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Electrospray ionisation (revision 4)

Old revision·11:52, 2 Oct 2024·TechnicianTeal

This is an old revision of this page, as it stood at 11:52, 2 Oct 2024, saved by TechnicianTeal with the summary correct the integration description — valley-to-valley, not drop-line. It may differ substantially from the current revision, and any error it contains may since have been corrected.
Electrospray ionisation
AbbreviationESI
ProducesMultiply charged ions from solution
NatureSoft; molecule survives intact
Compatible withLiquid chromatography
Analytical method infobox · conventions

Electrospray ionisation transfers molecules from solution into the gas phase as ions. A solution is sprayed from a capillary held at high potential, producing charged droplets whose solvent evaporates until ions are released.[1]

It is a soft technique — the molecule survives largely intact — and it produces multiply charged ions from peptides and proteins, so a large molecule appears at a mass-to-charge ratio within the range of ordinary analysers. A single peptide therefore produces a series of peaks at successive charge states, deconvolved by software into one neutral mass.[2]

Mechanism

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The applied potential draws the liquid into a cone from whose tip a fine spray of charged droplets emerges. Solvent evaporates, the droplets shrink until charge repulsion exceeds surface tension, and they divide. Ions are ultimately released either by field-driven ejection from very small droplets or by complete evaporation of the solvent around them.[1]

The charge states observed depend on the number of ionisable sites and on solution conditions. Acidic mobile phases favour protonation and positive-mode operation, which is why peptide LC-MS is usually run in positive mode with an acidic modifier.[2]

References

  1. ^ a b Fenn JB, Mann M, Meng CK, Wong SF, Whitehouse CM. "Electrospray ionization for mass spectrometry of large biomolecules." Science 246(4926):64–71 (1989). PMID 2675315.
  2. ^ a b Aebersold R, Mann M. "Mass spectrometry-based proteomics." Nature 422(6928):198–207 (2003). PMID 12634793.