Predicting Ion Mobility-Mass Spectrometry Trends of Polymers using the Concept of Apparent Densities

[en] Ion Mobility (IM) coupled to Mass Spectrometry (MS) has been used for several decades, bringing a fast separation dimension to the MS detection. IM-MS is a convenient tool for structural elucidation. The fold- ing of macromolecules is often assessed with the support of computational chemistry. However, this strat- egy is strongly dependent on computational initial guesses. Here, we propose the analysis of the Collision Cross-Section (CCS) trends of synthetic homopolymers based on a fitting method which does not rely on computational chemistry a prioris of the three-dimensional structures. The CCS trends were evaluated as a function of the polymer chain length and the charge state. This method is also applicable to mobility trends. It leads to two parameters containing all information available through IM(-MS) measurements. One parameter can be interpreted as an apparent density. The second parameter is related to the shape of the ions and leads us to introduce the concept of trends with constant apparent density. Based on the two fitting parameters, a method for IM trend predictions is elaborated. Experimental deviations from the predictions facilitate detect- ing structural rearrangements and three-dimensional structure differences of the cationized polymer ions. This leads for instance to an easy identification and prediction of the presence of different polymer topologies in complex polymer mixtures. The classification of predicted trends could as well allow for software-assisted data processing. Finally, we suggest the link between the CCS trends of homopolymers and those obtained from (monodisperse) biomolecules to interpret potential folding differences during IM-MS studies.

Research center :

MolSys - Molecular Systems - ULiège
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège
Center for Education and Research on Macromolecules (CERM)

Disciplines :

Chemistry

Author, co-author :

Haler, Jean ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)

Morsa, Denis ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Analytical Research and Technology (CART)

Lecomte, Philippe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)

Jérôme, Christine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM), Center for Education and Research on Macromolecules (CERM)

Far, Johann ; Université de Liège - ULiège > Département de chimie (sciences) > Center for Analytical Research and Technology (CART)

De Pauw, Edwin ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)

Language :

English

Title :

Predicting Ion Mobility-Mass Spectrometry Trends of Polymers using the Concept of Apparent Densities

Publication date :

2018

Journal title :

Methods

ISSN :

1046-2023

eISSN :

1095-9130

Publisher :

Elsevier, Atlanta, United States

Volume :

144

Pages :

125-133

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://www.sciencedirect.com/science/article/pii/S1046202317304656

Funders :

FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE]

Available on ORBi :

since 31 March 2018

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