2012
DOI: 10.1021/ac302789c
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Unraveling the Mechanism of Electrospray Ionization

Abstract: Electrospray ionization (ESI) generates intact gas-phase ions from analytes in solution for mass spectrometric investigations. ESI can proceed via different mechanisms. Low molecular weight analytes follow the ion evaporation model (IEM), whereas the charged residue model (CRM) applies to large globular species. A chain ejection model (CEM) has been proposed for disordered polymers.

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Cited by 564 publications
(768 citation statements)
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References 49 publications
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“…Specificity for certain matrices was reported in the development of MALDI (e.g., sinapinic acid for high mass proteins [64], DCTB for fullerenes and polymers [65], and tetracyanaquinodimethane for polycyclic aromatic hydrocarbons [66]), and ESI (e.g., metal salts [67] and peptides [4]). This is similar to questions raised for ESI and MALDI here and in other work [4,56,[68][69][70][71]. An explanation of how MAI can selectively ionize europium-containing species is of interest and may be determined with future work.…”
Section: Ionizationsupporting
confidence: 79%
“…Specificity for certain matrices was reported in the development of MALDI (e.g., sinapinic acid for high mass proteins [64], DCTB for fullerenes and polymers [65], and tetracyanaquinodimethane for polycyclic aromatic hydrocarbons [66]), and ESI (e.g., metal salts [67] and peptides [4]). This is similar to questions raised for ESI and MALDI here and in other work [4,56,[68][69][70][71]. An explanation of how MAI can selectively ionize europium-containing species is of interest and may be determined with future work.…”
Section: Ionizationsupporting
confidence: 79%
“…[8][9][10] The charged primary droplets produced by the DESI probe collide with the surface, wetting it and forming a thin film into which the analyte is dissolved by a solid-liquid microextraction mechanism 8 Subsequent droplet collisions result in momentum transfer and takeoff of secondary droplets containing the material extracted from the surface. 9,10 Ultimately, gas phase ions are believed to be produced through ESI-like processes following the ion evaporation, charge residue models or other models, 11 however the precise ion formation process in DESI has yet to be experimentally proven. 12 DESI sensitivity is strongly dependent upon the solubility of the analyte in the spray solvent, as desorption relies on the localized microextraction.…”
Section: Introductionmentioning
confidence: 99%
“…In the electrospray system under consideration, the ions are formed inside a heated capillary connecting the atmospheric and the subatmospheric chambers, either through the charge residue or ion evaporation mechanisms [29], and then move through the capillary toward its outlet. Ions will be tracked only after leaving the capillary.…”
Section: Flow Conditions and Numerical Methodsmentioning
confidence: 99%