Tocopherols and tocotrienols, parent congeners in the vitamin E family, function as phenolic antioxidants. However, there has been little interest in their quinone electrophiles formed as a consequence of oxidation reactions, even though unique biological properties were suggested by early studies conducted immediately after the discovery of vitamin E. Oxidation of tocopherols and tocotrienols produces para-and orthoquinones, and quinone methides, while oxidation of their carboxyethyl hydroxychroman derivatives produces quinone lactones. These quinone electrophiles are grouped in two subclasses, the nonarylating fully methylated -family and the arylating desmethyl b-, g-, and d-family. Arylating quinone electrophiles form Michael adducts with thiol nucleophiles, provided by cysteinyl proteins or peptides, which can be identified and quantified by tetramethylammonium hydroxide thermochemolysis. They have striking biological properties which diVer significantly from their nonarylating congeners. They are highly cytotoxic, inducing characteristic apoptotic changes in cultured cells. Cytotoxicity is intimately associated with the induction of endoplasmic reticulum stress and a consequent unfolded protein response involving the pancreatic ER kinase (PERK) signaling pathway that commits overstressed cells to apoptosis. The step-function diVerence between arylating and nonarylating tocopherol quinones is conceivably the basis for distinct biological properties of parent tocopherols, including the epigenetic modification of a histone thiol, the ceramide pathway, natriuresis, and the activity of COX-2, NF-kB, PPARg, and cyclin. The role of -tocopherol in the origin and evolution of the western hominin diet, the so-called ''Mediterranean'' diet, and the prominence of -tocopherol in colostrum, mother's milk, and infant nutrition are considered. Finally, the discordance introduced into the diet by arylating tocopherol quinone precursors through the wide use of vegetable oils in deep-frying is recognized.