Intriguing Mass Spectrometric Behavior of Guanosine Under Low Energy Collision-Induced Dissociation: H<sub>2</sub>O Adduct Formation and Gas-Phase Reactions in the Collision Cell

Tuytten, Robin; Lemière, Filip; Dongen, Walter Van; Esmans, Eddy L.; Witters, Erwin; Herrebout, Wouter A.; Veken, B. Van der; Dudley, Ed; Newton, Russell P.

doi:10.1016/j.jasms.2005.03.026

Cited by 61 publications

(67 citation statements)

References 29 publications

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“…With increased CE, the typical product ions of the [BH 2 ] ϩ -NH 3 dissociation pathway also appeared. The high affinity of m/z 135 for H 2 O is seen in the product ion observed at m/z 153, the result of scavenging traces of H 2 16 O available in the collision cell by the product ion at m/z 135 as reported earlier [5].…”

Section: : a Results Of Ch 3 Oh-adduct Formation And Ch 3 Oh-gas-phasesupporting

confidence: 68%

“…18 O-and CH 3 OH-adducts (respectively, at m/z 155 and 167) is clear from Figure 2: with increasing CV ϩ -NH 3 pathway have already been discussed [5,9], but a variety of new product ions were also observed in the MS/MS spectra of m/z 155 in the current study. ϩ -NHCNH in the fragmentation of guanine [9].…”

Section: H 2 O-and Ch 3 Oh-adduct Formation Of In-source Cid Product supporting

confidence: 64%

“…The following criteria were applied to distinguish "true" product ions from interferences in the spectra: (1) only ions with intensity above 1% of the base peaks intensity were included; (2) the product ions must be present in the spectra for at least two collision energy values applied to any given precursor ion; (3) the product ions must yield credible empirical formulas in respect of the parent ion from which they arose (taking into account possible adduct formation in the collision cell as described previously) [5,10].…”

Section: Instrumentation and Ms Conditionsmentioning

confidence: 99%

“…During an in-depth study of the fragmentation behavior of the nucleoside guanosine with the optimized in-source CID-QqTOF MS approach it became clear that some of its product ions have a high affinity for H 2 O. Additionally, some other product ions arose, which suggested even more sophisticated ion-molecule reactions [5]. 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: 95%

“…By in-source CID of the protonated guanosine the second generation product ion (Figure 1), was produced [5,9]. Its in-source formed adducts with H 2 18 O and CH 3 OH were subsequently submitted to tandem MS analysis by QqTOF MS and accurate mass data of the according product ions was acquired.…”

mentioning

confidence: 99%

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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-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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Section: : a Results Of Ch 3 Oh-adduct Formation And Ch 3 Oh-gas-phasesupporting

confidence: 68%

Section: H 2 O-and Ch 3 Oh-adduct Formation Of In-source Cid Product supporting

confidence: 64%

Section: Instrumentation and Ms Conditionsmentioning

confidence: 99%

mentioning

confidence: 95%

mentioning

confidence: 99%

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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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Formation of the unusual [M+H‐11 Da]⁺ ion peak in the collision‐induced dissociation mass spectrum of [M+H]⁺ ion of hydrochlorothiazide

