Diagnostic gas-phase ion-molecule reactions serve as a powerful alternative to collision-activated dissociation for the structural elucidation of analytes when using tandem mass spectrometry. The use of such ion-molecule reactions has been demonstrated to provide a robust tool for the identification of specific functional groups in unknown ionized analytes, differentiation of isomeric ions, and classification of unknown ions into different compound classes. During the past several years, considerable efforts have been dedicated to exploring various reagents and reagent inlet systems for functional-group selective ion-molecule reactions with protonated analytes. This review provides a comprehensive coverage of literature since 2006 on general and predictable functional-group selective ion-molecule reactions of protonated analytes, including simple monofunctional and complex polyfunctional analytes, whose mechanisms have been explored computationally. Detection limits for experiments involving high-performance liquid chromatography coupled with tandem mass spectrometry based on ion-molecule reactions and the application of machine learning to predict diagnostic ion-molecule reactions are also discussed.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/mas.21727 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Atomistic dynamics of elimination and substitution driven by entrance channel.
J Chem Phys
January 2025
Key Laboratory of Chemistry and Chemical Engineering on Heavy-Carbon Resources, School of Chemistry and Chemical Engineering, Yili Normal University, Yining 835000, People's Republic of China.
E2 elimination and SN2 substitution reactions are of central importance in preparative organic synthesis due to their stereospecificity. Herein, atomistic dynamics of a prototype reaction of ethyl chloride with hydroxide ion are uncovered that show strikingly distinct features from the case with fluoride anion. Chemical dynamics simulations reproduce the experimental reaction rate and reveal that the E2 proceeding through a direct elimination mechanism dominates over SN2 for the hydroxide ion reaction.
View Article and Find Full Text PDFA SIFT Study of Reactions of Positive and Negative Ions With Polyfluoroalkyl (PFAS) Molecules in Dry and Humid Nitrogen at 393 K.
Rapid Commun Mass Spectrom
March 2025
J Heyrovský Institute of Physical Chemistry of the CAS, Prague 8, Czechia.
Rationale: Data are required for SIFT-MS analysis of perfluoroalkyl and polyfluoroalkyl substances (PFAS), which are persistent in the environment and cause adverse health effects. Specifically, the rate coefficients and product ion branching ratios of the reactions of HO, NO, O •, O•, OH, O •, NO and NO with PFAS vapours are needed.
Methods: The dual polarity SIFT-MS instrument (Voice200) was used to generate these eight reagent ions and inject them into the flow tube with N carrier gas at a temperature of 393 K.
Roundabout Mechanism of Ion-Molecule Nucleophilic Substitution Reactions.
ACS Phys Chem Au
November 2024
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
Roundabout (RA) is an important indirect mechanism for gas-phase X + CHY → XCH + Y S2 reactions at a high collision energy. It refers to the rotation of the CH-group by half or multiple circles upon the collision of incoming nucleophiles before substitution takes place. The RA mechanism was first discovered in the Cl + CHI S2 reaction to explain the energy transfer observed in crossed molecular beam imaging experiments in 2008.
View Article and Find Full Text PDFCreation of Gas-Phase Organo-Uranium Species by Removal of "yl" Oxo Ligands From UO Carboxylate Precursor Ions.
Rapid Commun Mass Spectrom
February 2025
Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania, USA.
Rationale: These experiments were conducted to measure the diversity of organo-U (IV) and U (III) ions created using multiple-stage tandem MS and collision-induced dissociation of halogen-substituted UO-phenide complexes [UO(CHFX)], X = Cl, Br, or I.
Methods: Samples of UO(OC-CHFX) were prepared by digesting UO with appropriate halogen-substituted carboxylic acids in deionized water. Solutions for ESI were created by diluting the digested sample in 50:50 HO/CHOH.
Geant4-DNA development for atmospheric applications: N, O and CO models implementation.
Phys Med
December 2024
Physics Dep., Sapienza U. of Rome, p.le Aldo Moro, 2, 00185, Rome, Italy; INFN, Sec. of Rome, p.le Aldo Moro, 2, 00185, Rome, Italy.
Article Synopsis
- * New electron interaction models for nitrogen, oxygen, and carbon dioxide have been validated up to 10 MeV, which is important given carbon dioxide's role as a greenhouse gas.
- * Results show that the models align well with existing literature, confirming their reliability and enabling further research into the effects of ionization on atmospheric chemistry and climate impacts.
Want AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!