Characterization of products formed during the autoxidation of beta-carotene.
The anticarcinogenic action of carotenoids such as beta-carotene has been frequently ascribed to their antioxidant properties. However, very little is actually known about the nature of the antioxidant reaction or the products that are formed. beta-Carotene was exposed to either spontaneous autoxidation conditions or to radical-initiated autoxidation conditions. The products were separated by reverse-phase HPLC, and individual peaks were characterized with an on-line diode array detector. Carbonyl products were isolated and characterized by several procedures, including borohydride reduction to the corresponding alcohols, derivatization with O-ethyl-hydroxylamine to the corresponding O-ethyl-oximes of the carbonyls, and analysis by GC-MS. Under the conditions of the experiments, the formation of a homologous series of carbonyl products was demonstrated, including beta-apo-13-carotenone, retinal, beta-apo-14'-carotenal, beta-apo-12'-carotenal, and beta-apo-10'-carotenal. Several very hydrophobic compounds were formed, which have not been previously identified. In addition, the products of NaOCl-treatment of beta-carotene were analyzed, and shown to be significantly different from the autoxidation products. This type of product analysis should be useful in determining the nature of the oxidants reacting with beta-carotene in vivo.
Handelman
G J
GJ
Department of Biochemistry, Tufts University Health Sciences Campus, Boston, MA 02111.
van Kuijk
F J
FJ
Chatterjee
A
A
Krinsky
N I
NI
D000975:Antioxidants / Q000378:metabolism*; D002338:Carotenoids / Q000378:metabolism*; D002851:Chromatography, High Pressure Liquid; D005609:Free Radicals; D007700:Kinetics; D013058:Mass Spectrometry; D010084:Oxidation-Reduction / Q000187:drug effects; D012973:Sodium Hypochlorite / Q000494:pharmacology; D014810:Vitamin E / Q000494:pharmacology; D019207:beta Carotene
D000975:Antioxidants; D005609:Free Radicals; D019207:beta Carotene; D014810:Vitamin E; D002338:Carotenoids; D012973:Sodium Hypochlorite; C004984:apocarotenal