Journal of the American Society for Mass Spectrometry

, Volume 18, Issue 2, pp 285–293

Negative ion mode electrospray ionization mass spectrometry study of ammonium-counter ion clusters


DOI: 10.1016/j.jasms.2006.09.028

Cite this article as:
Lentz, N.B. & Houk, R.S. J Am Soc Mass Spectrom (2007) 18: 285. doi:10.1016/j.jasms.2006.09.028


Electrospray ionization mass spectrometry (ESI-MS) was used to examine clusters of protonated amine salt solutions with chloride counter ions in the negative ion mode. These ions have the general formula [(RNH3)xClx+1]. Primary amines generate a wide cluster distribution with clusters up to 14 mer for methylamine hydrochloride clusters. Secondary and quaternary amines only generate the monomer ion under identical conditions. Collision induced dissociation (CID) of the cluster ions generates cluster ions of lower m/z with the next lower cluster being the most abundant. The product ions from MeNH3Cl2, Me2NH2Cl2 and (MeNH3)2Cl3 have low threshold appearance energies of 1. 24 to 2. 22 eV center-of-mass frame. Secondary amine monomer ions have lower threshold CID energies than primary amine monomer ions. The amine threshold CID energy decreases as the carbon chain length increases. As an electrospray solvent, isopropyl alcohol (IPA) promotes the formation of counter ions and clustering.

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© American Society for Mass Spectrometry 2007

Authors and Affiliations

  1. 1.Ames Laboratory, U.S. Department of Energy, Department of ChemistryIowa State UniversityAmesUSA