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Mass Spectrometry: Molecular Fragmentation Overview01:20

Mass Spectrometry: Molecular Fragmentation Overview

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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...
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Nuclear Fusion

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The process of converting very light nuclei into heavier nuclei is also accompanied by the conversion of mass into large amounts of energy, a process called fusion. The principal source of energy in the sun is a net fusion reaction in which four hydrogen nuclei fuse and ultimately produce one helium nucleus and two positrons.
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Mass Spectrometry: Long-Chain Alkane Fragmentation01:18

Mass Spectrometry: Long-Chain Alkane Fragmentation

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The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond creates a stable carbocation and a stable radical. Consequently, the mass signals of linear alkanes feature intense peaks in the middle of the mass-to-charge ratio plot with weaker peaks on either end. The fragmentation of each carbon-carbon bond with the release of a methyl group in each splitting leads to prominent peaks in the mass spectra...
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Chemical Ionization (CI) Mass Spectrometry01:21

Chemical Ionization (CI) Mass Spectrometry

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The molecular ion peak of a molecule in the mass spectrum provides vital information for molecular identification. However, conventional electron impact ionization can lead to the rapid dissociation of some molecular ions before they reach the detector. A milder ionization method is required to increase the lifetime of such ionized analyte molecules. Chemical ionization (CI) is a gas-phase protonation reaction useful for mass-analyzing analyte molecules that are easily protonated to yield the...
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Carbocations02:10

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Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation01:01

Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation

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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...
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Charge Transfer, Complexes Formation and Furan Fragmentation Induced by Collisions with Low-Energy Helium Cations.

Tomasz J Wasowicz1, Marta Łabuda2, Boguslaw Pranszke3,4

  • 1Department of Physics of Electronic Phenomena, Gdansk University of Technology, ul. G. Narutowicza 11/12, 80-233 Gdansk, Poland.

International Journal of Molecular Sciences
|December 5, 2019
PubMed
Summary

Collisional fragmentation of furan molecules by helium cations (He+ and He2+) was investigated. Two main mechanisms, electron transfer and temporary cluster formation, were identified, influencing fragmentation pathways and product emission spectra.

Keywords:
DNA damagecharge transferfuran fragmentationion-induced collision

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Area of Science:

  • Chemical Physics
  • Atomic and Molecular Collisions
  • Spectroscopy

Background:

  • Furan molecule fragmentation under ion impact is complex.
  • Understanding collisional dynamics is crucial for chemical reaction studies.

Purpose of the Study:

  • To elucidate the collisional processes and fragmentation mechanisms of gas-phase furan molecules impacted by He+ and He2+ cations.
  • To analyze the role of projectile charge and velocity on fragmentation pathways.

Main Methods:

  • Collision-induced emission spectroscopy (CIES) to measure optical fragmentation spectra.
  • Ab initio quantum chemistry calculations to interpret experimental results.
  • Varying projectile kinetic energy (5-2000 eV) and charge states (He+, He2+).

Main Results:

  • Identified excited products through luminescence, including excited helium atoms, indicating charge transfer.
  • Observed significant variations in product emission intensities with projectile charge and velocity.
  • Noted resonance-like maxima in dissociation product cross-sections at lower He+ velocities.

Conclusions:

  • Two primary collisional mechanisms precede furan fragmentation: electron transfer and temporary He-furan cluster formation.
  • These mechanisms explain the observed fragmentation spectra and cross-section variations.
  • The study provides detailed insights into ion-molecule collision dynamics involving furan.