[en] Ion mobility–mass spectrometry (IM-MS) experiments are mostly used hand in hand with computational chemistry to correlate mobility measurements to the shape of the ions. Recently, we developed an automatable method to fit IM data obtained with synthetic homopolymers (i.e., collision cross sections; CCS) without resorting to computational chemistry. Here, we further develop the experimental IM data interpretation to explore physicochemical properties of a series of nine polymers and their monomer units by monitoring the relationship between the CCS and the degree of polymerization (DP). Several remarkable points of the CCS evolutions as a function of the DP were found: the first observed DP of each charge state (ΔDPfirst DP), the DPs constituting the structural rearrangements (ΔDPrearr), and the DPs at the half-rearrangement (DPhalf-rearr). Given that these remarkable points do not rely on absolute CCS values, but on their relative evolution, they can be extracted from CCS or raw IM data without accurate IM calibration. Properties such as coordination numbers of the cations, steric hindrance, or side chain flexibility can be compared. This leads to fit parameter predictions based on the nature of the monomer unit. The interpretation of the fit parameters, extracted using solely experimental data, allows a rapid screening of the properties of the polymers.
Disciplines :
Chemistry
Author, co-author :
Haler, Jean ; Université de Liège - ULiège + LIST-Luxembourg > Département de chimie (sciences) + LIST Materials Research and Technology Department > Chimie analytique inorganique
Far, Johann ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie analytique inorganique
de la Rosa, Victor; Ghent University > Department of Organic and Macromolecular Chemistry > Supramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC)
Kune, Christopher ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de spectrométrie de masse (L.S.M.)
Hoogenboom, Richard; Ghent University > Department of Organic and Macromolecular Chemistry > Supramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC)
De Pauw, Edwin ; Université de Liège - ULiège > Département de chimie (sciences) > Chimie analytique inorganique
Language :
English
Title :
Using Ion Mobility-Mass Spectrometry to Extract Physicochemical Enthalpic and Entropic Contributions from Synthetic Polymers
Publication date :
2021
Journal title :
Journal of the American Society for Mass Spectrometry
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