Manipulating Non-Dissociative Transformations of Gaseous Ion Ensembles Prior to Ion-Mobility Separation.
J Am Soc Mass Spectrom
; 35(6): 1197-1207, 2024 Jun 05.
Article
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| MEDLINE
| ID: mdl-38718179
ABSTRACT
Molecules with multiple sites capable of accepting protons form ensembles of protomers. The manifested protomer ratios in such ensembles are influenced by many experimental conditions. In a Synapt G2 ion mobility (IM)-enabled mass spectrometry system, there are several physical locations where ion population changes can be manifested. Using APCI-generated protomers of aminonaphthalenes, we investigated its intramolecular proton transfers from the N-protomer to the C-protomer. This lossless transformation of the N-protomer to the thermodynamically favored C-protomer can take place in the ion source itself. Initially, we learned that the cone gas slows down the transformation to the C-protomer. Gaseous ions are then accelerated in the first vacuum region, where ions undergo collisional activation (heating), which facilitates the transformation to the C-protomer. Afterward, the ions are mass selected and transferred to the pre-IM (Trap)-collision cell, where ions can also be transformed to the thermodynamically favored protomers. Trap accumulated ions are then released to the IM separator via a helium-filled entry cell. The role of helium is to minimize ion activation and scattering taking place upon entry to the high-pressure T-Wave IM separator (TWIMS). The helium cell is known to increase the IM peak resolution. However, we found that significant changes occur depending on the presence or absence of helium. Without helium, source-generated protomers rapidly changed to a predominantly thermodynamically favorable ensemble protomers. Apparently, the introduction of helium into the precell induced a dramatic decrease in collisional "heating" effect, which effectively slowed down the conversion rate of the amino-protomer into the more favorable ring-protomer. The final message is that mobilograms should not be considered as direct real-time, or intrinsic, representations of the protomer ratios in the ion source.
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01-internacional
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MEDLINE
Idioma:
En
Revista:
J Am Soc Mass Spectrom
Año:
2024
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Estados Unidos