In situ analysis of unsaturated fatty acids in human serum by negative-ion paper spray mass spectrometry

In situ identification and quantification of unsaturated fatty acid (FA) C=C positional isomers in human serum is herein performed by negative-ion paper spray (PS) mass spectrometry. Typically, by direct application of an alternating current (AC) voltage to the wet paper, the PS ionization could perform stably in the negative-ion mode without severe discharge. We suppose epoxidation reaction between unsaturated C=C bonds and reactive oxidative species might be initiated by a mild electrical discharge, which could be rapidly and controllably produced via a low amplitude AC voltage. Upon collision-induce dissociation (CID), the epoxide was fragmented to generate diagnostic ions indicating the C=C location. The intensity of the characteristic product ions could also be used for absolute quantification of the FA C=C positional isomers. The limits of detection (LODs) and limits of quantification (LOQs) were roughly in the range of 0.0178–0.0506  μ M and 0.0218–0.3634  μ M for standard FAs. Without the additional sample preparations or reactive chemical reagents , epoxidation of unsaturated FAs and ionization of the epoxide could be achieved in one-step by negative-ion mode PS, which enable a promising methodology for on-site clinical diagnosis.