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Related Concept Videos

Mass Spectrometry: Overview01:19

Mass Spectrometry: Overview

Mass spectrometry is an analytical technique used to determine the molecular mass and molecular formula of a compound. The basic principle of mass spectrometry is to generate ions from the analyte molecule and measure these ion abundances against their molecular mass. One common type of ionization, known as electron ionization or EI, bombards the analyte molecules in the gas phase with high-energy electron beams. The electron beams displace an electron from the molecule and leave behind a...
Mass Spectrum: Interpretation01:24

Mass Spectrum: Interpretation

An unknown compound can be established by identifying the molecular ion peak in the mass spectrum. The molecular ion peak is often weak or absent due to the predominance of fragmentation in high-energy electron beams. In such cases, a soft-energy electron beam can be used to scan the spectrum to enhance the intensity of the molecular ion peak. Additionally, chemical ionization, field ionization, and desorption ionization spectra are used to obtain a relatively intense molecular ion peak.To...
Mass Spectrometry: Molecular Fragmentation Overview01:20

Mass Spectrometry: Molecular Fragmentation Overview

The ionization of a molecule into a molecular ion inside the mass spectrometer causes instability in the molecule's structure due to the loss of an electron. This eventually leads to the fragmentation or breaking of some bonds in the molecule. The fragmentation occurs predominantly at specific bonds to yield relatively stable fragments.
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
Mass Spectrometers01:16

Mass Spectrometers

This lesson details the instrumentation of a mass spectrometer—a physical instrument to perform mass spectrometry on analyte molecules and record the characteristic mass spectra. This is achieved via three chief functions:
Mass Spectrometry: Amine Fragmentation00:55

Mass Spectrometry: Amine Fragmentation

Amines can be identified using mass spectroscopy based on their characteristic fragmentation patterns. The molecular ions of amines undergo fragmentation via ⍺-cleavage. The ⍺-cleavage of the carbon-carbon bonds in amines generates an alkyl radical and resonance-stabilized nitrogen-containing cation.
In amines, the number of nitrogen atoms affects the mass of the molecular ion, which is described by the nitrogen rule of mass spectrometry. This rule states that a compound containing a single or...
Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation01:01

Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation

The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include ⍺-cleavage and McLafferty rearrangement. Fragmentation by ⍺-cleavage preferentially occurs at the carbon-carbon bond at the ⍺-position next to the carboxylic group to generate a neutral radical and a cation. Long chain compounds with hydrogen at their γ-carbon undergo McLafferty rearrangement to give a radical cation and a neutral alkene.
For example, the fragmentation of...

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Using a Cyclic Ion Mobility Spectrometer for Tandem Ion Mobility Experiments
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Molecular Framework Modification in Mass Spectrometry: Atom Exchange, Insertion, and Deletion.

Myles Q Edwards1, Dylan T Holden2, R Graham Cooks1

  • 1Tarpo Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907, United States.

Journal of the American Society for Mass Spectrometry
|June 26, 2026
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Summary

Electrospray ionization mass spectrometry (ESI-MS) can induce molecular skeletal rearrangements, including atom exchange and insertion, within ring systems. This reactivity expands possibilities for mass spectrometry derivatization and late-stage functionalization.

Keywords:
ambient ionizationelectrospray ionizationmicrodroplet reactionsreactive ionizationskeletal rearrangementstandem mass spectrometry

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Area of Science:

  • Analytical Chemistry
  • Organic Chemistry
  • Mass Spectrometry

Background:

  • Mass spectrometry (MS) is known to induce molecular rearrangements in gas-phase ions.
  • Electrospray ionization (ESI) is a common ionization technique used in MS.
  • Skeletal rearrangements involve changes in the carbon framework of molecules.

Purpose of the Study:

  • To explore skeletal rearrangements occurring during the electrospray ionization (ESI) process.
  • To investigate atom exchange, insertion, and deletion reactions within ring systems.
  • To demonstrate the intrinsic reactivity of ESI-MS for molecular transformations.

Main Methods:

  • Electrospray ionization mass spectrometry (ESI-MS).
  • MSn and high-resolution MS (HRMS) for detailed analysis.
  • Exact-mass measurements and isotopic distribution analysis for product identification.
  • MS/MS fragmentation analysis and comparison with authentic standards.

Main Results:

  • Observed skeletal rearrangements including atom exchange, insertion, and deletion in pre-existing ring systems.
  • Demonstrated ESI-MS reactivity through reactions like Baeyer-Villiger oxidation, Beckmann rearrangement, Favorskii rearrangement, and a novel sulfur-for-oxygen exchange.
  • Confirmed product identities using HRMS, isotopic patterns, and MS/MS fragmentation.

Conclusions:

  • ESI-MS is an intrinsically reactive technique capable of inducing significant molecular framework modifications.
  • These findings expand the scope of reactive MS derivatization.
  • The study opens avenues for novel strategies in late-stage functionalization of molecules.