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Chemical Ionization (CI) Mass Spectrometry01:21

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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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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...
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Updated: Feb 7, 2026

Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry
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Insulator Nanostructure Desorption Ionization Mass Spectrometry.

Todd A Duncombe1,2, Markus De Raad3, Benjamin P Bowen4,3

  • 1DOE Joint BioEnergy Institute , 5885 Hollis Street , Emeryville , California 94608 , United States.

Analytical Chemistry
|August 1, 2018
PubMed
Summary

We developed insulator nanostructure desorption ionization mass spectrometry (INDI-MS), a novel polymer substrate for laser desorption mass spectrometry. This method achieves attomole-femtomole sensitivity for analyzing small molecules and peptides.

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Area of Science:

  • Analytical Chemistry
  • Materials Science
  • Mass Spectrometry

Background:

  • Surface-assisted laser desorption ionization (SALDI) typically requires conductive or semiconductive nanostructures for gas-phase ion generation.
  • A need exists for versatile SALDI substrates compatible with diverse analytes and analytical workflows.

Purpose of the Study:

  • To introduce insulator nanostructure desorption ionization mass spectrometry (INDI-MS) as a novel SALDI substrate.
  • To characterize the performance and fabrication of INDI-MS surfaces for small molecule and peptide analysis.
  • To demonstrate the potential for integrated sample preparation on INDI-MS platforms.

Main Methods:

  • Fabrication of nanostructured polymer surfaces using self-assembly of perfluoroalkyl silsesquioxane via chemical vapor deposition.
  • Characterization of nanostructure morphology (height, diameter) using microscopy.
  • Evaluation of analyte sensitivity (attomole-femtomole) for small molecules and peptides.
  • Demonstration of on-chip self-desalting using micropatterned hydrophobic/hydrophilic surfaces.

Main Results:

  • Perfluorooctyltrichlorosilane monomer self-assembly yielded semielliptical nanostructures (10 nm height, 10-50 nm diameter).
  • INDI-MS surfaces exhibited attomole-femtomole sensitivity for targeted analytes.
  • Substrates lacking specific functional groups (trichloro or perfluoro) showed reduced sensitivity.
  • Successful micropatterning enabled on-chip self-desalting in an array format.

Conclusions:

  • INDI-MS offers a sensitive and versatile platform for SALDI mass spectrometry using nanostructured polymer insulators.
  • The fabrication method is adaptable, allowing for tailored surface properties and integrated functionalities like self-desalting.
  • INDI-MS represents a significant advancement in substrate design for mass spectrometry applications.