Collision-Induced Dissociation of Hydrated Ion Complexes
Summary
The process of collision-induced dissociation (CID) of hydrated ion complexes has become a cornerstone technique in mass spectrometry for elucidating the structure, stability and dynamics of microsolvated ions in the gas phase. By subjecting mass-selected hydrated ions to energetic collisions with inert gas molecules, controlled fragmentation of the solvation shell occurs, typically via stepwise loss of water ligands. The resulting fragmentation patterns yield quantitative measures of sequential binding enthalpies, reveal coordination geometries and provide insight into non-covalent interactions between ions and water molecules. Advances in tandem mass spectrometry instrumentation—most notably high-resolution ion cyclotron resonance and orbitrap platforms—have enabled precise determination of dissociation thresholds and mapping of water-loss pathways across a wide range of cluster sizes and charge states. These experiments are complemented by theoretical frameworks such as molecular dynamics simulations and density functional theory calculations, which rationalise observed energetics and geometries. Understanding CID of hydrated ions holds global significance, informing models of atmospheric aerosol formation, guiding the optimisation of electrospray desolvation protocols and offering benchmarks for force-field development in biomolecular mass spectrometry. Concrete examples include the delineation of shell-closure effects in alkali metal hydrates and the characterisation of charge-induced structural rearrangements in multivalent microdroplets.
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Collision-Induced Dissociation of Hydrated Ion Complexes publication trend
The graph below shows the total number of articles in collision-induced dissociation of hydrated ion complexes across all publications each year (not limited to Nature Index journals).
Technical terms
Collision-induced dissociation (CID): fragmentation of gas-phase ions by energetic collisions with neutral gas molecules, leading to bond cleavage or loss of ligands.
Hydrated ion complex: a gas-phase cluster comprising an ion non-covalently bound to one or more water molecules.
Microsolvation: the study of solvation effects at the level of individual solvent molecules surrounding an ion or molecule.
Sequential binding enthalpy: the energy change associated with the stepwise removal of a single solvent molecule from a microsolvated cluster.
Tandem mass spectrometry: a multi-stage mass analysis technique in which precursor ions are selected, fragmented, and the resulting product ions analysed to reveal structural information.
References
- Sequential water molecule binding enthalpies for aqueous nanodrops containing a mono-, di- or trivalent ion and between 20 and 500 water molecules. Chemical Science (2017).
- Coordination structure and charge transfer in microsolvated transition metal hydroxide clusters [MOH] + (H 2 O) 1–4. Physical Chemistry Chemical Physics (2015).
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