title: The peroxidative coupling of hemigossypol to (+)- and (-)-gossypol in cottonseed extracts.
abstract: Peroxidase(s) present in embryo extracts of Gossypium hirsutum cv. Texas Marker 1 catalyzed a bimolecular coupling of [4-(3)H]-hemigossypol to [4,4'-(3)H(2)]-gossypol. The reaction was dependent on the addition of H(2)O(2) and was inhibited 71-94% by 1 and 10mM sodium azide. The phenolic coupling produced 53% (+)-gossypol and 47% (-)-gossypol in close agreement to the 49% (+)-gossypol and 51% (-)-gossypol found in the intact seed. The nearly racemic mixture of (+)-and (-)-gossypol produced in these embryo extracts can be accounted for by non-enzymatic random coupling of the free radicals of hemigossypol produced by the peroxidase. In contrast, peroxidase reaction mixtures containing crude embryo extracts of G. hirsutum var. marie-galante produced 73% (+)-gossypol and 27% (-)-gossypol. These data from the marie-galante extracts and the fact that these intact seed contain 95% (+)-gossypol suggest a regio-stereoselective bimolecular coupling of hemigossypol to gossypol. The development of the peroxidative coupling of hemigossypol to gossypol in maturing seed of G. hirsutum cv. Texas Marker 1 was correlated to the formation of gossypol and suggests that peroxidative coupling of hemigossypol contributes to gossypol biosynthesis.
authors.affiliation: TAMU, College Station, TX 77843, USA.
authors.forename: Chauncey R
authors.initials: CR
authors.lastname: Benedict
authors.forename: Jinggao
authors.initials: J
authors.lastname: Liu
authors.forename: Robert D
authors.initials: RD
authors.lastname: Stipanovic
mesh_terms: D002851:Chromatography, High Pressure Liquid; D003369:Cottonseed Oil / Q000737:chemistry*; D005609:Free Radicals / Q000378:metabolism; D003368:Gossypium / Q000378:metabolism*; D006072:Gossypol / Q000031:analogs & derivatives / Q000378:metabolism*; D007536:Isomerism; D009904:Optical Rotation; D009195:Peroxidase / Q000378:metabolism*; D010936:Plant Extracts / Q000737:chemistry / Q000378:metabolism; D019810:Sodium Azide / Q000494:pharmacology; D013997:Time Factors
chemical_list: D003369:Cottonseed Oil; D005609:Free Radicals; D010936:Plant Extracts; D019810:Sodium Azide; D009195:Peroxidase; D006072:Gossypol