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Application of high-resolution, two-dimensional 1H and 13C nuclear magnetic resonance techniques to the characterization of lipid oxidation products in autoxidized linoleoyl/linolenoylglycerols

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Lipids

Abstract

Subjection of polyunsaturated fatty acid (PUFA)-rich culinary oils to standard frying episodes generates a range of lipid oxidation products (LOP), including saturated and α,β-unsaturated aldehydes which arise from the thermally induced fragmentation of conjugated hydroperoxydiene precursors. Since such LOP are damaging to human health, we have employed high-resolution, two-dimensional 1H-1H relayed coherence transfer, 1H-1H total correlation, 1H-13C heteronuclear multiple quantum correlation, and 1H-1H J-resolved nuclear magnetic resonance (NMR) spectroscopic techniques to further elucidate the molecular structures of these components present in (i) a model linoleoylglycerol compound (1,3-dilinolein) allowed to autoxidize at ambient temperature and (ii) PUFA-rich culinary oils subjected to repeated frying episodes. The above techniques readily facilitate the resolution of selected vinylic and aldehydic resonances of LOP which appear as complex overlapping patterns in conventional one-dimensional spectra, particularly when employed in combination with solvent-induced spectral shift modifications. Hence, much useful multi-component information regarding the identity and/or classification of glycerol-bound conjugated hydroperoxydiene and hydroxydiene adducts, and saturated and α,β-unsaturated aldehydes, present in autoxidized PUFA matrices is provided by these NMR methods. Such molecular information is of much value to researchers investigating the deleterious health effects of LOP available in the diet.

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Abbreviations

CHPD:

conjugated hydroperoxydiene

HMQC:

heteronuclear multiple quantum coherence transfer

LOP:

lipid oxidation products

NMR:

nuclear magnetic resonance

PUFA:

polyunsaturated fatty acids

RCT:

relayed coherence transfer

RD:

relaxation delay

TMS:

tetramethylsilane

TOCSY:

total correlation

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  1. Bone and Joint Research, Unit, London Hospital Medical College, ARC Building 25-29 Ashfield St., E1 2AD, London, UK

    Christopher J. L. Silwood & Martin Grootveld

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  1. Christopher J. L. Silwood
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  2. Martin Grootveld
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Silwood, C.J.L., Grootveld, M. Application of high-resolution, two-dimensional 1H and 13C nuclear magnetic resonance techniques to the characterization of lipid oxidation products in autoxidized linoleoyl/linolenoylglycerols. Lipids 34, 741–756 (1999). https://doi.org/10.1007/s11745-999-0421-5

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  • DOI: https://doi.org/10.1007/s11745-999-0421-5

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