Kinetics of solvent addition on electrosprayed ions in an electrospray source and in a quadrupole ion trap

In-source collision induced dissociation was applied to access second generation ions of protonated guanosine. The in-source gas-phase behavior of [BH 2 ] ϩ -NH 3 (m/z 135, C 5 H 3 N 4 O ϩ ) was investigated. Adduct formation and reactions with available solvent molecules (H 2 O and CH 3 OH) were demonstrated. Several addition/elimination sequences were observed for this particular ion and solvent molecules. Dissociation pathways for the newly formed ions were developed using a QqTOF mass spectrometer, permitting the assignment of elemental compositions of all product ions produced. Reaction schemes were suggested arising from the ring-opened intermediate of the protonated base moiety [BH 2 ] ϩ , obtained from fragmentation of guanosine. The mass spectral data revealed that the in-source CH 3 OH-reaction product underwent more complex fragmentations than the comparable ion following reaction with H 2 O. A rearrangement and a parallel radical dissociation pathway were discerned. Apart from the mass spectrometric evidence, the fragmentation schemes are supported by density functional theory calculations, in which the reaction of the ring-opened protonated guanine intermediate with CH 3 OH and a number of subsequent fragmentations were elaborated. uring the last decade, most fragmentation pathways were elaborated on triple quadrupole (QqQ) and particularly quadrupole ion-trap (QIT) instruments. The latter's capabilities of accessing MS n product ions by applying repeated stages of mass selection and fragmentation proved to be very useful [1]. The maturation of the time of flight (TOF) technology and, more importantly, its use in hybrid-arrangements such as the popular orthogonal QqTOF mass spectrometer made accurate mass data of product ions more readily available [2]. In many cases, the elemental compositions of the product ions can unambiguously be assigned when using a QqTOF mass spectrometer. Product ions lower in the genealogical ladder are also accessible by applying relatively high collision energies in the collision cell. Yet disentanglement of different dissociation pathways originating from a communal progenitor is -in general-still confined to QIT set ups, although the interpretation of energy resolved spectra also has proven its usefulness [3].Recently we and others showed [4 -6] that by making optimal use of in-source CID, combined with the inherent tandem MS capabilities of the QqTOF, what is in effect up to MS 5 data can be acquired. Compared to QIT data the QqTOF data obtained is superior in respect of higher mass accuracy. On the other hand QIT-CID experiments, in general, access almost exclusively the dissociation reaction channels of the lowest energy of activation [7]. This energy-dependent information can

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“…It has to be noted that in-source addition of solvent molecules has been observed before by Gabelica et al for benzylpyridinium cations [8].…”

mentioning

confidence: 63%

In-source CID of guanosine: Gas phase ion-molecule reactions

Tuytten

Lemière

Esmans

et al. 2006

J. Am. Soc. Mass Spectrom.

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“…In establishing the fragmentation pathways and associating mass spectral fragmentation with chemical structure, it is assumed that product ions are subunits of their precursor ion. However, during the course of using ion trap-based ESI-MS/MS to characterize natural products, it has been reported earlier [9][10][11][12][13][14][15] that certain fragmentation products react with H 2 o and other commonly used ESI solvent molecules, thereby complicating MS/MS data interpretation.…”

Section: Journal Of Mass Spectrometrymentioning

confidence: 99%

Solvation in Gas-Phase Reactions of Sulfonic Groups Containing Ionic Liquids in Electrospray Ionization Quadrupole Ion Trap Mass Spectrometry

Cao

et al. 2009

Eur J Mass Spectrom (Chichester)

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In electrospray ionization (ESI) quadrupole ion trap mass spectrometry, certain fragment ions generated in the ion trap from a series of sulfonic groups containing ionic liquids (ILs) are found to undergo ion-molecule reactions with ESI solvent molecules (water, acetonitrile and methanol) to form adduct species. These unexpected solvated fragment ions severely complicate the interpretation of mass spectrometric data. Multi-stage fragmentation mass spectra were used to ascertain the chemical structures of these adduct species. It is important that solvation must be taken into account in order to prevent erroneous data interpretation for sulfonic groups containing ILs.

