RESUMO

The performances of distinct BDD anodes (boron doping of 100, 500 and 2500 ppm, with sp3/sp2 carbon ratios of 215, 325, and 284, respectively) in the electrochemical degradation of ciprofloxacin - CIP (0.5 L of 50 mg L-1 in 0.10 M Na2SO4, at 25 °C) were comparatively assessed using a recirculating flow system with a filter-press reactor. Performance was assessed by monitoring the CIP and total organic carbon (TOC) concentrations, oxidation intermediates, and antimicrobial activity against Escherichia coli as a function of electrolysis time. CIP removal was strongly affected by the solution pH (kept fixed), flow conditions, and current density; similar trends were obtained independently of the BDD anode used, but the BDD100 anode yielded the best results. Enhanced mass transport was achieved at a low flow rate by promoting the solution turbulence within the reactor. The fastest complete CIP removal (within 20 min) was attained at j = 30 mA cm-2, pH = 10.0, and qV = 2.5 L min-1 + bypass turbulence promotion. TOC removal was practically accomplished only after 10 h of electrolysis, with quite similar performances by the distinct BDD anodes. Five initial oxidation intermediates were identified (263 ≤ m/z ≤ 348), whereas only two terminal oxidation intermediates were detected (oxamic and formic acids). The antimicrobial activity of the electrolyzed CIP solution was almost completely removed within 10 h of electrolysis. The characteristics of the BDD anodes only had a marked effect on the CIP removal rate (best performance by the least-doped anode), contrasting with other data in the literature.

Assuntos

RESUMO

This work reports the green organic chemistry synthesis of E-2-cyano-3(furan-2-yl) acrylamide under microwave radiation (55 W), as well as the use of filamentous marine and terrestrial-derived fungi, in the first ene-reduction of 2-cyano-3-(furan-2-yl) acrylamide to (R)-2-cyano-3-(furan-2-yl)propanamide. The fungal strains screened included Penicillium citrinum CBMAI 1186, Trichoderma sp. CBMAI 932 and Aspergillus sydowii CBMAI 935, and the filamentous terrestrial fungi Aspergillus sp. FPZSP 146 and Aspergillus sp. FPZSP 152. A compound with an uncommon CN-bearing stereogenic center at the α-C position was obtained by enantioselective reactions mediated in the presence of the microorganisms yielding the (R)-2-cyano-3-(furan-2-yl) propanamide 3a. Its isolated yield and e.e. ranged from 86% to 98% and 39% to 99%, respectively. The absolute configuration of the biotransformation products was determined by time-dependent density functional theory (TD-DFT) calculations of electronic circular dichroism (ECD) spectra. Finally, the tautomerization of 2-cyano-3-(furan-2-yl) propanamide 3a to form an achiral ketenimine was observed and investigated in presence of protic solvents.

RESUMO

The electrochemical degradation of ciprofloxacin-CIP (50 mg L-1 in 0.10 mol L-1 Na2SO4) was investigated using a double-sided Ti-Pt/ß-PbO2 anode in a filter-press flow reactor, with identification of oxidation intermediates and follow-up of antimicrobial activity against Escherichia coli. The effect of solution pH, flow rate, current density, and temperature on the CIP removal rate was evaluated. All of these parameters did affect the CIP removal performance; thus, optimized electrolysis conditions were further explored: pH = 10, qV = 6.5 L min-1, j = 30 mA cm-2, and θ = 25 °C. Therefore, CIP was removed within 2 h, whereas ~75% of the total organic carbon concentration (TOC) was removed after 5 h and then, the solution no longer presented antimicrobial activity. When the electrochemical degradation of CIP was investigated using a single-sided boron-doped diamond (BDD) anode, its performance in TOC removal was similar to that of the Ti-Pt/ß-PbO2 anode; considering the higher oxidation power of BDD, the surprisingly good comparative performance of the Ti-Pt/ß-PbO2 anode was ascribed to significantly better hydrodynamic conditions attained in the filter-press reactor used with this electrode. Five initial oxidation intermediates were identified by LC-MS/MS and completely removed after 4 h of electrolysis; since they have also been determined in other degradation processes, there must be similarities in the involved oxidation mechanisms. Five terminal oxidation intermediates (acetic, formic, oxamic, propionic, and succinic acids) were identified by LC-UV and all of them (except acetic acid) were removed after 10 h of electrolysis.

Assuntos

RESUMO

This paper reports the investigation of the chiral interaction between 3,4-methylenedioxy-methamphetamine (MDMA) enantiomers and an immobilized polysaccharide-based chiral phase. For that, suspended-state high-resolution magic angle spinning nuclear magnetic resonance spectroscopy (1H HR-MAS NMR) was used. 1H HR-MAS longitudinal relaxation time and Saturation Transfer Difference (STD NMR) titration experiments were carried out yielding information at the molecular level of the transient diastereoisomeric complexes of MDMA enantiomers and the chiral stationary phase. The interaction of the enantiomers takes place through the aromatic moiety of MDMA and the aromatic group of the chiral selector by π-π stacking for both enantiomers; however, a stronger interaction was observed for the (R)-enantiomer, which is the second one to elute at the chromatographic conditions.

RESUMO

The oxidation of atrazine (ATZ) was studied in the presence of hydrogen peroxide (H(2)O(2)) and ferrihydrite at different concentrations and pHs. The rate of ATZ oxidation increased with H(2)O(2) concentration and is independent of pH ranging from 4 to 8. However, at pH 3 an increase of ten times in the rate of ATZ oxidation was observed due to the mineral dissolution. The decomposition rate of H(2)O(2) was three times higher at pH 8 than 3 and increased with increase of both H(2)O(2) and ferrihydrite concentrations. The results indicate that ferrihydrite controls oxidation of ATZ by H(2)O(2) in two different ways: (i) mineral dissolution at low pH allowing the Fenton reaction to proceed in solution and (ii) surface-mediated decomposition of H(2)O(2) producing non-reactive oxygen species in particular at higher pH. Three degradation products (desethylatrazine, desisopropylatrazine, and 2-hydroxyatrazine) were identified and corroborate with a Fenton reaction taking place in solution.

Assuntos