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Many mass spectrometry methods using various ionization sources provide bulk composition of airborne particles, but little is known about the surface species that play a major role in determining their physicochemical properties that impact air quality, climate, and health. The present work shows that the composition of surface layers of atmospherically relevant submicron organic particles can be probed without the use of an external ionization source. Solid dicarboxylic acid particles are used as models, with glutaric acid being the most efficient at generating ions. Coating with small diacids or products from α-pinene ozonolysis demonstrates that ions are ejected from the surface, providing surface molecular characterization of organic particles on the fly. This unique approach provides a path forward for elucidating the role of the surface in determining chemical and physical properties of particles, including heterogeneous reactions, particle growth, water uptake, and interactions with biological systems.
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Modeling the ionization mechanism of amorphous solid particles without an external energy source coupled to mass spectrometry
Description: Mechanistic analysis of ion desorption from glutaric acid particles used in the development of surface-sensitive mass spectroscopy ionization methods. Abstract: Ionization via desorption of charged analytes from the surface of solid amorphous glutaric acid particles, without the assistance of an external energy source, has been shown to be a promising method that can be coupled to mass spectrometry. We conduct mechanistic studies of the later stages of this ionization process using atomistic molecular dynamics. Our analysis focuses on the hydrogen bonding, diffusion, and ion desorption from nano-aggregates of glutaric acid. These nano-aggregates exhibit an extended H-bonded network, often comprising H-bonded chains, linear dimeric assemblies, and occasionally cyclic trimeric assemblies. These local structures serve as centers for proton transfer reactions. The intermediate hydrocarbon chain between the proton-carrying oxygen sites prevents proton diffusion over a long distance unless there is significant translational or rotational movement of the proton-carrying diacid molecule. Our calculations show that diffusion on the surface is an order of magnitude faster than in the core of the nano-aggregate, which aids effective proton transfer on the particle's exterior. We find that ionic species desorb from the aggregate's surface through independent evaporation events of small clusters, where the ion is coordinated by only a few glutaric acid molecules. Near the nano-aggregate's Rayleigh limit, jets capable of releasing multiple ions were not observed. These observations suggest a more general ion-evaporation mechanism that applies to low-dielectric particles of various sizes, complementing the original ion-evaporation mechanism proposed for aqueous droplets with an approximate radius of 10–15 nm. The combined evidence from molecular modeling presented here and the thermodynamic properties of solid and supercooled liquid glutaric acid indicates that the stronger signals of glutaric acid observed in the mass spectra, relative to other experimentally tested diacids, can be attributed to its significantly lower melting point and the reduced enthalpy of vaporization of its amorphous state compared to other tested diacids.
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- PAR ID:
- 10553724
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- ISSN:
- 1463-9076
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1039/D4CP03597F
