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Related Concept Videos

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...
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael acceptor.
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...
Ion Exchange01:17

Ion Exchange

Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or basic...
Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...

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Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications
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Fragmentation pathways of polymer ions.

Chrys Wesdemiotis1, Nilüfer Solak, Michael J Polce

  • 1Department of Chemistry, The University of Akron, OH 44325-3601, USA. wesdemiotis@uakron.edu

Mass Spectrometry Reviews
|July 13, 2010
PubMed
Summary

Understanding polymer ion fragmentation in tandem mass spectrometry (MS/MS) is key for structural analysis. This review details fragmentation pathways, predominantly charge-remote processes, crucial for polymer characterization.

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Synthesis and Mass Spectrometry Analysis of Oligo-peptoids
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Area of Science:

  • Polymer Chemistry
  • Analytical Chemistry
  • Mass Spectrometry

Background:

  • Tandem mass spectrometry (MS/MS) is vital for characterizing synthetic polymers.
  • Understanding polymer ion fragmentation mechanisms is essential for accurate structural assignments.
  • Collisionally activated dissociation (CAD) is the primary activation method in polymer MS/MS.

Purpose of the Study:

  • To review fragmentation pathways of synthetic polymer ions subjected to CAD.
  • To provide guidelines for deducing polymer structure from MS/MS spectra.
  • To discuss factors influencing fragmentation, including ionization agent and internal energy.

Main Methods:

  • Review of existing literature on polymer ion fragmentation.
  • Analysis of fragmentation pathways for various synthetic polymers (polystyrenes, polyethers, polyesters, etc.).
  • Categorization of fragmentation pathways into charge-directed and charge-remote processes.

Main Results:

  • Identified three main fragmentation pathway categories: charge-directed, charge-remote rearrangements, and charge-remote fragmentations via radical intermediates.
  • Charge-remote processes were found to predominate in synthetic polymer ion fragmentation.
  • Observed formation of ion-molecule complexes enabling inter-fragment transfers.

Conclusions:

  • Fragmentation mechanisms are critical for interpreting MS/MS data of synthetic polymers.
  • Charge-remote pathways are dominant, offering significant structural insights.
  • Further understanding of fragmentation aids in detailed polymer architecture and substituent characterization.