The effects of stearyl and cetyl alcohol on the electrospray mass spectrometry of proteins and their implications on the electrospray mechanism

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Eur. J. Mass Spectrom. 1, 253 - 260 (1995)

The effects of stearyl and cetyl alcohol on the electrospray mass spectrometry of proteins and their implications on the electrospray mechanism

Fu Ke, J.C. Yves Le Blanc, Roger Guevremont and K.W. Michael Siu^*
Institute for Environmental Research and Technology, National Research Council of Canada, Montreal Road, Ottawa, Ontario, Canada K1A 0R6

ABSTRACT:

The presence of a low percentage of a long-chained n alkanol, such as stearyl or cetyl alcohol, in a micrometer-size water droplet is known to retard significantly the droplet's evaporation rate due to formation of a layer of the alcohol on its surface. If solvent evaporation from electrospray-generated droplets played a crucial role in the electrospray mechanism, the presence of a long-chained n-alkanol would interfere with the gas-phase ion formation and cause a drastic decrease in analyte response. As it turned out, the electrospray responses of proteins tested with and without the presence of n-alkanols were comparable. In these experiments, the n-alkanols were added either as solutes in water/methanol solutions of proteins or in hexane solutions delivered coaxially to aqueous protein solutions during their electrospray. These results lend further support to our hypothesis that solvent evaporation is not a necessary prerequisite to ion formation in electrospray, and that ions are formed early rather than late during the electrospray process; the earliest point that this can occur is at the Taylorcone.

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