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New Mechanism of Extractive Electrospray Ionization Mass Spectrometry for Heterogeneous Solid Particles
S Kumbhani1, T Longin2, L M Wingen1
1Department of Chemistry, University of California-Irvine , Irvine, California 92697-2025, United States.
Analytical Chemistry
|January 12, 2018
Summary
Extractive electrospray ionization mass spectrometry (EESI-MS) primarily analyzes particle surfaces, not entire particles, due to dissolution kinetics and surface properties. This technique is sensitive to surface layers, with limited sampling of the particle core.
Area of Science:
- Atmospheric Chemistry
- Analytical Chemistry
- Mass Spectrometry
Background:
- Real-time analysis of airborne particles is crucial for exposure studies, visibility, and climate impact assessments.
- Characterizing heterogeneous solid or semisolid particles, especially their molecular and 3D structure, remains challenging.
- Extractive electrospray ionization mass spectrometry (EESI-MS) is a technique for analyzing airborne particles.
Purpose of the Study:
- To investigate the sampling efficiency of EESI-MS for solid particles with organic coatings.
- To determine the sensitivity of EESI-MS to particle surface layers versus the core.
- To elucidate the factors influencing EESI-MS analysis of coated particles.
Main Methods:
- Analysis of sodium nitrate (NaNO3) particles coated with glutaric acid (GA) and malonic acid (MA) using EESI-MS.
- Comparison with conventional electrospray ionization mass spectrometry (ESI-MS) of extracted filter samples.
- Experiments on single-component particles (NaNO3, GA, citric acid) to study dissolution kinetics.
Main Results:
- EESI-MS showed higher sensitivity to the organic coating than the NaNO3 core for coated NaNO3 particles.
- Significant signals from both coating and core were observed for GA particles coated with MA.
- Conventional ESI-MS detected substantially more core material than EESI-MS in both cases.
- EESI-MS sampling was found to be sensitive to surface layers, not the entire particle.
- Kinetics of dissolution, surface energies, and solubility were identified as key factors influencing EESI-MS sensitivity.
Conclusions:
- EESI-MS does not necessarily sample the entire solid particle under the tested conditions.
- The technique is more sensitive to the surface layers of coated particles.
- A new mechanism for EESI solvent droplet interaction with solid particles was proposed, accounting for experimental observations.
- Solubility, surface energies, and dissolution kinetics are critical for understanding EESI-MS analysis of solid particles.
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