Olli Sjövall

Diet and lipoprotein oxidation: analysis of oxidized triacylglycerols in pig lipoproteins.

Oxidized lipoproteins have a recognized role in atherogenesis, but molecular-level research on oxidized lipids in lipoproteins and the effect of diet on these molecules have been limited. In the present study, the effects of three sunflower seed oil diets differing in oxidation levels (PV in oils 1, 84, and 223 mequiv O2/kg) on lipoprotein lipid oxidation in growing pigs were investigated. The emphasis was on the investigation of oxidized TAG molecules found in chylomicrons and VLDL. A method based on RP-HPLC and electrospray ionization-MS was used for the analysis of oxidized TAG molecules. The baseline diene conjugation method was used for the estimation of in vivo levels of lipoprotein lipid oxidation. Several oxidized TAG structures were found in the samples. These products consisted of TAG molecules with a hydroxy, an epoxy, or a keto group attached to a FA, and of TAG molecules containing an aldehyde structure derived from a FA. The lipoprotein lipids and TAG were more oxidized in the pigs fed on the most oxidized oil compared with those fed on nonoxidized oil. Oxidation of dietary fat was reflected in the lipoprotein oxidation. New, detailed information on oxidized TAG molecules of chylomicrons and VLDL was obtained.

New approach to the analysis of oxidized triacylglycerols in lipoproteins.

The oxidation of human LDL lipids and the structures of oxidized TAG molecules found in LDL were investigated. Pooled samples of 10 normolipidemic and 10 hyperlipidemic subjects were analyzed. For determination of the oxidation levels, the LDL baseline diene conjugation (LDL-BDC) method was used. A method based on HPLC and electrospray ionization-MS was optimized and applied to the analysis of molecular structures of oxidized TAG in LDL. Differences were found between the oxidation levels of the samples. The LDL-BDC value was 22.2 μmol/L serum in the normolipidemic group, and 88.1 μmol/L serum in the hyperlipidemic group. The amounts of oxidized TAG molecules were small. However, several species of oxidized TAG were identified. These included TAG molecules with a keto or an epoxy group attached to a FA, and TAG molecules with a FA core aldehyde. In some TAG, the keto/epoxy ratio was greater in the hyperlipidemic group compared to the normolipidemic group. The results show that our approach is applicable to research on lipid oxidation in lipoproteins.

Rapid complexing of oxoacylglycerols with amino acids, peptides and aminophospholipids.

We prepared model Schiff bases from 2-[9-oxo]nonanoyl glycerol (2-MAG-ALD) and various amino compounds. 2-MAG-ALD was obtained by pancreatic lipase hydrolysis of trioleoyl glycerol and reductive ozonolysis of the resulting 2-monooleoyl glycerol. The reaction products were purified by thin-layer chromatography. Schiff bases were synthesized in greater than 50% yield by reacting 2-MAG-ALD with twofold molar excess of valine, Nα-acetyl-l-lysine methyl ester and the tripeptides glycyl-glycyl-glycine, glycyl-glycyl-histidine, and glycyl-histidyl-lysine in aqueous methanol and with 1-palmitoyl-2-stearoyl glycerophosphoethanolamine (PE) in chloroform.methanol for 16 h at room temperature. Prior to analysis the bases were reduced with sodium cyanoborohydride in methanol for 30 min at 4°C. Reaction products were analyzed by high-performance liquid chromatography/electrospray ionization/mass spectrometry (HPLC/ESI/MS). Reduced Schiff bases of 2-MAG-ALD with PF and amino acids were analyzed by normal-phase HPLC/ESI/MS and those with peptides by reversed-phase HPLC/ESI/MS. Single adducts were obtained in all cases and both the α-amino group of valine and the ε-amino group of Nα-acetyl-l-lysine methyl ester were reactive. Molecular ions of reaction products were the only detected ions in the negative ionization mode, whereas in the positive ion mode sodiated molecular ions were also detected. The present study suggests that 2-MAG-ALD may form Schiff base adducts with amino compounds in other aqueous media, such as the intestinal lumen and in the hydrophobic environment of cell membranes.

The effects of gamma-irradiation on some pure aroma compounds of spices

ZusammenfassungAn elf gewürztypischen Aromastoffen wurden die von derγ-Strahlung verursachten Veränderungen untersucht. Die Proben wurden unter Verwendung von60Co als Strahlungsquelle mit Dosen von 0, 10 und 50 kGy bestrahlt. Die bestrahlten und unbestrahlten Proben wurden gaschromatographisch (GC) und GC-massenspektrometrisch untersucht. Erhebliche Veränderungen zeigten sich nur beim (±)-Linalool und beimα-Terpineol, die zum Beispiel für die ätherischen Öle von Koriander und Lorbeerblatt typisch sind. Die Peaks dieser Aromastoffe reduzierten sich um 4–13%, und dem entsprechend waren einige kleinere Peaks zu beobachten. Es kann dennoch zu unterschiedlichen Resultaten kommen, wenn Gewürze bestrahlt werden.SummaryChemical changes due to gamma-irradiation were investigated in 11 pure aroma compounds typically found in spices. Samples were irradiated with doses of 0, 10, and 50 kGy. The irradiation source was60Co. Irradiated samples and unirradiated controls were analyzed by gas chromatography alone and coupled with mass spectrometry. Significant changes due to the irradiation occurred only in (±)-linalool andα-terpineol, which are typical components of, for example, coriander and bay leaf. Their total amounts decreased by about 4–13% and some minor peaks increased as a result of irradiation. However, different results may be obtained when the spices themselves are irradiated.