New basis for a method for the estimation fo seconary ion internal energy distribution in ‘soft’ ionization techniques

Derwa, F.; Pauw, Edwin De; Natalis, P.

doi:10.1002/oms.1210260215

Cited by 94 publications

(109 citation statements)

References 8 publications

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“…Since its initial development, the SY method has been applied for measuring the internal energy distributions of ions produced in such ionization methods as ESI [49], matrix assisted laser desorption ionization (MALDI) [50], secondary ion mass spectrometry (SIMS) [51], and fast atom bombardment (FAB) [48]. Studies involving the effect of various instrumental parameters on the energetics of the ESI source have also been conducted, and they aimed at gaining a better understanding of the ionization mechanism and of the possibility of efficiently tuning the internal energy of the ions generated [49,[52][53][54].…”

Section: Esorption Electrospray Ionization (Desi) Is An Ambient Ionmentioning

confidence: 99%

Internal energy distributions in desorption electrospray ionization (DESI)

Nefliu

Smith

Venter

et al. 2008

J. Am. Soc. Mass Spectrom.

108

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The internal energy distributions of typical ions generated by desorption electrospray ionization (DESI) were measured using the "survival yield" method, and compared with corresponding data for electrospray ionization (ESI) and electrosonic spray ionization (ESSI). The results show that the three ionization methods produce populations of ions having internal energy distributions of similar shapes and mean values (1.7-1.9 eV) suggesting similar phenomena, at least in the later stages of the process leading from solvated droplets to gas-phase ions. These data on energetics are consistent with the view that DESI involves "droplet pick-up" (liquid-liquid extraction) followed by ESI-like desolvation and gas-phase ion formation. The effects of various experimental parameters on the degree of fragmentation of p-methoxy-benzylpyridinium ions were compared between DESI and ESSI. The results show similar trends in the survival yields as a function of the nebulizing gas pressure, solvent flow rate, and distance from the sprayer tip to the MS inlet. These observations are consistent with the mechanism noted above and they also enable the user to exercise control over the energetics of the DESI ionization process, through manipulation of external and internal ion source parameters. [1, 24, 29 -32], and explosives detection [4,8,[33][34][35][36][37]. Investigations into the fundamentals of the droplet dynamics and ionization mechanism have also been conducted through systematic measurements of the droplet size and velocity [38], computer simulations [39], surface charging effects [40], or more simply, by evaluating the mass spectra of various types of analytes in conjunction with variations in the experimental parameters [41]. These investigations suggested that the primary ionization mechanism in DESI is "droplet pick-up", i.e., extraction of the analyte into the droplet, followed by electrospray ionization (ESI)-like mechanism in which the progeny droplets are desolvated yielding ionized molecules. One of the arguments supporting this conclusion, the similarity between the ESI and DESI mass spectra, also implies that the two ion sources should generate populations of ions with similar internal energy distributions, P(E). It should be noted though, that the initial events in the two experiments are quite different, and recent simulations show that the process of formation of progeny droplets from the initial ϳ4 m droplets in DESI is not dependent on charge build-up as it is in ESI. These dissimilarities need not result in differences in the final internal energy (E) since the later processes occurring in the atmospheric pressure interface are probably the same for these two processes and, as we will show later, dominate the energetics of the process.Here we use the "survival yield" (SY) method [42] applied to a set of thermometer ions (benzylpyridinium cations) to judge internal energy deposition associated with soft ionization techniques [43] to measure and compare the internal energy distributions of the ions generated b...

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Section: Esorption Electrospray Ionization (Desi) Is An Ambient Ionmentioning

confidence: 99%

Internal energy distributions in desorption electrospray ionization (DESI)

Nefliu

Smith

Venter

et al. 2008

J. Am. Soc. Mass Spectrom.

108

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“…The extent of fragmentation is correlated with the activation energy (or energy barrier E b ) for dissociation. If it is assumed that the dissociation proceeds via a loose transition state (simple bond cleavage) [5,6] with no reverse energy barrier (see figure 2), E b is assumed to be equal to ΔH f (F + ) + ΔH f (Py) -ΔH f (M + ) [4]. According to the nature and the position of the substituent R, the energy barrier changes: the more electron-withdrawing the substituent, the higher the energy barrier for pyridine loss, and the slower the reaction 1.…”

Section: Introductionmentioning

confidence: 99%

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

Gabelica

Lemaire

Laprévôte

et al. 2001

International Journal of Mass Spectrometry

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:Benzylpyridinium cations readily fragment in the electrospray source by loss of pyridine to give benzyl cations (M -79). The full-scan spectra obtained with some instruments also show, in addition, an m/z (M -38) peak corresponding to the addition of acetonitrile, being present in the solvent mixture, on the benzyl cations. Here we report that the addition reaction can occur in the source region of ES-MS instruments, and in a quadrupole ion trap. The kinetics of acetonitrile addition was monitored in an ion trap, acetonitrile being provided by leakage from the source, through the heated capillary. For benzyl ions with different substituents, the addition kinetics has been found positively correlated with the Brown parameter σ + of the benzyl radical, and therefore with the effective charge density on the α-carbon atom of the benzyl ion. This is consistent with the Langevin or ADO theory of ion-molecule reaction kinetics.Introduction :

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“…The efficiency of the fragmentation can be described quantitatively by the survival yield (SY) [6][7][8]. The SY is defined according to eq 1:…”

Section: Evaluation Of the Survival Yield Curvesmentioning

confidence: 99%

Fast identification of phthalic acid esters in poly(vinyl chloride) samples by Direct Analysis In Real Time (DART) tandem mass spectrometry

Kuki

Nagy

Zsuga

et al. 2011

International Journal of Mass Spectrometry

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It was found that the collision energy/voltage necessary to obtain 50% fragmentation (CV 50 ) was linearly dependent on the molecular weight of phthalic acid esters (PAEs). Based on this observation a fast screening technique for the detection of PAEs in Poly Vinyl Chloride (PVC) samples was developed using Direct Analysis in Real Time (DART) ionization tandem mass spectrometry. Based on this observation an automated data acquisition method, including mass-dependent tuning of the collision energy/voltage in DART-MS/MS, was developed thereby reducing the analysis time.

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New basis for a method for the estimation fo seconary ion internal energy distribution in ‘soft’ ionization techniques

Cited by 94 publications

References 8 publications

Internal energy distributions in desorption electrospray ionization (DESI)

Internal energy distributions in desorption electrospray ionization (DESI)

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

Fast identification of phthalic acid esters in poly(vinyl chloride) samples by Direct Analysis In Real Time (DART) tandem mass spectrometry

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