Clopyralid degradation by AOPs enhanced with zero valent iron.

Four different technologies have been compared (photolysis, ZVI + photolysis, electrolysis and ZVI + electrolysis) regarding the: (1) degradation of clopyralid, (2) extent of its mineralization, (3) formation of by-products and main reaction pathways. Results show that photolysis is the less efficient treatment and it only attains 5 % removal of the pollutant, much less than ZVI, which reaches 45 % removal and that electrolysis, which attains complete removal and 78 % mineralization within 4 h. When ZVI is used as pre-treatment of electrolysis, it was obtained the most efficient technology. The identification of transformation products was carried out for each treatment by LCMS. In total, ten products were identified. Tentative pathways for preferential clopyralid degradation for all processes were proposed. This work draws attention of the synergisms caused by the coupling of techniques involving the treatment of chlorinated compound and sheds light on how the preferential mechanisms of each treatment evaluated occurred.

Conformational and reactivity study of dithiophenyl-fucosyl ketals with theoretical chemical methods.

Carbohydrates can be used as substrates to synthesize new complex molecules; these molecules contain several chiral centers that can be used in organic synthesis. D-Fucose diphenyl thioacetal reacts differentially with acetone, and this paper describes a study of the mechanism of this reaction using theoretical chemistry methods. The conformer distribution was studied using a Monte Carlo method for the reaction products, and the obtained conformers were validated by calculating the hydrogen spin-spin coupling constants with the DFT/B3LYP/DGDZVP method. Results agreed with the experimental coupling constants with an adequate root mean squared deviation. The free energies and enthalpies of formation of the resulting global minimum conformers were calculated with the same method and with the thermochemical compound method CBS-4 M. This technique, combined with the conformational analysis, allowed comparison of the formation enthalpies of the compounds involved in this reaction, and, with this information, we can postulate the correct reaction pathway. Graphical abstract Reaction pathway.