow for the formulation of general rules in fragmentation behavior. Conclusions: Instruments equipped with two different excitation schemes for MS/MS are today widely available. Nonetheless, direct comparisons between the individual results are scarcely made. Such comparative studies bear a powerful analytical potential to elucidate fragmentation reaction mechanism.zeige mehrzeige weniger

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Metadaten
Autor*innen:Stefanie Ickert, Jens RiedelORCiD, S. Beck, M. W. Linscheid
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Rapid Communications in Mass Spectrometry
Jahr der Erstveröffentlichung:2018
Organisationseinheit der BAM:1 Analytische Chemie; Referenzmaterialien
1 Analytische Chemie; Referenzmaterialien / 1.9 Chemische und optische Sensorik
Verlag:Wiley & Sons, Ltd.
Jahrgang/Band:32
Ausgabe/Heft:7
Erste Seite:597
Letzte Seite:603
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Freie Schlagwörter:CID; DNA; HCD; Tandem MS
Themenfelder/Aktivitätsfelder der BAM:Chemie und Prozesstechnik
DOI:10.1002/rcm.8062
ISSN:0951-4198
ISSN:1097-0231
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:12.03.2018
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:29.03.2018
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