Combining Charge-Switch Derivatization with Ozone-Induced Dissociation for Fatty Acid Analysis
Jazyk angličtina Země Spojené státy americké Médium print-electronic
Typ dokumentu časopisecké články
Grantová podpora
DP150101715
Australian Research Council
DP190101486
Australian Research Council
PubMed
31347025
DOI
10.1007/s13361-019-02285-5
PII: 10.1007/s13361-019-02285-5
Knihovny.cz E-zdroje
- Klíčová slova
- Fatty Acids, Lipids, ozone-induced dissociation, vernix caseosa,
- MeSH
- lidé MeSH
- mastné kyseliny analýza chemie MeSH
- ozon chemie MeSH
- plynová chromatografie s hmotnostně spektrometrickou detekcí MeSH
- triglyceridy analýza chemie MeSH
- vernix caseosa chemie MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Názvy látek
- mastné kyseliny MeSH
- ozon MeSH
- triglyceridy MeSH
The specific positions of carbon-carbon double bond(s) within an unsaturated fatty acid exert a significant effect on the physical and chemical properties of the lipid that ultimately inform its biological function(s). Contemporary liquid chromatography-mass spectrometry (MS) strategies based on electrospray ionization coupled to tandem MS can easily detect fatty acyl lipids but generally cannot reveal those specific site(s) of unsaturation. Herein, we describe a novel and versatile workflow whereby fatty acids are first converted to fixed charge N-(4-aminomethylphenyl)pyridinium (AMPP) derivatives and subsequently subjected to ozone-induced dissociation (OzID) on a modified triple quadrupole mass spectrometer. The AMPP modification enhances the detection of fatty acids introduced by direct infusion. Fragmentation of the derivatized fatty acids also provides diagnostic fragment ions upon collision-induced dissociation that can be targeted in precursor ion scans to subsequently trigger OzID analyses in an automated data-dependent workflow. It is these OzID analyses that provide unambiguous assignment of carbon-carbon double bond locations in the AMPP-derivatized fatty acids. The performance of this analysis pipeline is assessed in profiling the patterns of unsaturation in fatty acids within the complex biological secretion vernix caseosa. This analysis uncovers significant isomeric diversity within the fatty acid pool of this sample, including a number of hitherto unreported double bond positional isomers that hint at the activity of potentially new metabolic pathways.
Central Analytical Research Facility Queensland University of Technology Brisbane Australia
CSIRO Agriculture and Food St Lucia Queensland 4067 Australia
School of Medicine and Molecular Horizons University of Wollongong Wollongong Australia
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