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“…Neutral gain of H 2 O or MeOH was already briefly mentioned in an APCI ion trap MS study for fragments of some nucleobases (except guanine) [26],°and°addition°of°acetonitrile°to°benzyl°cations°was monitored°in°a°ion°trap°mass°spectrometer° [27].°In°both cases the solvent molecules were provided during passage from the source into the MS.…”

Section: Study Of the H 2 O Addition In The Collision Cell Neutral Gamentioning

confidence: 99%

Intriguing Mass Spectrometric Behavior of Guanosine Under Low Energy Collision-Induced Dissociation: H₂O Adduct Formation and Gas-Phase Reactions in the Collision Cell

Tuytten

Lemière

Dongen

et al. 2005

J. Am. Soc. Mass Spectrom.

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An in-depth study of the fragmentation pathway of guanosine was conducted by using an in-source collision-induced dissociation high-mass accuracy tandem mass spectrometry experiment. The equivalent of MS 4 data, a level of information normally achieved on ion trap instruments, was obtained on a Q-TOF mass spectrometer. The combination of the features of high-resolution, accuracy, and in-source CID permitted the unambiguous elucidation of the different fragmentation pathways. Furthermore the elemental compositions of the product ions generated were assigned and their mutual genealogical relationships established. Formerly proposed dissociation pathways of guanosine were revisited and elaborated on more deeply. Furthermore, the presence of H 2 O in the collision cell of several tandem MS instruments was demonstrated and its effect on the product ion spectra investigated. The neutral gain of H 2 O by particular fragments of guanosine was experimentally proven by using argon, saturated with H 2 18 O, as the collision gas. Data indicating the occurrence of more complex reactions in the collision cell as a result of the presence of H 2 O were produced, specifically relating to neutral gain/neutral loss sequences. In silico calculations supported the experimental observation of neutral gain by guanosine fragments and predicted a similar behavior for adenosine. The latter was subsequently experimentally confirmed. , and nucleoside levels in urine have the potential to act as cancer biomarkers [2][3][4][5]. As their occurrence is both ubiquitous and quantitatively varying [6,7] their unequivocal characterization is crucial.For guanine alone over 20 natural variants are known to occur in RNA [6], which makes structural identification a challenging task. In our earlier LC-ESI-MS/MS experiments of urinary nucleosides [8], unexpected product ions of guanosine and its methylated derivatives were detected. The presence of these ions prompted us to perform additional mass spectrometric studies since their origin was not straightforward. This report provides an in-depth study of the fragmentation behavior of guanosine under lowenergy CID conditions, revealing H 2 O addition to specific fragments.We also wish to demonstrate the use of a Q-TOF mass spectrometer in the collection of the equivalent of MS 4 data, a level of information normally acquired only in ion trap-or FT-MS n experiments [9,10]. This was achieved by making optimal use of "in

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Kinetics of solvent addition on electrosprayed ions in an electrospray source and in a quadrupole ion trap

Cited by 20 publications

References 15 publications

In-source CID of guanosine: Gas phase ion-molecule reactions

In-source CID of guanosine: Gas phase ion-molecule reactions

Solvation in Gas-Phase Reactions of Sulfonic Groups Containing Ionic Liquids in Electrospray Ionization Quadrupole Ion Trap Mass Spectrometry

Intriguing Mass Spectrometric Behavior of Guanosine Under Low Energy Collision-Induced Dissociation: H₂O Adduct Formation and Gas-Phase Reactions in the Collision Cell

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Kinetics of solvent addition on electrosprayed ions in an electrospray source and in a quadrupole ion trap

Cited by 20 publications

References 15 publications

In-source CID of guanosine: Gas phase ion-molecule reactions

In-source CID of guanosine: Gas phase ion-molecule reactions

Solvation in Gas-Phase Reactions of Sulfonic Groups Containing Ionic Liquids in Electrospray Ionization Quadrupole Ion Trap Mass Spectrometry

Intriguing Mass Spectrometric Behavior of Guanosine Under Low Energy Collision-Induced Dissociation: H2O Adduct Formation and Gas-Phase Reactions in the Collision Cell

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Intriguing Mass Spectrometric Behavior of Guanosine Under Low Energy Collision-Induced Dissociation: H₂O Adduct Formation and Gas-Phase Reactions in the Collision Cell