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Mass spectrometry (revision 5)

Old revision·15:52, 23 Jul 2024·DiluentDiya

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Mass spectrometry
MeasuresMass-to-charge ratio of ions
Usual ionisation for peptidesElectrospray
AnswersWhat the molecule is; not how much unless calibrated
Analytical method infobox · conventions

Mass spectrometry measures the mass-to-charge ratio of ionised molecules. For peptides it is the ordinary means of confirming identity: an observed molecular mass agreeing with the calculated mass excludes most alternatives, and fragmentation can confirm the sequence itself.[1]

A purity determination by chromatography establishes that one species dominates a sample; it does not establish which species. These are separate questions and require separate determinations. A certificate reporting purity but no identity leaves the more fundamental of the two unanswered.[2]

Ionisation and mass analysis

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Electrospray disperses a solution into charged droplets in an electric field; solvent evaporates and ions are released into the gas phase. It is a soft technique — the molecule survives largely intact — which is why it suits peptides and proteins. Matrix-assisted laser desorption is the other common soft method and tends to produce singly charged ions.[1]

Mass analysers differ in resolution and in mass accuracy. A quadrupole gives unit resolution and is adequate for confirming a mass to within a dalton; time-of-flight and orbital-trap analysers give sufficient resolution to determine a mass to a few parts per million, which distinguishes species a quadrupole cannot.

References

  1. ^ a b Aebersold R, Mann M. "Mass spectrometry-based proteomics." Nature 422(6928):198–207 (2003). DOI:10.1038/nature01511. PMID 12634793.
  2. ^ United States Pharmacopeia, General Chapter <1503>, Quality Attributes of Synthetic Peptide Drug Substances.