Internal energy distribution in electrospray ionization: Towards the evaluation of a thermal-like distribution from the multiple-collision model

David Rondeau, L. Drahos, K. Vékey

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Abstract

RATIONALE The internal energy deposition in ions that cross the desolvation region of an electrospray ionization (ESI) source affects the mass spectra that are obtained using in-source collision-induced dissociation (CID) or in tandem mass spectrometry (MS/MS) mode. It is thus important to evaluate the internal energy distributions of the ions in different parts of an ESI mass spectrometer. METHODS The desolvation region is considered as a collision zone and a partially elastic multiple-collision model is used to account for the accumulation of internal energy in the ions. The ion survival yields (SY Theo) of the theoretical mass spectra calculated by MassKinetics software are fitted with the experimental ion survival yields (SYExp) of the substituted benzylpyridinium cations that have been obtained with an ESI source interfaced with a quadrupole mass spectrometer. The theoretical parameters used for fitting the calculation data with the experimental results are the center-of-mass collision energy (Ecom) of the colliding ions and a term related to the pressure of the desolvation area of the ESI interface. RESULTS In the proposed model, an average number of 'effective' collisions of close to 30 in the desolvation area is employed. The voltages applied to the orifice of this interface are correlated to a theoretical initial kinetic energy (Einit,Kin) in the laboratory frame of the ions. In the present case, these theoretical initial kinetic energies range from 5.5 to 9 eV. The internal energy distributions evaluated from this model resemble the thermal distributions of ions having 'characteristic temperatures' between 1020 and 1550 K, and the results of calculations show that the mean internal energy of the ions increases linearly with the orifice voltage. CONCLUSIONS The model used in this study can account for the energy build-up of the ions in an ESI interface and allows the change in the internal energy distribution of the electrosprayed ions in different regions of a mass spectrometer to be evaluated.

Original languageEnglish
Pages (from-to)1273-1284
Number of pages12
JournalRapid Communications in Mass Spectrometry
Volume28
Issue number11
DOIs
Publication statusPublished - Jun 15 2014

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Electrospray ionization
Ions
Mass spectrometers
Ion sources
Orifices
Kinetic energy
Hot Temperature
Electric potential
Mass spectrometry
Cations

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Organic Chemistry

Cite this

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title = "Internal energy distribution in electrospray ionization: Towards the evaluation of a thermal-like distribution from the multiple-collision model",
abstract = "RATIONALE The internal energy deposition in ions that cross the desolvation region of an electrospray ionization (ESI) source affects the mass spectra that are obtained using in-source collision-induced dissociation (CID) or in tandem mass spectrometry (MS/MS) mode. It is thus important to evaluate the internal energy distributions of the ions in different parts of an ESI mass spectrometer. METHODS The desolvation region is considered as a collision zone and a partially elastic multiple-collision model is used to account for the accumulation of internal energy in the ions. The ion survival yields (SY Theo) of the theoretical mass spectra calculated by MassKinetics software are fitted with the experimental ion survival yields (SYExp) of the substituted benzylpyridinium cations that have been obtained with an ESI source interfaced with a quadrupole mass spectrometer. The theoretical parameters used for fitting the calculation data with the experimental results are the center-of-mass collision energy (Ecom) of the colliding ions and a term related to the pressure of the desolvation area of the ESI interface. RESULTS In the proposed model, an average number of 'effective' collisions of close to 30 in the desolvation area is employed. The voltages applied to the orifice of this interface are correlated to a theoretical initial kinetic energy (Einit,Kin) in the laboratory frame of the ions. In the present case, these theoretical initial kinetic energies range from 5.5 to 9 eV. The internal energy distributions evaluated from this model resemble the thermal distributions of ions having 'characteristic temperatures' between 1020 and 1550 K, and the results of calculations show that the mean internal energy of the ions increases linearly with the orifice voltage. CONCLUSIONS The model used in this study can account for the energy build-up of the ions in an ESI interface and allows the change in the internal energy distribution of the electrosprayed ions in different regions of a mass spectrometer to be evaluated.",
author = "David Rondeau and L. Drahos and K. V{\'e}key",
year = "2014",
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doi = "10.1002/rcm.6899",
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TY - JOUR

T1 - Internal energy distribution in electrospray ionization

T2 - Towards the evaluation of a thermal-like distribution from the multiple-collision model

AU - Rondeau, David

AU - Drahos, L.

