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Updated: Nov 5, 2025

Using a Cyclic Ion Mobility Spectrometer for Tandem Ion Mobility Experiments
Published on: January 20, 2022
Probing Polyester Branching by Hybrid Trapped Ion-Mobility Spectrometry-Tandem Mass Spectrometry.
Robert L C Voeten1,2,3, Bram van de Put2,3, Jan Jordens4
1Division of BioAnalytical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMMS), Vrije Universiteit Amsterdam, de Boelelaan 1085, 1081 HV Amsterdam, The Netherlands.
Trapped ion-mobility spectrometry combined with quadrupole time-of-flight mass spectrometry (TIMS-QTOFMS) effectively distinguishes linear and branched polyester isomers. This method provides rapid analysis of isomeric polyester oligomers up to 3000 Da, offering valuable structural insights.
Area of Science:
- Analytical Chemistry
- Polymer Chemistry
- Physical Chemistry
Background:
- Distinguishing between linear and branched isomeric polyester oligomers is crucial for understanding their properties.
- Traditional methods for isomer separation can be time-consuming and complex.
Purpose of the Study:
- To evaluate trapped ion-mobility spectrometry combined with quadrupole time-of-flight mass spectrometry (TIMS-QTOFMS) for resolving linear and branched polyester isomers.
- To assess the speed and reliability of TIMS-QTOFMS for analyzing polyester oligomers.
Main Methods:
- Direct infusion electrospray ionization (ESI) of polyester samples into TIMS-QTOFMS.
- Utilizing extracted-ion mobilograms (EIMs) to analyze mobility and m/z data.
- Employing TIMS-MS/MS and liquid chromatography-TIMS-MS/MS for detailed structural analysis.
- Applying molecular supercharging with m-nitrobenzyl alcohol (NBA) for larger oligomers.
- Implementing post-TIMS analyte-decharging to simplify fragmentation spectra.
Main Results:
- TIMS-MS successfully resolved linear and branched polyester oligomers based on multimodal EIM patterns and mobility differences.
- Direct TIMS-MS achieved rapid distinction (500 ms/scan) between small linear and branched oligomers.
- Molecular supercharging enabled analysis of larger oligomers (up to 3000 Da), enhancing separation but increasing spectral complexity.
- Distinction between linear and branched oligomers was possible by analyzing collisional cross sections (CCSs).
Conclusions:
- TIMS-QTOFMS is a reliable and rapid analytical approach for obtaining branching information on isomeric polyester molecules up to 3000 Da.
- The method offers a significant reduction in analysis time (less than 1 min) compared to conventional techniques.
- TIMS-QTOFMS provides valuable insights into the conformational differences and structural variations of polyester oligomers.
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