lecture 15: vitamin E Flashcards
vitamin E
lipid soluble, trapping of lipophilic free radicals
all structurally related tocopherols and tocotrienols
vitamin E deficiency
species-specific abnormalities
a-TTP or lipoprotein deficiencies, lipid malabsorption, doesn’t have to do with vitamin E itself
a-tocopherol
primary form, major lipid-soluble antioxidant in plasma, RBCs, tissues
absorption and transport
follows transport of cholesterol absorption
incorporated in chylomicrons, eventually transported by other lipoproteins
excreted through urine after being metabolized to water-soluble compounds
plasma concentrations
linearly related to intake from foods, intake possible from diet
nonlinearly related to higher intakes (supplements), saturation only increases plasma concentrations slightly
secretion of a-tocopherol from liver
repackaged and sent out via VLDLs, crucial to maintaining normal plasma vitamin E levels
a-TTP facilitates secretion of a-tocopherol in plasma lipoprotein pool
a-tocopherol transfer protein (a-TTP)
predominantly in liver
preferentially binds a-tocopherol relative to other forms, high affinity
transfers a-tocopherol from one membrane to another
cytochrome P450
involved in vitamin E metabolism
stronger affinity for all forms of vitamin E OTHER than a-tocopherol > initiates its breakdown
post-absorptive metabolism for these other forms
pathway: selective tissue deposition of a-tocopherol
OVERALL: takes other forms of vitamin E for breakdown
antioxidant activity
vitamin E protects lipids from free-radical induced oxidative damage
reaction of a-tocopherol with peroxyl radicals to prevent uncontrolled lipid peroxidation, terminate chain reaction of radicals
tocopherol oxidation pathway
all forms of vitamin E except a-tocopherol are degraded via cytochrome P450
relative proportions of tocopherols in body lie in stark contrast to those found in foods
free radical initiators
free Fe2+, UV, ionizing radiation, free electrons etc can produce carbon-centered lipid radicals
lipid peroxidation process
1) initiation: initiator forms free radical, reacts with O2 to form peroxyl radical
2) propagation: ROO. reacts with unsaturated FA to form ROOH and a new radical R’.
3) propagation process occurs until antioxidant quenches free radical
6-hydroxyl group
reactive portion of vitamin E
hydroxyl donates hydrogen atom > tocopheroxyl radical, which is stable due to resonance/delocalized electrons
tocopheroxyl radical
stable due to resonance/delocalized electrons, relatively unreactive
tocopherols react more rapidly with peroxyl radicals than do polyunsaturated FAs (protects polyunsaturated FAs from being oxidized)
radical reduced back to tocopherol by vitamin C (see diagram) > REPLENISHED
reversible reaction
single electron oxidation is reversible, e can be replenished by vitamin C, full oxidation is irreversible