AU - Vékey, K.

PY - 2014/6/15

Y1 - 2014/6/15

N2 - RATIONALE The internal energy deposition in ions that cross the desolvation region of an electrospray ionization (ESI) source affects the mass spectra that are obtained using in-source collision-induced dissociation (CID) or in tandem mass spectrometry (MS/MS) mode. It is thus important to evaluate the internal energy distributions of the ions in different parts of an ESI mass spectrometer. METHODS The desolvation region is considered as a collision zone and a partially elastic multiple-collision model is used to account for the accumulation of internal energy in the ions. The ion survival yields (SY Theo) of the theoretical mass spectra calculated by MassKinetics software are fitted with the experimental ion survival yields (SYExp) of the substituted benzylpyridinium cations that have been obtained with an ESI source interfaced with a quadrupole mass spectrometer. The theoretical parameters used for fitting the calculation data with the experimental results are the center-of-mass collision energy (Ecom) of the colliding ions and a term related to the pressure of the desolvation area of the ESI interface. RESULTS In the proposed model, an average number of 'effective' collisions of close to 30 in the desolvation area is employed. The voltages applied to the orifice of this interface are correlated to a theoretical initial kinetic energy (Einit,Kin) in the laboratory frame of the ions. In the present case, these theoretical initial kinetic energies range from 5.5 to 9 eV. The internal energy distributions evaluated from this model resemble the thermal distributions of ions having 'characteristic temperatures' between 1020 and 1550 K, and the results of calculations show that the mean internal energy of the ions increases linearly with the orifice voltage. CONCLUSIONS The model used in this study can account for the energy build-up of the ions in an ESI interface and allows the change in the internal energy distribution of the electrosprayed ions in different regions of a mass spectrometer to be evaluated.

AB - RATIONALE The internal energy deposition in ions that cross the desolvation region of an electrospray ionization (ESI) source affects the mass spectra that are obtained using in-source collision-induced dissociation (CID) or in tandem mass spectrometry (MS/MS) mode. It is thus important to evaluate the internal energy distributions of the ions in different parts of an ESI mass spectrometer. METHODS The desolvation region is considered as a collision zone and a partially elastic multiple-collision model is used to account for the accumulation of internal energy in the ions. The ion survival yields (SY Theo) of the theoretical mass spectra calculated by MassKinetics software are fitted with the experimental ion survival yields (SYExp) of the substituted benzylpyridinium cations that have been obtained with an ESI source interfaced with a quadrupole mass spectrometer. The theoretical parameters used for fitting the calculation data with the experimental results are the center-of-mass collision energy (Ecom) of the colliding ions and a term related to the pressure of the desolvation area of the ESI interface. RESULTS In the proposed model, an average number of 'effective' collisions of close to 30 in the desolvation area is employed. The voltages applied to the orifice of this interface are correlated to a theoretical initial kinetic energy (Einit,Kin) in the laboratory frame of the ions. In the present case, these theoretical initial kinetic energies range from 5.5 to 9 eV. The internal energy distributions evaluated from this model resemble the thermal distributions of ions having 'characteristic temperatures' between 1020 and 1550 K, and the results of calculations show that the mean internal energy of the ions increases linearly with the orifice voltage. CONCLUSIONS The model used in this study can account for the energy build-up of the ions in an ESI interface and allows the change in the internal energy distribution of the electrosprayed ions in different regions of a mass spectrometer to be evaluated.

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