et al. 2009

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Formation of the unusual [M+H-11 Da] + ion peak in the collisioninduced dissociation mass spectrum of [M+H] + ion of hydrochlorothiazideHydrochlorothiazide (HCT) is one of the diuretics that is banned in sport by the World Anti-Doping Agency (WADA). In continuation of our diuretics confirmation work for anti-doping purposes, the tandem mass (MS/MS) spectrum of the HCT under low-energy collision-induced dissociation (CID) mass spectrometry with positive electrospray ionization (ESI) was investigated and interpreted in detail. The CID of the protonated HCT at m/z 298 generated the unexpected product ion at m/z 287 corresponding to the + ion of HCT on a 3D-ion trap mass spectrometer (MS). Although it is well known that ions undergo gas-phase rearrangements under low-energy CID conditions, the formation of this unexpected product ion could not be easily explained by the conventional mechanism. [1 -8] Therefore, the aim of the present study is essentially to rationalize the uncommon behavior resulting in the unusual [M+H-11 Da] + ion peak under the lowenergy CID.CID experiments were performed using three MS systems: Agilent 1100 series LC/MSD (3D) ion trap, Thermo hybrid-linear (2D) ion trap/Orbitrap and Sciex API-2000 triple-quadrupole (TQ) mass spectrometers, each equipped with an electrospray interface using nitrogen gas. Samples (10 µg/ml) in MeOH/water/formic acid (50 : 50 : 0.1, vol : vol : vol) solution were infused into the ESI source in a positive ion mode at a rate of 5 µl/min via a syringe pump. For ion traps and the TQ mass analyzer, ion spray voltage was adjusted to 4500 and 5500 V, respectively. Helium and nitrogen were used as collision gases for the tandem mass spectrometric experiments. For accurate mass measurement, highresolution (R = 60 000) and high-accuracy 2D ion trap mass spectrometric analyses were conducted using a Finnigan LTQ Orbitrap mass spectrometry (Thermo Fisher Scientific Inc., MA, USA) operated in a positive-ion electrospray mode, whereas others followed the 2D ion trap mass spectrometer.The MS/MS spectrum of the protonated HCT (m/z 298) on the 2D-ion trap MS is depicted in Fig. 1(A). Representative fragment ions of HCT were observed at m/z 287, 281 and 269, and the product ions at m/z 281 and 269 could be rationalized by the neutral loss of NH 3 (17 Da) and NH CH 2 (29 Da), respectively. As shown in Fig. 1(B) and (C), the product ion at m/z 269 was not observed in the 3D-ion trap MS and it was shown to have a relatively high intensity on TQ MS. Among these product ions, we were especially interested in the ion at m/z 287 corresponding to the unusual + ion. In order to examine the origin of the unexpected ion at m/z 287, the respective ions at m/z 287 and 269 were isolated and then subjected to collisional activation in 2D-ion trap MS. As shown in Fig. 2, the attempt to isolate the ion at m/z 269 was unsuccessful, and the ion at m/z 287 was constantly present. When the ion at m/z 269 regenerated by the CID of the ion at m/z 287 was isolated, the same result was observed. Consequen...

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Reactivity of gaseous sodiated ions derived from benzene dicarboxylate salts toward residual water in the collision gas

Chan

Axe²,

Bolgar

et al. 2010

J. Mass Spectrom.

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The sodium adduct of disodium salts of benzene dicarboxylic acids (m/z 233), when subjected to collision-induced dissociation (CID), undergoes a facile loss of CO(2) to produce an ion of m/z 189, which retains all the three sodium atoms of the precursor. The CID spectrum of this unusual m/z 189 ion shows significant peaks at m/z 167, 63 and 85. The enigmatic m/z 167 ion, which appeared to represent a loss of a 22-Da neutral fragment from the precursor ion is in fact a fragment produced by the interaction of the m/z 189 ion with traces of water present in the collision gas. The change of the m/z 167 peak to 168, when D(2)O vapor was introduced to the collision gas of a Q-ToF instrument, proved that such an intervention of water could occur even in collision cells of tandem-in-space mass spectrometers. The m/z 189 ion has such high affinity for water; it forms an ion/molecule complex even during the brief residence time of ions in collision cells of triple quadrupole instruments. The complex formed in this way then eliminates elements of NaOH to produce the ion observed at m/z 167. In an ion trap, the relative intensity of the m/z 167 peak increases with longer activation time even at the lowest possible collision energy setting. Similarly, the m/z 145 ion (which represents the sodium adduct of phenelenedisodium, formed by two consecutive losses of CO(2) from the m/z 233 ion of meta- and para-isomers) interacts with water to produce a fragment ion at m/z 123 for the sodium adduct of phenylsodium. Other uncommon ions that originate also from water/ion interactions are observed at m/z 85 and 63 for [Na(3)O](+) and [Na(2)OH](+), respectively. Tandem mass spectrometric experiments conducted with appropriately deuterium-labeled compounds confirmed that the proton required for the formation of the [Na(2)OH](+) ion originates from traces of water present in the collision gas and not from the ring protons of the aromatic moiety.

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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

Cited by 61 publications

References 29 publications

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

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

Formation of the unusual [M+H‐11 Da]⁺ ion peak in the collision‐induced dissociation mass spectrum of [M+H]⁺ ion of hydrochlorothiazide

Reactivity of gaseous sodiated ions derived from benzene dicarboxylate salts toward residual water in the collision gas

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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

Cited by 61 publications

References 29 publications

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

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

Formation of the unusual [M+H‐11 Da]+ ion peak in the collision‐induced dissociation mass spectrum of [M+H]+ ion of hydrochlorothiazide

Reactivity of gaseous sodiated ions derived from benzene dicarboxylate salts toward residual water in the collision gas

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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

Formation of the unusual [M+H‐11 Da]⁺ ion peak in the collision‐induced dissociation mass spectrum of [M+H]⁺ ion of hydrochlorothiazide