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Diphenylamine metabolism and ethylene action were evaluated as factors influencing the development of 'Braeburn' apple internal browning and cavitation during cold storage. Apples treated with the antioxidant diphenylamine (DPA) and/or the ethylene action inhibitor 1-methylcyclopropene (1-MCP) were held at 1 degrees C for up to 6 months in air or a controlled atmosphere (CA) containing 1 kPa of O2 and 3 kPa of CO2. Cortex tissues from fruit without disorders as well as from symptomatic and asymptomatic areas of fruit with disorders were analyzed for DPA and DPA derivative content. Internal browning and cavities developed in control and 1-MCP-treated fruit stored in CA, whereas air-stored and CA fruit treated with DPA or with DPA and 1-MCP prior to storage did not develop disorders. Depending on the storage regimen and duration, less DPA was detected in 1-MCP-treated fruit. The 4-hydroxydiphenylamine (4OHDPA) content of control fruit decreased during air storage duration but increased between 2 and 4 months in CA storage. 4OHDPA content in 1-MCP-treated fruit increased with storage duration in CA but not air. N-Nitrosodiphenylamine (NODPA) was detected after 2 months in control fruit stored in air or CA and in 1-MCP-treated fruit stored in CA, and NODPA content in control fruit was higher compared to that in 1-MCP-treated fruit. Accumulation of 4-methoxydiphenylamine (4MeODPA) in control fruit stored in air increased with storage duration, but 4MeODPA content did not change in 1-MCP-treated fruit stored in air or CA. 2-Nitrodiphenylamine content was reduced by prestorage treatment with 1-MCP, but storage environment and duration had no effect on its accumulation. The results indicate that CA storage increases the risk of disorder development in 'Braeburn' apples, that DPA can prevent disorder development, and that the content of DPA and DPA derivatives is influenced by storage environment and ethylene action. A clear relationship between DPA derivative formation and storage conditions that promote internal browning was not apparent.

The application of diphenylamine (DPA) to prevent the apple peel disorder superficial scald can result in accumulation of a number of DPA derivatives resulting from C-nitration, C-hydroxylation, O-methylation, and N-nitrosation during fruit storage. As the presence of these compounds may be indicative of metabolic processes leading to superficial scald development, the contents of DPA and DPA derivatives were determined in fruits treated at harvest with DPA or DPA plus the ethylene action inhibitor 1-methylcyclopropene (1-MCP), which also prevents scald development. Influences of fruit maturity, storage environment, storage duration, and a 14 day poststorage ripening period on accumulation of DPA metabolites were also assessed. Poststorage ripening, 1-MCP treatment, and controlled atmosphere storage had varied effects on DPA derivative contents suggesting that reactive oxygen and nitrogen species, such as *OH, *NO, and *NO2, or enzyme-catalyzed reactions may be present during certain ripening and senescence-related physiological processes. Definitive correlations between superficial scald incidence and contents of specific derivatives were not observed.

Cv. Granny Smith apple fruit, treated at harvest with aqueous emulsions containing diphenylamine (DPA) and DPA derivatives, were evaluated for the peel disorder superficial scald (scald) after 6 months of cold storage at 1 degrees C plus 0 or 7 days at 20 degrees C. Metabolism of these derivatives and alpha-farnesene oxidation were also evaluated after 6 months. Derivatives substituted at the para position prevented scald, but scald developed on fruit treated with derivatives substituted in the amino, ortho, or meta positions. The extent of scald control was also dependent on the chemical nature of the functional group used to derivatize DPA. Hydroxylation of DPA and DPA derivatives during storage was not associated with scald control. Methoxylated DPA derivatives produced during storage resulted from O-methylation of C-hydroxylated derivatives rather than C-methoxylation of DPA. N-Nitrosodiphenylamine provided partial scald control, possibly resulting from its degradation to DPA, indicating that the amino hydrogen of DPA may be crucial for scald control. Results suggest that functional group position and chemical properties both contribute to the efficacy of DPA derivatives for scald control.

A method was developed for extracting, identifying, and quantifying diphenylamine (DPA) derivatives in the peel of DPA-treated apples using gradient reversed-phase liquid chromatography with ultraviolet-visible absorption and atmospheric pressure chemical ionization detection (LC-UV-vis-APCI-MS). Compounds routinely analyzed using this method included hydroxylated, nitrosated, nitrated, and methoxylated diphenylamine derivatives. Analysis of peel treated with 0-8 g L(-1) DPA showed that peel DPA content was a limiting factor in derivative production and that recovery of most compounds over this range was linear.