Charge Retention/Charge Depletion in ESI-MS: Experimental Evidence.

Journal of the American Society for Mass Spectrometry
Marco ThiniusThorsten Benter

Abstract

The effects of liquid and gas phase additives (chemical modifiers) on the ion signal distribution for Substance P (SP), recorded with a nanoelectrospray setup, are evaluated. Depletion of the higher charge state of Substance P ([SP+3H]3+) is observed with polar protic gas phase modifiers. This is attributed to their ability to form larger hydrogen-bonded clusters, whose proton affinity increases with cluster size. These clusters are able to deprotonate the higher charge state. "Supercharging agents" (SCAs) as well as aprotic polar gas phase modifiers, which promote the retention of the higher charge state of Substance P, do not form such large clusters under the given conditions and are therefore not able to deprotonate Substance P. Both SCAs and aprotic modifiers form clusters with the higher charge state, leading to stabilization of the charge. Whereas supercharging agents have low vapor pressures and are therefore enriched in late-stage electrospray droplets, the gas phase modifiers are volatile organic solvents. Collision induced dissociation experiments revealed that the addition of a modifier significantly delays the droplet evaporation and ion release process. This indicates that the droplet takes up the gas phase modifi...Continue Reading

Citations

Mar 3, 2020·Rapid Communications in Mass Spectrometry : RCM·Alexander HaackHendrik Kersten
Dec 19, 2020·Journal of the American Society for Mass Spectrometry·Leanne M Martin, Lars Konermann
Mar 19, 2021·Journal of the American Society for Mass Spectrometry·Christian IeritanoW Scott Hopkins

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