Issue 9, 2019

The chemical reactions in electrosprays of water do not always correspond to those at the pristine air–water interface

Abstract

The recent application of electrosprays to characterize the air–water interface, along with the reports on dramatically accelerated chemical reactions in aqueous electrosprays, have sparked a broad interest. Herein, we report on complementary laboratory and in silico experiments tracking the oligomerization of isoprene, an important biogenic gas, in electrosprays and isoprene–water emulsions to differentiate the contributions of interfacial effects from those of high voltages leading to charge-separation and concentration of reactants in the electrosprays. To this end, we employed electrospray ionization mass spectrometry, proton nuclear magnetic resonance, ab initio calculations and molecular dynamics simulations. We found that the oligomerization of isoprene in aqueous electrosprays involved minimally hydrated and highly reactive hydronium ions. Those conditions, however, are non-existent at pristine air–water interfaces and oil–water emulsions under normal temperature and pressure. Thus, electrosprays should be complemented with surface-specific platforms and theoretical methods to reliably investigate chemistries at the pristine air–water interface.

Graphical abstract: The chemical reactions in electrosprays of water do not always correspond to those at the pristine air–water interface

Associated articles

Supplementary files

Article information

Article type
Edge Article
Submitted
11 Dec 2018
Accepted
21 Dec 2018
First published
21 Dec 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 2566-2577

The chemical reactions in electrosprays of water do not always correspond to those at the pristine air–water interface

A. Gallo, A. S. F. Farinha, M. Dinis, A. Emwas, A. Santana, R. J. Nielsen, W. A. Goddard and H. Mishra, Chem. Sci., 2019, 10, 2566 DOI: 10.1039/C8SC05538F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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