The mineralization of tetracycline by electrochemical advanced oxidation processes (EAOPs) as well as the study of the toxicity of its intermediates and degradation products are presented. Electro-Fenton (EF), anodic oxidation (AO), and electro-Fenton coupled with anodic oxidation (EF/AO) were used to degrade tetracycline on carbon felt (cathode) and a sub-stoichiometric titanium oxide (Ti4O7) layer deposited on Ti (anode). As compared to EF and AO, the coupled EF/AO system resulted in the highest pollutant removal efficiencies: total organic carbon removal was 69 ± 1% and 68 ± 1%, at 20 ppm and 50 ppm of initial concentration of tetracycline, respectively. The effect of electrolysis current on removal efficiency, mineralization current efficiency, energy consumption, and solution toxicity of tetracycline mineralization were investigated for 20 ppm and 50 ppm tetracycline. The EF/AO process using a Ti4O7 anode and CF cathode provides low energy and high removal efficiency of tetracycline caused by the production of hydroxyl radicals both at the surface of the non-active Ti4O7 electrode and in solution by the electro-Fenton process at the cathodic carbon felt. Complete removal of tetracycline was observed from HPLC data after 30 min at optimized conditions of 120 mA and 210 mA for 20 ppm and 50 ppm tetracycline concentrations. Degradation products were elucidated, and the toxicity of the products were measured with luminescence using Microtox® bacteria toxicity test.
In hydrolysis and electro-oxidation of the borohydride anion BH4−, key reactions in the field of energy, one critical short-living intermediate is BH3OH−. When water was used as both solvent and reactant, only BH3OH− is detected by 11B NMR. By moving away from such conditions and using DMF as solvent and water as reactant in excess, four 11B NMR quartets were observed. These signals were due to BH3-based intermediates as suggested by theoretical calculations; they were DMF·BH3, BH3OH−, and B2H7− (i.e., [H3B−H−BH3]− or [H4B−BH3]−). Our results shed light on the importance of BH3 stemming from BH4− and on its capacity as Lewis acid to interact with Lewis bases such as DMF, OH−, and BH4−. These findings are important for a better understanding at the molecular level of hydrolysis of BH4− and production of impurities in boranes synthesis.
30 April 2011 in Microporous and Mesoporous Materials
Cyclic oxyterpenes are natural products that are mostly used as fragrances, flavours and drugs by the cosmetic, food and pharmaceutical industries. However, only a few cyclic oxyterpenes are accessible via chemical syntheses, which are far from being ecofriendly. We report here the synthesis of six cyclic oxyterpenes derived from ß-pinene while respecting the principles of green and sustainable chemistry. Only natural or biosourced catalysts were used in mild conditions that were optimised for each synthesis. A new generation of ecocatalysts, derived from Mn-rich water lettuce, was prepared via green processes, characterised by MP-AES, XRPD and TEM analyses, and tested in catalysis. The epoxidation of ß-pinene led to the platform molecule, ß-pinene oxide, with a good yield, illustrating the efficacy of the new generation of ecocatalysts. The opening ß-pinene oxide was investigated in green conditions and led to new and regioselective syntheses of myrtenol, 7-hydroxy-α-terpineol and perillyl alcohol. Successive oxidations of perillyl alcohol could be performed using no hazardous oxidant and were controlled using the new generation of ecocatalysts generating perillaldehyde and cuminaldehyde.