Unraveling the Mechanism of Electrospray Ionization

Konermann, Lars; Ahadi, Elias; Rodriguez, Antony D.; Vahidi, Siavash

doi:10.1021/ac302789c

Cited by 578 publications

(768 citation statements)

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%

Matrix-Assisted Ionization-Ion Mobility Spectrometry-Mass Spectrometry: Selective Analysis of a Europium–PEG Complex in a Crude Mixture

Fischer

Lutomski

El‐Baba

et al. 2015

J. Am. Soc. Mass Spectrom.

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Abstract. The analytical utility of a new and simple to use ionization method, matrixassisted ionization (MAI), coupled with ion mobility spectrometry (IMS) and mass spectrometry (MS) is used to characterize a 2-armed europium(III)-containing poly(-ethylene glycol) (Eu-PEG) complex directly from a crude sample. MAI was used with the matrix 1,2-dicyanobenzene, which affords low chemical background relative to matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). MAI provides high ion abundance of desired products in comparison to ESI and MALDI. Inductively coupled plasma-MS measurements were used to estimate a maximum of 10% of the crude sample by mass was the 2-arm Eu-PEG complex, supporting evidence of selective ionization of Eu-PEG complexes using the new MAI matrix, 1,2-dicyanobenzene. Multiply charged ions formed in MAI enhance the IMS gas-phase separation, especially relative to the singly charged ions observed with MALDI. Individual components are cleanly separated and readily identified, allowing characterization of the 2-arm Eu-PEG conjugate from a mixture of the 1-arm Eu-PEG complex and unreacted starting materials. Size-exclusion chromatography, liquid chromatography at critical conditions, MALDI-MS, ESI-MS, and ESI-IMS-MS had difficulties with this analysis, or failed.

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Section: Ionizationsupporting

confidence: 79%

Matrix-Assisted Ionization-Ion Mobility Spectrometry-Mass Spectrometry: Selective Analysis of a Europium–PEG Complex in a Crude Mixture

Fischer

Lutomski

El‐Baba

et al. 2015

J. Am. Soc. Mass Spectrom.

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“…[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%

Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry

Bennet

Gamage

Fernández

2013

JoVE

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Mass spectrometry imaging (MSI) provides untargeted molecular information with the highest specificity and spatial resolution for investigating biological tissues at the hundreds to tens of microns scale. When performed under ambient conditions, sample pre-treatment becomes unnecessary, thus simplifying the protocol while maintaining the high quality of information obtained. Desorption electrospray ionization (DESI) is a spray-based ambient MSI technique that allows for the direct sampling of surfaces in the open air, even in vivo. When used with a softwarecontrolled sample stage, the sample is rastered underneath the DESI ionization probe, and through the time domain, m/z information is correlated with the chemical species' spatial distribution. The fidelity of the DESI-MSI output depends on the source orientation and positioning with respect to the sample surface and mass spectrometer inlet. Herein, we review how to prepare tissue sections for DESI imaging and additional experimental conditions that directly affect image quality. Specifically, we describe the protocol for the imaging of rat brain tissue sections by DESI-MSI. Video LinkThe video component of this article can be found at

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“…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%

Numerical Analysis of Ion-Funnel Transmission Efficiency in an API-MS System with a Continuum/Microscopic Approach

Gimelshein

Lilly

Moskovets

2015

J. Am. Soc. Mass Spectrom.

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Abstract. A multi-step numerical approach is used to analyze the efficiency of an ionfunnel to transport ions over a wide range of m/z. A continuum approach based on the solution of the Navier-Stokes equations is applied to model the gas flow through a capillary connecting the atmospheric and subatmospheric sections of a mass spectrometer. A microscopic, fully kinetic approach based on the solution of the Boltzmann equation is used to examine the ion and gas transport through an ionfunnel kept at a 0.1-3 Torr pressure to the quadrupole section kept at a 0.01 Torr pressure. In addition to aerodynamic drag, the developed approach takes into account the combined effect of the DC field driving the ions downstream toward the funnel exit, the rf field confining the ions in radial direction, and the space charge causing ion repulsion. The sensitivity of the ion transmission to the gas pressure in the ion-funnel, the rf, and the total ion current injected to the funnel from capillary nozzle is shown.

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Unraveling the Mechanism of Electrospray Ionization

Cited by 578 publications

References 49 publications

Matrix-Assisted Ionization-Ion Mobility Spectrometry-Mass Spectrometry: Selective Analysis of a Europium–PEG Complex in a Crude Mixture

Matrix-Assisted Ionization-Ion Mobility Spectrometry-Mass Spectrometry: Selective Analysis of a Europium–PEG Complex in a Crude Mixture

Imaging of Biological Tissues by Desorption Electrospray Ionization Mass Spectrometry

Numerical Analysis of Ion-Funnel Transmission Efficiency in an API-MS System with a Continuum/Microscopic Approach

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