title: Rapid liquid chromatography-tandem mass spectrometry analysis of 4-hydroxynonenal for the assessment of oxidative degradation and safety of vegetable oils.
abstract: A novel method for the UHPLC-MS/MS analysis of (E)-4-hydroxynonenal (4-HNE) is described. The method is based on derivatization of 4-HNE with pentafluorophenylhydrazine (1) or 4-trifluoromethylphenylhydrazine (2) in acetonitrile in the presence of trifluoroacetic acid as catalyst at room temperature and allows complete analysis of one sample of vegetable oil in only 21 min, including sample preparation and chromatography. The method involving hydrazine 1, implemented in an ion trap instrument with analysis of the transition m/z 337→154 showed LOD=10.9 nM, average accuracy of 101% and precision ranging 2.5-4.0% RSD intra-day (2.7-4.1% RSD inter-day), with 4-HNE standard solutions. Average recovery from lipid matrices was 96.3% from vaseline oil, 91.3% from sweet almond oil and 105.3% from olive oil. The method was tested on the assessment of safety and oxidative degradation of seven samples of dietary oil (soybean, mixed seeds, corn, peanut, sunflower, olive) and six cosmetic-grade oils (avocado, blackcurrant, apricot kernel, echium, sesame, wheat germ) and effectively detected increased 4-HNE levels in response to chemical (Fenton reaction), photochemical, or thermal stress and aging, aimed at mimicking typical oxidation associated with storage or industrial processing. The method is a convenient, cost-effective and reliable tool to assess quality and safety of vegetable oils.
authors.affiliation: BeC S.r.l., R&D Division, Via C. Monteverdi 49, 47122 Forlì, Italy.
authors.forename: Simone
authors.initials: S
authors.lastname: Gabbanini
authors.affiliation: BeC S.r.l., R&D Division, Via C. Monteverdi 49, 47122 Forlì, Italy.
authors.forename: Riccardo
authors.initials: R
authors.lastname: Matera
authors.affiliation: University of Bologna, Department of Chemistry "G. Ciamician", Via S. Giacomo 11, 40126 Bologna, Italy.
authors.forename: Alice
authors.initials: A
authors.lastname: Valvassori
authors.affiliation: University of Bologna, Department of Chemistry "G. Ciamician", Via S. Giacomo 11, 40126 Bologna, Italy. Electronic address: luca.valgimigli@unibo.it.
authors.forename: Luca
authors.initials: L
authors.lastname: Valgimigli
mesh_terms: D000447:Aldehydes / Q000032:analysis* / Q000737:chemistry* / Q000302:isolation & purification; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D005506:Food Contamination / Q000032:analysis*; D059022:Food Safety; D006835:Hydrazones / Q000737:chemistry; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D010938:Plant Oils / Q000737:chemistry*; D015203:Reproducibility of Results; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013696:Temperature
chemical_list: D000447:Aldehydes; D006835:Hydrazones; D010938:Plant Oils; C027576:4-hydroxy-2-nonenal
keywords: 4-Hydroxynonenal; Cosmetics; Derivatization; Food; Mass spectrometry; Plant oil