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Issue 8, 2011
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Blurring the line between solution and the gas phase: collision-induced dissociation of hypersolvated lanthanide trications provides insights into solution acidity

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Abstract

Lanthanide ions provide a classic example of the distortion of speciation that sometimes occurs during the electrospray ionization (ESI) process. Under normal conditions, M3+ ions are not observed as such from aqueous solution; rather, they appear as charge-reduced species such as [M(OH)]2+ or even [MO]+ ions. However, source conditions can be tuned to a “cold-flooding” mode such that [M(H2O)n]3+ ions can be readily obtained, thus providing spectra that are much more representative of the solution speciation. Examination of heavily hydrated trications by MS/MS enables the step-by-step progression of a small droplet to a solvated ion and eventually to a solvent-free ion to be examined in detail, and the point at which charge reduction occurs can be established. We find a strong correlation between the solution acidity of each lanthanide ion and the number of water molecules at which charge reduction occurs under MS/MS conditions. Examination of previously published data on a range of dications supports this conclusion. So not only can ESI-MS provide an accurate picture of the solution speciation, it can also provide insights into chemical behavior in solution.

Graphical abstract: Blurring the line between solution and the gas phase: collision-induced dissociation of hypersolvated lanthanide trications provides insights into solution acidity

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Article information


Submitted
10 Feb 2011
Accepted
24 Mar 2011
First published
18 Apr 2011

New J. Chem., 2011,35, 1582-1587
Article type
Paper

Blurring the line between solution and the gas phase: collision-induced dissociation of hypersolvated lanthanide trications provides insights into solution acidity

J. Pape, K. McQuinn, F. Hof and J. S. McIndoe, New J. Chem., 2011, 35, 1582
DOI: 10.1039/C1NJ20105K

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