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Related Concept Videos

Mass Spectrometry: Aromatic Compound Fragmentation01:23

Mass Spectrometry: Aromatic Compound Fragmentation

2.5K
Upon ionization, aromatic compounds generate a molecular ion that is observed as a prominent peak in their mass spectra. For example, the molecular ion peak for benzene appears at a mass-to-charge ratio of 78, while toluene is observed at a mass-to-charge ratio of 92. The molecular ion benzene is highly stable and does not readily undergo further fragmentation due to the significant amount of energy required to disrupt the aromatic stability of the benzene ring. In contrast, the molecular ion...
2.5K
Mass Spectrometry: Alkene Fragmentation00:59

Mass Spectrometry: Alkene Fragmentation

3.6K
Alkenes lose one electron from the unsaturated π bond upon ionization and form stable molecular ions. Further fragmentation of alkenes occurs through three different reaction pathways. The most prominent fragmentation is the cleavage at the allylic position. The resultant allylic carbocation is resonance stabilized. In the mass spectra of terminal alkenes, this fragment appears at a mass-to-charge ratio of 41. In the internal alkenes, where there are two choices of allylic cleavage, the...
3.6K
Mass Spectrometry: Amine Fragmentation00:55

Mass Spectrometry: Amine Fragmentation

2.3K
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...
2.3K
Mass Spectrometry: Cycloalkane Fragmentation01:05

Mass Spectrometry: Cycloalkane Fragmentation

2.2K
In mass spectrometry, cycloalkanes exhibit distinct fragmentation patterns due to the inherent stability of their molecular ions compared to linear or branched alkanes. The ring structure of cycloalkanes provides additional stability to the molecular ions, often resulting in prominent ion peaks in the mass spectrum.
For example, cyclohexane molecular ions have a mass-to-charge ratio (m/z) of 84, which tends to produce a stronger signal than linear alkanes like hexane. This stability comes from...
2.2K
Mass Spectrometry: Cycloalkene Fragmentation00:54

Mass Spectrometry: Cycloalkene Fragmentation

1.6K
The molecular ions of cycloalkenes undergo fragmentation via a retro-Diels–Alder reaction.
1.6K
Mass Spectrometry: Alkyne Fragmentation00:53

Mass Spectrometry: Alkyne Fragmentation

2.2K
The fragmentation of alkynes preferentially occurs at the carbon–carbon bond between the α and β carbon of the alkyne bond to generate a 3-propynyl cation (or propargyl cation). In terminal alkynes, there is the only type of fragmentation that yields the 3-propynyl cation. The unsubstituted 3-propynyl cation exhibits a peak at a mass-to-charge ratio of 39. In internal alkynes, the 3-propynyl cation is substituted. For example, 2-pentyne fragments into methyl-substituted 3-propynyl cation,...
2.2K

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Standardized Identification of Compound Structure in Tibetan Medicine Using Ion Trap Mass Spectrometry and Multiple-Stage Fragmentation Analysis
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Fragmentation Resilience Energy Mass Spectrometry (FREMS): Methods Validation and Compound Differentiation.

Alexander Yevdokimov1, Kevin Colizza2, James L Smith1

  • 1Department of Chemistry, University of Rhode Island, Kingston, RI 02881, USA.

Molecules (Basel, Switzerland)
|January 28, 2026
PubMed
Summary
This summary is machine-generated.

Fragmentation Resilience Energy Mass Spectrometry (FREMS) offers enhanced resolution for compound identification and structural analysis. This energy-resolved mass spectrometry technique provides reliable differentiation of molecules by analyzing ion breakdown energies.

Keywords:
2D-MS3D-MSFREMSFragmentation Resiliency (FR)MS/MSOrbitrapSurvival Yield (SY)compound discriminationcross-intersectenergy calibrationenergy resolved mass spectrometry (ERMS)glutathionelinear ion trap (LT)mass spectrometry (MS)structural elucidationthermometer ion

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Quantitative Metabolomics of Saccharomyces Cerevisiae Using Liquid Chromatography Coupled with Tandem Mass Spectrometry
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Area of Science:

  • Analytical Chemistry
  • Physical Chemistry

Background:

  • Energy-resolved mass spectrometry methods like Survival Yield are established techniques.
  • Existing methods provide foundational understanding for advanced approaches.

Purpose of the Study:

  • To introduce Fragmentation Resilience Energy Mass Spectrometry (FREMS) as a novel technique.
  • To enhance compound differentiation, contaminant identification, and structural elucidation.
  • To establish a reliable and high-resolution method for analyzing ion breakdown energies.

Main Methods:

  • Acquiring ion breakdown/formation curves with incrementally increased collision energy.
  • Utilizing near "continuous" ramp (0.2% NCE increments) for detailed energy analysis.
  • Analyzing breakdown curves to derive the Fragmentation Resilience (FR50) metric.

Main Results:

  • FREMS provides experimentally interchangeable metrics with modified-Survival Yield (m-SY50) and Cross-Intersect (C-I).
  • Breakdown energies are dependent on ion trap parameters: number of ions, Maximum Inject time, and Activation Time.
  • A linear relationship (R2 > 0.95) was observed between FR50, m-SY50, C-I metrics and controllable parameters, enabling reliable calibration.

Conclusions:

  • FREMS is applicable to ions from any atmospheric pressure ionization process.
  • The technique allows for in vacuo experimental treatment of ions.
  • FREMS demonstrates that precursor ion decomposition rate equals fragment formation rate under CAD conditions.