Low-Field Benchtop NMR Spectroscopy for Quantification of Aldehydic Lipid Oxidation Products in Culinary Oils during Shallow Frying Episodes.

Abstract

Toxic aldehydic lipid oxidation products (LOPs) arise from the thermo-oxidative deterioration of unsaturated fatty acids present in heated culinary oils when exposed to high-temperature frying episodes, and currently these effects represent a major public health concern. In this study, we investigated the applications of low-field (LF), benchtop NMR analysis to detect and quantify toxic aldehyde species in culinary oils following their exposure to laboratory-simulated shallow frying episodes (LSSFEs) at 180 °C. Four culinary oils of variable fatty acid (FA) composition were investigated to determine the analytical capabilities of the LF NMR instrument. Oil samples were also analysed using a medium-field (400 MHz) NMR facility for comparative purposes. Aldehydes were quantified as total saturated and total α,β-unsaturated classes. The time-dependent production of α,β-unsaturated aldehydes decreased in the order chia > rapeseed ≈ soybean > olive oils, as might be expected from their polyunsaturated and monounsaturated FA (PUFA and MUFA, respectively) contents. A similar but inequivalent trend was found for saturated aldehyde concentrations. These data strongly correlated with medium-field 1H NMR data obtained, although LF-determined levels were significantly lower in view of its inability to detect or quantify the more minor oxygenated aldehydic LOPs present. Lower limit of detection (LLOD) values for this spectrometer were 0.19 and 0.18 mmol/mol FA for n-hexanal and trans-2-octenal, respectively. Aldehydic lipid hydroperoxide precursors of aldehydic LOPs were also detectable in LF spectra. We therefore conclude that there is scope for application of these smaller, near-portable NMR facilities for commercial or 'on-site' quality control determination of toxic aldehydic LOPs in thermally stressed frying oils.