Simple chemical syntheses of TAG monohydroperoxides

For the purpose of synthesizing standards to be used in the quantification of TAG hydroperoxides, three TAG (1,2-dioleoyl-3-palmitoylglycerol, 1-oleoyl-2-linoleoyl-3-palmitoylglycerol, and triolein) monohydroperoxides were chemically synthesized as authentic specimens. TAG were prepared by using a simple condensation in pyridine of glycerol and the corresponding acid chlorides. These TAG were then converted into monohydroperoxides by a photosensitized peroxidation. The synthesized monohydroperoxides were analyzed by normal-phase and RP-HPLC. The results of normal-phase HPLC analysis showed that monohydroperoxides from a corresponding TAG were a mixture of regioisomers. In RP-HPLC, however, the regioisomers of monohydroperoxides were not separated and gave a single peak, which may improve the sensitivity for the detection of TAG monohydroperoxides. In this study TAG monohydroperoxide standards were synthesized; these will be useful for the study of yet unknown biological and pathological roles of TAG hydroperoxides.