Assessment of fungicide systemicity in wheat using LC-MS/MS

BACKGROUND: Systemicity is an important attribute of fungicides that is difficult to measure in early‐stage screening without labeling the compound with a radioisotope. A method of measuring translocation that does not require potent fungicidal activity or a radiolabel would guide identification of compounds with desirable attributes. RESULTS: The authors developed an analytical technique that mimics field application, using LC‐MS/MS to screen compounds for translocation in wheat leaves. The method sorted commercial and experimental fungicides appropriately into systemic and non‐systemic categories. A model using LC‐MS/MS data was equivalent to a lipophilicity model and superior to a water solubility model at predicting compound systemicity. CONCLUSION: Early‐stage compounds can be screened for systemicity on whole plants using LC‐MS/MS. Copyright © 2008 Society of Chemical Industry     

Kinetics of heterogeneous photocatalytic decomposition of 2,4-dichlorophenoxyacetic acid over titanium dioxide and zinc oxide in aqueous solution

The photocatalytic transformation of 2,4-D in aqueous solution containing a suspension of titanium dioxide or zinc oxide leads to the formation of intermediates which are totally mineralised to carbon dioxide and hydrogen chloride (2,4-dichlorophenol and chlorohydroquinone are the major intermediates). The products at the initial stage of the reaction were 2,4-dichlorophenol (2,4-DCP), chlorohydroquinone, 4-chloropyrocatechol, 2,4-dichloropyrocatechol and 1,4-chlorobenzoquinone. The initial rate of photodegradation was studied as a function of the initial concentration of reactants by the linearised form of the Langmuir–Hinshelwood equation, by which rate constants k and equilibrium adsorption constants K were evaluated. These constants were calculated at different temperatures between 25 and 60°C. The photodegradation rate increased with increase of pH. The photocatalytic transformation of 2,4-D over titanium dioxide or zinc oxide in solution containing hydrogen peroxide was studied. The latter accelerated the reaction rate of 2,4-D significantly. It was found that chloride or bicarbonate ions slowed down the photodegradation rate of 2,4-D by scavenging hydroxyl radicals. Partial inhibition by ethanol is attributed to scavenging of the OH radicals involved in the first step of the reaction. © 1998 Society of Chemical Industry     

Solar photo-inactivation of phytopathogens by trace level hydrogen peroxide and titanium dioxide photocatalysis

Plant pathogenic bacteria in recirculated greenhouse water were inactivated by two distinct photochemical approaches: photo-inactivation in the presence of 0.005% to 0.01% hydrogen peroxide (H₂O₂), and photocatalytic inactivation with 0.01% titanium dioxide (TiO₂). In both processes photo-inactivation is achieved by exposure to sunlight. Total inactivation, with 6–8 log units decrease in viable counts, was achieved in the study of the phytopathogensErwinia carotovora (E.c.), Clavibacter michiganensis (C.m.) andPseudomonas syringae pv.tomato (P.t.) by 10 to 30 min solar irradiation, in the presence of 0.15 to 0.3 mM (50–100 mgl ⁻¹) H₂O₂. Different responses of the examined pathogens towards TiO₂ photo-inactivation were noticed. Whereas 10 min of solar illumination in the presence of both 100 mgl ⁻¹ H₂O₂ and 100 mgl ⁻¹ TiO₂ resulted in total inactivation ofP.t. andE.c., this treatment had no effect onC.m. However, with traces of H₂O₂ (e.g. 50–100 mgl ⁻¹), and in the absence of TiO₂,C.m. was deactivated by 20 min of solar irradiation.P.t. was fully inactivated in the dark by H₂O₂ at 3,000 mgl ⁻¹ (0.3%), but not with H₂O₂ at ≤ 1000 mgl ⁻¹. Also, no inactivation occurred with solar illumination in the absence of H₂O₂. The mechanism of the bactericidal photoreaction and the special significance of plant pathogen inactivation by natural sunlight in the presence of trace levels of H₂O₂ is discussed. http://www.phytoparasitica.org posting May 20, 2005.