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Chloride anion attachment in negative ion electrospray ionization mass spectrometry†

✍ Scribed by Richard B. Cole; Junhua Zhu

Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
67 KB
Volume
13
Category
Article
ISSN
0951-4198

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✦ Synopsis

An approach to enable negative ion electrospray ionization (ESI) mass spectrometric detection of analytes that lack acidic sites and thus exhibit weak [MÀH] À signals has been developed. The method relies upon attachment of Cl À ions present in electrosprayed solutions of chlorinated solvents such as chloroform.

Attachment of these chloride ions to form [MCl] À ions was observed for compounds characterized by pK a values as high as 27 (aniline). Low-energy collision-induced dissociation (CID) mass spectra of the chloride adducts produced [MÀH]

À and Cl À . For analytes that have gas-phase acidities lower than HCl, CID of [MCl] À at higher laboratory energies (e.g., above 20 eV) can dramatically promote initial formation of [MÀH] À , and lead to production of structurally informative daughter ions via consecutive decompositions.

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