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Related Concept Videos

Electrospray Ionization (ESI) Mass Spectrometry01:12

Electrospray Ionization (ESI) Mass Spectrometry

Higher molecular weight biomolecules are nonvolatile compounds that may decompose before ionizing or vaporizing during mass analysis with conventional electron impact ionization methods. Accordingly, electrospray ionization (ESI) is the favored method for vaporizing and ionizing biomolecules as it circumvents rapid fragmentation and enables the recording of mass signals for the entire biomolecule.
ESI utilizes electrical energy to transfer ions from the liquid phase of the sample into the...
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 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...
Peptide Identification Using Tandem Mass Spectrometry01:33

Peptide Identification Using Tandem Mass Spectrometry

Tandem mass spectrometry, also known as MS/MS or MS2, is an analytical technique that employs two mass analyzers. Essentially it is a series of mass spectrometers that helps isolate a particular biomolecule and then helps study its chemical properties.
This technique helps gather information regarding the protein from which the peptide was obtained and to study the peptides’ amino acid sequence. Identifying peptides from a complex mixture is an important component of the growing field of...
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 of Amines01:15

Mass Spectrometry of Amines

In mass spectroscopy, amines undergo fragmentation to give parent ions with odd molecule weights. This observed mass spectrum follows the nitrogen rule; a molecule with an odd number of nitrogen atoms produces a molecular ion with an odd molecular weight. Amines undergo fragmentation through α cleavage, producing nitrogen-containing cations—iminium ions—and alkyl radicals. Mass spectra of aromatic and cyclic aliphatic amines exhibit strong molecular ion peaks, but acyclic aliphatic amines show...

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Updated: Jun 11, 2026

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids
11:44

Synthesis and Mass Spectrometry Analysis of Oligo-peptoids

Published on: February 21, 2018

Peptide fragmentation during nanoelectrospray ionization.

He Wang1, Zheng Ouyang, Yu Xia

  • 1Weldon School of Biomedical Engineering, Purdue University, West Lafayette, Indiana 47907-2032, USA.

Analytical Chemistry
|July 9, 2010
PubMed
Summary
This summary is machine-generated.

Intensive peptide ion fragmentation during nanoelectrospray (nanoESI) is linked to high solution conductivity and low flow rates. This process generates fragment ions while preserving phosphorylation, offering new analytical possibilities.

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Area of Science:

  • Analytical Chemistry
  • Mass Spectrometry
  • Biochemistry

Background:

  • Electrospray ionization (ESI) is typically a soft ionization technique with minimal peptide fragmentation.
  • Unusual, intensive peptide fragmentation has been observed in nanoESI under specific conditions, like high salt concentrations.

Purpose of the Study:

  • To systematically characterize peptide fragmentation during nanoESI.
  • To identify key parameters influencing this fragmentation phenomenon.
  • To propose a mechanism for the observed fragmentation.

Main Methods:

  • Systematic characterization of peptide fragmentation in nanoESI.
  • Analysis of various peptides (MW < 3000 Da) and phosphorylated peptides.
  • Investigation of solution electrical conductivity and flow rate effects.

Main Results:

  • Peptide fragmentation yielding a, b, and y ions was observed.
  • Phosphorylated peptides showed minimal loss of phosphate groups.
  • High solution conductivity (0.4 S/m) and low flow rate (2 nL/min) were key factors.

Conclusions:

  • NanoESI of conductive solutions at low flow rates can induce significant peptide fragmentation.
  • Formation of highly charged, fine droplets with high surface electric fields is proposed.
  • Solvation of peptide ions and phosphate groups influences fragmentation and phosphorylation preservation.