ABSTRACT
Headspace-solid-phase microextraction-gas chromatography (HS-SPME-GC) was used to identify in total 74 volatile lipid oxidation compounds altogether in thermally stressed conventional and high-oleic sunflower (HOSF) oil samples (in accelerated storage conditions for 14 days at 80°C). Out of the volatile compounds identified, six volatile compounds were selected as marker compounds for the assessment of lipid oxidation of sunflower (SF) and HOSF oils due to their low odour threshold values and fatty-rancid odour impression. Additionally, other oxidation parameters such as fatty acid composition, peroxide value (PV), anisidine value and tocopherol and tocotrienol composition were determined. Multivariate statistical methods (principal component analysis and agglomerative hierarchical cluster analysis) were applied to identify sensitive oxidation marker compounds. Preliminary results revealed that hexanal, E-2-heptenal, E-2-decenal and E,E-2,4-nonadienal were the most suitable in differentiating HOSF and SF oil varieties from each other and SF samples with differing oxidative properties. Differentiation of SF samples according to their volatile compound composition was done in accordance with the results from the well-known oil quality parameters (e.g. PV or fatty acid composition). In conclusion, the combination of volatile compound analysis with HS-SPME-GC and multivariate statistical methods provides a sensitive tool in differentiating conventional SF and HOSF oils by means of volatile lipid oxidation marker compounds.
Subject(s)
Chromatography, Gas/methods , Helianthus/chemistry , Lipid Peroxidation , Oleic Acid/metabolism , Plant Oils/metabolism , Solid Phase Microextraction/methods , Volatile Organic Compounds/metabolism , Cluster Analysis , Dietary Fats/metabolism , Fatty Acids/analysis , Fatty Acids/metabolism , Hot Temperature , Multivariate Analysis , Odorants , Oxidation-Reduction , Principal Component Analysis , Reproducibility of Results , Stress, Physiological , Sunflower Oil , Tocopherols/metabolism , Tocotrienols/analysis , Tocotrienols/metabolismABSTRACT
During gamma-irradiation (5 kGy) of aqueous tryptophan (Trp) solutions small amounts of 5-, 6-, and 7-hydroxytryptophan (OH-Trp) (0.04-0.08 Mol-%) are formed. Protein rich food like shrimps contain reasonable amounts of non-protein bound Trp (100 mg/kg). In order to detect the treatment of shrimps with gamma-irradiation a method for the determination of OH-Trp in gamma-irradiated shrimps was developed. After homogenization, squeezing of shrimp samples and protein precipitation, a two-step-SPE-clean up was performed using a C18-cartridge and a propylsulfonic acid cation-exchange SPE followed by HPLC analysis with electrochemical detection (750 mV). Results showed that 5-OH-Trp contents in shrimp samples increased with applied doses up to 3 kGy and then decreased with higher doses. Other OH-Trp isomers were not detectable in the irradiated shrimps. Similarly no formation of 4-, 6-, and 7-OH-Trp was detected in model solutions containing the same amino acid composition as in shrimps. This indicates a suppression of the reaction of OH-radicals with Trp by the 300 fold molar excess of other amino acids acting as well as radical scavengers. Therefore, non-physiological OH-Trp isomers formed from free Trp are not suitable as markers for the detection of gamma-irradiated protein-rich foodstuff.