Antioxidant activity of all-trans-retinol in homogeneous solution and in phosphatidylcholine liposomes.
A kinetic quantification of the lipoperoxyl radical-scavenging activity of all-trans-retinol has been carried out in homogeneous solution, when radicals were produced from the oxidation of methyl linoleate in methanol, initiated by the lipid-soluble 2,2'-azobis (2,4-dimethylvaleronitrile) (AMVN) as well as in a soybean phosphatidylcholine membrane model, in which peroxidation was induced either by AMVN or the hydrophylic 2,2'-azobis(2-amidinopropane)hydrochloride (AAPH). The physical microenvironment contributes to the determination of antioxidant efficiency of all-trans-retinol. In homogeneous solution the kinetic constant kinh is 3.5 x 10(5) M-1 s-1 and appears of the same order of magnitude as the inhibition constant measured for alpha-tocopherol under the same experimental conditions. Nevertheless, despite its very high chemical reactivity toward lipoperoxyl radicals, the overall antioxidant efficiency of all-trans-retinol in this system appears quite limited, since the evaluated stoichiometric factor is 0.21. When the polyenoic chain of all-trans-retinol is incorporated into a phosphatidylcholine lipid bilayer, the antioxidant efficiency depends on the site of peroxyl-radical production. The highest lipoperoxyl radical-scavenging activity is measured when radicals are generated by AHVN inside the bilayer multilamellar liposomes. Under these conditions, the relative antioxidant efficiency is similar to that of alpha-tocopherol, and the stoichiometric factor is 3.1. When radicals are generated by AAPH in the aqueous phase of an unilamellar liposomal system, the antioxidant effectiveness of all-trans-retinol appears reduced and lower than that measured with equivalent amounts of alpha-tocopherol. Synergistic antioxidant effects between all-trans-retinol and alpha-tocopherol are observed when both antioxidants are simultaneously incorporated into unilamellar liposomes in which peroxidation is induced by AAPH. This suggests that all-trans-retinol may interact with tocopheroxyl radicals, thereby regenerating alpha-tocopherol. This interaction, which may be related to molecular features and to the relative location of the antioxidants in the bilayer, could provide an effective antioxidant system that may be of great importance in vivo.
Tesoriere
L
L
Istituto di Chimica Biologica, Università di Palermo, Italy.
Ciaccio
M
M
Bongiorno
A
A
Riccio
A
A
Pintaudi
A M
AM
Livrea
M A
MA
D000578:Amidines; D001391:Azo Compounds; D002851:Chromatography, High Pressure Liquid; D016166:Free Radical Scavengers; D005609:Free Radicals; D007700:Kinetics; D008051:Lipid Bilayers; D015227:Lipid Peroxidation; D008081:Liposomes; D009570:Nitriles; D016877:Oxidants; D010713:Phosphatidylcholines / Q000737:chemistry*; D012996:Solutions; D014316:Tritium; D014801:Vitamin A
D000578:Amidines; D001391:Azo Compounds; D016166:Free Radical Scavengers; D005609:Free Radicals; D008051:Lipid Bilayers; D008081:Liposomes; D009570:Nitriles; D016877:Oxidants; D010713:Phosphatidylcholines; D012996:Solutions; C055792:2,2'-azobis(2,4-dimethylvaleronitrile); D014316:Tritium; D014801:Vitamin A; C046728:2,2'-azobis(2-amidinopropane)