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

Gallo, Adair, Jr. and Farinha, Andreia S. F. and Dinis, Miguel and Emwas, Abdul-Hamid and Santana, Adriano and Nielsen, Robert J. and Goddard, William A., III and Mishra, Himanshu (2019) The chemical reactions in electrosprays of water do not always correspond to those at the pristine air–water interface. Chemical Science, 10 (9). pp. 2566-2577. ISSN 2041-6520.

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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.

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URLURL TypeDescription Information Paper
Gallo, Adair, Jr.0000-0001-5015-8111
Nielsen, Robert J.0000-0002-7962-0186
Goddard, William A., III0000-0003-0097-5716
Mishra, Himanshu0000-0001-8759-7812
Additional Information:© The Royal Society of Chemistry 2019. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Received 11th December 2018. Accepted 21st December 2018. The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (#OSR-2016-CRG5-2992). The authors thank Mr Ivan Gromicho, Scientific Illustrator at KAUST, for preparing Fig. 1. The authors also thank Professor Richard Saykally and Professor Evan Williams (University of California Berkeley), and Dr Manuel Monge Palacios (KAUST) for fruitful discussions. This research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia. There are no conflicts to declare.
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King Abdullah University of Science and Technology (KAUST)OSR-2016-CRG5-2992
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ID Code:92098
Deposited By: George Porter
Deposited On:05 Jan 2019 00:23
Last Modified:28 Jun 2019 20:00

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