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Ion mobility–mass spectrometry of supramolecular complexes and assemblies

Nature Reviews Chemistry volume 3, pages 4–14 (2019)Cite this article

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Abstract

Despite their structural and functional differences, synthetic supramolecular assemblies share many similarities with biological assemblies, especially enzymes. The assemblies can be on the same length scale, and their structures and guest binding are typically governed by non-covalent interactions. Thus, only relatively weak interactions define the shape of a synthetic supramolecule or the secondary and tertiary structure of a protein, such that the resulting dynamism makes structure elucidation challenging. For biomolecules such as peptides, proteins, glycans and lipids this has often been tackled using ion mobility–mass spectrometry (IM-MS), whereby analyte ions are separated according to their gas-phase mobility and their mass-to-charge ratio. IM-MS is an established method in omics, separation sciences and small-molecule structural chemistry, but has only recently grown in popularity for the study of synthetic supramolecular assemblies in the gas phase. This Review describes IM-MS techniques and how they can help us understand the structures of molecular self-assemblies, host–guest complexes and metallosupramolecular complexes.

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Fig. 1: Layout of an ion mobility–mass spectrometer and common ion mobility cells.
Fig. 2: Non-covalent interactions between PDF and three bacterial PDF inhibitors monitored by TWIM-MS.
Fig. 3: Endo and exo complexes of organic hosts and guests are distinguishable by ion mobility–mass spectrometry.
Fig. 4: Redox-triggered threading of [1]pseudorotaxane can be observed using ion mobility spectrometry.
Fig. 5: Ion mobility–mass spectrometry can help us to identify complexes with overlapping m/z values and isotopic patterns.
Fig. 6: Transformation of a superchiral metal complex through displacement of the ligands by Cl– ions monitored by DTIM-MS.

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Acknowledgements

The authors thank the Academy of Finland (project numbers 284562 and 312514) and the University of Jyväskylä for financial support.

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  1. Department of Chemistry, University of Jyväskylä, Jyväskylä, Finland

    Elina Kalenius & Kari Rissanen

  2. Department of Nephrology and Hypertension, Department of BioMedical Research, Inselspital, University of Bern, Bern, Switzerland

    Michael Groessl

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Kalenius, E., Groessl, M. & Rissanen, K. Ion mobility–mass spectrometry of supramolecular complexes and assemblies. Nat Rev Chem 3, 4–14 (2019). https://doi.org/10.1038/s41570-018-0062-2

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