Comparative measurements of multicomponent phospholipid mixtures by electrospray mass spectroscopy: relating ion...

Electrospray mass spectrometry allows direct identification and sensitive detection of multiple phospholipids in non-derivatized cell extracts. However, quantitative analyses are not straightforward, and are confounded by analyte and mass discrimination effects, and non-linear dependence of the ion intensity on concentration. This non-linearity is particularly severe in the negative mode and precludes even comparative measurements of anion concentrations. Herein, we report a general method for relating negative electrospray ion intensity to concentration when analyzing multicomponent phospholipid samples. In this method, the intensity of individual ions is measured at several different concentrations of the total mixture and the slope (n(E)) of the double log plot of sample concentration vs. intensity for each analyte is determined. The n(E) is then used to map intensity data to a quantity proportional to concentration for each analyte. The method allows facile and accurate comparison of negative spectra of complex mixtures containing structurally different anions.