Aminoparathion: a highly reactive metabolite of parathion. 1. Reactions with polyphenols and polyphenol oxidase.
Spiking of tomato and apple fruits with parathion at different levels of about 1-4 mg/kg irradiation and under simulated sunlight conditions resulted in nearly complete photodegradation within 13 h, but extractable parathion degradation products could not be found in any case. However, after irradiation of an unrealistically spiked apple (134 mg/kg) different photoproducts including aminoparathion (AP) were detectable by HPLC, proving that the hitherto postulated photochemistry of parathion indeed takes place in the fruit cuticle environment. Besides the photoreduction pathway it was shown for the first time that AP is also easily formed by reduction of the primary photoproduct nitrosoparathion with thiols (cysteine, glutathione), while ascorbic acid only leaves hydroxylaminoparathion. In the presence of polyphenols, AP was effectively bound to quinone intermediates formed by both silver oxide and polyphenol oxidases. For pyrocatechol, a disubstituted o-quinone derivative could be isolated as a dark red addition product and structurally be elucidated. However, in the presence of caffeic acid, catechol, naringin, and quercetin, respectively, insoluble dark colored polymers precipitated within 48 h, while in the supernatants AP was not detectable any more. Polymer-bound and nonextractable AP was proven by transesterification with sodium ethoxide releasing O,O,O-triethyl thiophosphate which was determined by GC. Additionally, AP itself was a substrate for polyphenol oxidases, resulting in a quinone imine intermediate which in turn reacted with excessive AP yielding deep red colored di- and trimerization products.
Rung
Bruno
B
Institut für Lebensmittelchemie, Universität Hohenheim, Garbenstrasse 28, D-70599 Stuttgart, Germany.
Schwack
Wolfgang
W
D004156:Catechol Oxidase / Q000378:metabolism*; D002851:Chromatography, High Pressure Liquid; D005419:Flavonoids / Q000378:metabolism*; D005638:Fruit; D007306:Insecticides; D018551:Solanum lycopersicum; D027845:Malus; D010278:Parathion / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism*; D010636:Phenols / Q000378:metabolism*; D010777:Photochemistry; D059808:Polyphenols
D005419:Flavonoids; D007306:Insecticides; D010636:Phenols; D059808:Polyphenols; C016224:aminoparathion; D010278:Parathion; D004156:Catechol Oxidase