Sweep Jet Collection Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization for Lipid Analysis Applications
Laser-induced acoustic desorption coupled to microplasma-based atmospheric pressure photoionization (LIAD-APPI) using a nebulized sweep jet to aid in dopant introduction and ion transmission has been applied to the analysis of model, apolar lipid compounds. Specifically, several sterols, sterol esters, and triacylglycerols were detected using dopants such as anisole and toluene. Additionally, several triacylglycerols, sterols, carboxylic acids, and hopanoids were detected from complex mixtures of olive oil and Australian shale rock extract as a first demonstration of the applicability of LIAD-APPI on real-world samples. Detection limits using a sweep jet configuration for α-tocopherol and cholesterol were found to be 609 ± 61 and 292 ± 29 fmol, respectively. For sterol esters and triacylglycerols with a large number of double bonds in the fatty acid chain, LIAD-APPI was shown to yield greater molecular ion or [M+NH4]+ abundances than those with saturated fatty acid chains. Dopants such as anisole and toluene, with ionization potentials (IPs) of 8.2 and 8.8 eV, respectively, were tested. A greater degree of fragmentation with several of the more labile test compounds was observed using toluene. Overall, LIAD-APPI with a nebulized sweep jet requires minimal sample preparation and is a generally useful and sensitive analysis technique for low-polarity mixtures of relevance to biochemical assays and geochemical profiling.
KeywordsLaser-induced acoustic desorption Atmospheric pressure photoionization Microplasma Microhollow cathode discharge Olive oil Shale rock Lipids
The authors thank David Deamer and Andrew Knoll for providing a black shale sample from the Australian Corcoran Formation. This work was supported by the NSF and NASA Astrobiology Program under the NSF Center for Chemical Evolution grant number CHE-1504217. The Bruker Q-TOF mass spectrometer was acquired through NSF grant CHE-0923179.
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