Characterization of glycerophospholipid isomers is of significant importance as they play different roles in physiological and pathological processes. In this work, we present a novel and bifunctional derivatization method utilizing...
Characterization of nonpolar lipids is of significance, as they serve a variety of key biological functions and can naturally exist in isomeric forms. Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool for most lipid analysis, but nonpolar lipids do not easily ionize in electrospray, complicating their analyses. In this work, we use the Du Bois catalyst (Rh2(esp)2) for aziridina-tion of carbon-carbon double bonds (C=C bond) of six nonpolar sterol lipids, simultaneously increasing ionization efficiency of nonpolar lipids and facilitating C=C bond identification. The incorporation of nitrogen expands the lipid categories detected by MS, and higher-energy C-trap dissociation of the aziridines generates diagnostic ions that can be used to locate C=C bond positions.
Microdroplets have recently emerged as a unique form of a chemical reactor that has gained significant attention due to the interfacial chemistry that produces dramatic reaction acceleration. In this work, we have developed a strategy that allows a thin film to be delivered directly to the interface by electromigration in a theta capillary. Additional acceleration was observed due to reactants being transferred to the interface in electro-oxidative C-H/N-H coupling of phenothiazine with N, N’-dimethylaniline, and short-lived intermediates were captured in the radical radical coupling of DMA. Importantly, we applied the combination of electromigration and interfacial microreactor for in-situ extraction of lipids from small-volume plasma samples and accelerated electro-epoxidation of unsaturated lipids to determine the double bond positional isomers in the small-volume serum. The unique feature of electromigration of thin film to the interface and accelerated interfacial reactions holds great potential in small-volume sample analysis for disease diagnosis and prevention.
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