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  • Title: Sensitivity improvement of amino acids by N-terminal diisopropyloxyphosphorylation in electrospray ionization mass spectrometry.
    Author: Chen Y, Zhang J, Chen J, Cao XY, Wang J, Zhao YF.
    Journal: Rapid Commun Mass Spectrom; 2004; 18(4):469-73. PubMed ID: 14966855.
    Abstract:
    With the introduction of a diisopropyloxyphosphoryl (DIPP) group at the N-terminus of amino acids, the signal response in electrospray ionization mass spectrometry can be enhanced by 10-100-fold in positive mode and even more in negative mode. An enhancement of proton affinity due to the N-terminal DIPP derivatization was considered to be responsible for the sensitivity improvement in positive mode, which was supported by kinetic method studies. Two possible mechanisms, i.e., an increase in gas-phase acidity due to the introduction of the electron-withdrawing DIPP group, and the effect of pH on the formation of anions of amino acids and their phosphorylated derivatives, were considered for the signal response enhancement in negative mode.
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