Correlation between structure and phytotoxic activities of nitrodiphenyl ethers

Abstract

Various nitrodiphenyl ethers were assayed using a cell-free photosynthetic system and intact microalgae to approach a correlation between chemical structure and their effect upon three biochemical processes: (1) linear photosynthetic electron transport (Hill reaction); (2) photophosphorylation (energy-transfer inhibition by affecting the ATP synthetase); and (3) light-induced peroxidative degradation of thylakoid lipids (formation of short-chain hydrocarbons). Diphenyl ethers with a p-nitro group at one phenyl ring and one or two chloro substituents at the other exhibit energy-transfer inhibition. Analogs with different substituents are ineffective. A moderate electron-transport inhibition is seen with almost all derivatives. The most obvious phytotoxic effect is the occurrence of light-induced peroxidation (of polyunsaturated fatty acids) by p-nitro- and p-nitrosodiphenyl ethers. Substituents such as -OCH 3, -OC 2H 5, -NHC 2H 5, or -COOCH 3, -CONHCH 3 next to the p-nitro group enhance peroxidative activity and are apparently important for stabilization and/or reactivity of a diphenyl ether radical originating through photosynthetic electron flow. Activity is further enhanced by substituents with positive Hammett parameters in ortho or para positions at the phenyl ring not carrying the nitro group.