Details
| Original language | English |
|---|---|
| Pages (from-to) | 773-784 |
| Number of pages | 12 |
| Journal | Journal of the American Society for Mass Spectrometry |
| Volume | 31 |
| Issue number | 4 |
| Publication status | Published - 21 Feb 2020 |
| Externally published | Yes |
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 modifier to a certain extent (accommodation). Depending on the modifier's properties either charge depletion or retention may eventually be promoted.
Keywords
- charge retention, chemical modifier, cluster chemistry, delayed evaporation, ESI, ion-solvent interactions, nanoelectrospray, Substance P, supercharging
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Structural Biology
- Chemistry(all)
- Spectroscopy
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In: Journal of the American Society for Mass Spectrometry, Vol. 31, No. 4, 21.02.2020, p. 773-784.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Charge Retention/Charge Depletion in ESI-MS
T2 - Experimental Evidence
AU - Thinius, Marco
AU - Polaczek, Christine
AU - Langner, Markus
AU - Bräkling, Steffen
AU - Haack, Alexander
AU - Kersten, Hendrik
AU - Benter, Thorsten
PY - 2020/2/21
Y1 - 2020/2/21
N2 - 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 modifier to a certain extent (accommodation). Depending on the modifier's properties either charge depletion or retention may eventually be promoted.
AB - 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 modifier to a certain extent (accommodation). Depending on the modifier's properties either charge depletion or retention may eventually be promoted.
KW - charge retention
KW - chemical modifier
KW - cluster chemistry
KW - delayed evaporation
KW - ESI
KW - ion-solvent interactions
KW - nanoelectrospray
KW - Substance P
KW - supercharging
UR - http://www.scopus.com/inward/record.url?scp=85082780334&partnerID=8YFLogxK
U2 - 10.1021/jasms.9b00044
DO - 10.1021/jasms.9b00044
M3 - Article
C2 - 32150403
AN - SCOPUS:85082780334
VL - 31
SP - 773
EP - 784
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 4
ER -