Fragmentation, structure, and energetics of small sodium formate clusters: Evidence for strong influence of entropic effects

Révész, Ágnes; Rokob, Tibor András; Maász, Gábor; Márk, László; Hevér, Helga; Drahos, László; Vékey, Károly

doi:10.1016/j.ijms.2013.06.029

Cited by 5 publications

(7 citation statements)

References 79 publications

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“…These interferences can mask analyte signals through the formation of matrix ion clusters 33 and reduce the overall abundance of analytes through ion suppression 34 . Using the solvent modifiers (FA and SA) shown earlier, sodium formate clusters will be readily formed through electrospray ion formation process when sodium formate is formed by nebulizing formate with sodium 35 . Sodium formate cluster ions, [NaOOCH] n Na + (1 ≤ n), can be produced from the carboxylate anions [HCOO] − and sodium cations [Na] + 35 .…”

Section: Resultsmentioning

confidence: 99%

“… 34 Using the solvent modifiers (FA and SA) shown earlier, sodium formate clusters will be readily formed through electrospray ion formation process when sodium formate is formed by nebulizing formate with sodium. 35 Sodium formate cluster ions, [NaOOCH] n Na + (1 ≤ n), can be produced from the carboxylate anions [HCOO] − and sodium cations [Na] + . 35 The [NaOOCH] n Na + (1 ≤ n) ions with bonding order (n) between 1 and 7 were monitored as they covered the scan range from m/z 50 to 450 that the cocaine metabolites were analysed over in this study.…”

Section: Resultsmentioning

confidence: 99%

“…(1 ≤ n), can be produced from the carboxylate anions [HCOO] À and sodium cations [Na] + . 35 The [NaOOCH] n Na + (1 ≤ n) ions with bonding order (n) between 1 and 7 were monitored as they covered the scan range from m/z 50 to 450 that the cocaine metabolites were analysed over in this study. It is possible to detect over this range 7 of these cluster ions which were observed at m/z 90.98 S5 (supporting information).…”

Section: Surface Activity Separationmentioning

confidence: 99%

Section: Surface Activity Separationmentioning

confidence: 99%

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Development of a rapid, in‐situ analysis method using sheath‐flow probe electrospray ionisation‐mass spectrometry for the direct identification of cocaine metabolites in dried blood spots

Kim

Kelly

Turner

et al. 2022

Rapid Comm Mass Spectrometry

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Small amounts of biofluid samples are frequently found at crime scenes, however existing gold standard methods such as LC-MS frequently require destructive extraction of the sample before a time-consuming analysis which puts strain on forensic analysis providers and can preclude further sample analysis. This study presents the application of Sheath Flow Probe Electrospray Ionization -Mass Spectrometry (sfPESI-MS) to the direct analysis of drug metabolites in dried blood spots as a high throughput, minimally destructive alternative. METHODS:A rapid direct analysis method using a sfPESI ionisation source coupled to an Orbitrap Exactive mass spectrometer was applied to detect cocaine metabolites (benzoylecgonine, BZE, cocaethylene, CE, and ecgonine methyl ester, EME) from dried blood spots. An optimisation study exploring the use of different chemical modifiers (formic acid and sodium acetate) in the sfPESI probe extraction solvent was conducted to enhance the sensitivity and reproducibility of the sfPESI-MS method. RESULTS:Optimization of the extraction solvent significantly enhanced the sensitivity and reproducibility of the sfPESI-MS method. A quantitative response over a 5-point calibration range 0.5 to 10 µg/mL was obtained for benzoylecgonine (R 2 = 0.9979) and cocaethylene (R 2 = 0.9948). Limits-of-detection (LoD) of 1.31, 0.29 and 0.15 µg/mL were achieved for EME, BZE and CE respectively from 48-hour aged dried blood spots with % RSD across the calibration range ranging between 19 -28 % for [BZE+H] + , 13 -21 % for [CE+H] + and 12 -29 % for [EME+H] + .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Surface Activity Separationmentioning

confidence: 99%

Section: Surface Activity Separationmentioning

confidence: 99%

See 2 more Smart Citations

Development of a rapid, in‐situ analysis method using sheath‐flow probe electrospray ionisation‐mass spectrometry for the direct identification of cocaine metabolites in dried blood spots

Kim

Kelly

Turner

et al. 2022

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

show abstract

“…38 We note that CID using collisions in the ion trap would not result in a similar extent of fragmentation as only the parent ions are activated and not the resulting product ions. 39 Fig. 3A displays the breakdown graphs of the (odd electron) C 60 F 45 2À dianion.…”

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confidence: 99%

Energy-dependent gas-phase fragmentation of fluorofullerene multiply charged anions (MCAs)

Kirschbaum

Hausmann

Boltalina

et al. 2015

Phys. Chem. Chem. Phys.

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Long-lived di- and trianions have been formed from fluorofullerenes in the gas phase by electrospray ionization. Fragmentation of multiply charged anions has been induced by multiple low-energy collisions. Two complementary dissociation experiments have been conducted. Firstly, unequivocal connectivity has been established between the precursor ion and the first and second generation of its product ions. Secondly, dianions have been studied in energy-resolved collisions, allowing the elucidation of the energetic demands of the dissociations. It was possible to study dianions with odd and even F numbers, possessing even and odd electron configurations, respectively. The fragmentation behavior is governed by the electronic stability of the anionic protagonists, in that ions with the less stable odd-electron configuration dissociate into species with the more stable even-electron configuration. Dianions with an odd electron count release an F˙ atom to turn into an even electron system while retaining the charge state. Dianions with an even electron count undergo a more energy demanding charge separation reaction (Coulomb explosion) into an F(-) anion and an even electron monoanion. The studied trianions behave accordingly. F2 loss is prominent only with monoanions within an even-to-even electron fragmentation cascade. The trianions are long-lived with lifetimes of at least 0.1 s.

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Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

Shukla

Bogdanov

2015

The Journal of Chemical Physics

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Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N2). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi)nLi(+), (HCOOLi)nLim (m+), (HCOOLi)nHCOO(-), and (HCOOLi)n(HCOO)m (m-). Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi)3Li(+) being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi)2) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi)3Li(+) as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

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Fragmentation, structure, and energetics of small sodium formate clusters: Evidence for strong influence of entropic effects

Cited by 5 publications

References 79 publications

Development of a rapid, in‐situ analysis method using sheath‐flow probe electrospray ionisation‐mass spectrometry for the direct identification of cocaine metabolites in dried blood spots

Development of a rapid, in‐situ analysis method using sheath‐flow probe electrospray ionisation‐mass spectrometry for the direct identification of cocaine metabolites in dried blood spots

Energy-dependent gas-phase fragmentation of fluorofullerene multiply charged anions (MCAs)

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

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