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Anal Chim Acta. 2019 Oct 10;1075:120-127. doi: 10.1016/j.aca.2019.05.055. Epub 2019 May 25.

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

Author information

1
Department of Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China (USTC), Hefei, 230026, China.
2
State Key Laboratory of Particle Detection and Electronics, University of Science and Technology of China (USTC), Hefei, 230026, China; Department of Modern Physics, University of Science and Technology of China (USTC), Hefei, 230026, China.
3
Department of Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China (USTC), Hefei, 230026, China; National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, 230026, PR China. Electronic address: gmhuang@ustc.edu.cn.

Abstract

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 μM and 0.0218-0.3634 μM 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.

KEYWORDS:

Epoxidation; Fatty acid C=C positional isomers; In situ analysis; Negative-ion paper spray

PMID:
31196417
DOI:
10.1016/j.aca.2019.05.055

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