Removal of paracetamol from aqueous solution by activated carbon and silica. Experimental and computational study.

The presence of pharmaceutical residues in the aquatic environment is a known problem worldwide. Paracetamol is widely used as an analgesic and antipyretic. Its high consumption implies a continuous discharge in aqueous environments through industrial and domestic wastewater that requires mitigation and remediation strategies. The aim of the present study was to analyse the removal of the paracetamol from aqueous solutions using the adsorption technique. For this, three commercial adsorbents with different textural properties were used: two activated carbons (CAT and CARBOPAL) and silica gel. A series of batch adsorption experiments were conducted at different values of pH (3.0, 7.0 and 10.5) and ionic strength (0.01, 0.5 and 1 M) to investigate the effects on the removal of paracetamol from the aqueous solution. In addition, we investigated the adsorption mechanism using the density functional theory. Adsorption was found to be higher in the acidic pH range, as varying pH showed significant influence on the surface charge of the adsorbents and degree of ionization of the paracetamol. Adsorption capacity of the adsorbents increased with an increase in the ionic strength of solution. At 25 °C, pH 3, ionic strength 1 M, 167 mg L-1 of adsorbent and initial concentrations of paracetamol between 25 and 150 mg L-1, the maximum adsorption capacity was 560 mg g-1, 450 mg g-1 and 95 mg g-1, for CAT, CARBOPAL and silica respectively. The experimental kinetic data fitted well the pseudo-second order model and the equilibrium isotherm data the Langmuir model. The functional density theory methods provided atomistic details about paracetamol adsorbed on the surface of carbon and silica through molecular modeling.

Evidence of the presence of minor tautomeric forms in selected nitroanilines.

RATIONALE: Nitroanilines can exist in several tautomeric forms: nitro-amino, nitro-imino, and aci-imino. The importance of evaluating minor tautomeric species comes from the fact that even less abundant tautomers have been proved to play important roles in reaction mechanisms. METHODS: Electron ionization mass spectra of the pesticide Pendimethalin and four related nitroanilines were recorded at 70 eV to find information about the presence of minor tautomeric forms in the gas phase. The existence of the possible tautomers was evaluated by studying specific fragmentation pathways, which were confirmed by tandem mass spectrometry (MS/MS) experiments. Further supporting information was obtained by studying the structures of some intermediate compounds by theoretical calculations at the B3LYP 6-311++G(d,p) level. RESULTS: The mass spectrum of Pendimethalin suggests the coexistence of the nitro-amine tautomer (the most stable form) with four possible less stable tautomers in equilibrium. The fragmentation routes were used to explain analogous peaks in two related compounds. However, the spectra of two other related compounds that cannot follow the proposed route of fragmentation for nitro-imine tautomers do not show the analogous peak. Theoretical calculations were used to correlate the precursor cation with the proposed fragmentation pathway. CONCLUSIONS: By the study of mass spectra and proposed fragmentation pathways it can be concluded that, although the nitro-amine is the most abundant species within the system, minor tautomers (nitro-imine and aci-imine) coexist in the gas phase.

Tautomerism of uracil and related compounds: A mass spectrometry study.

It has been demonstrated that uracil has a preponderant tautomeric form, but it is also known that different tautomers co-exist in this equilibrium. In this work, mass spectrometry is used as a helpful tool to analyse the equilibria, using derivative compounds to forbid the presence of some tautomers and ion trap mass spectrometry to follow relevant fragmentation pathways. Theoretical calculations were performed to confirm tautomers abundance by energy minimization in gas phase. Analysis of mass spectra of uracil, three methyl-substituted uracils, 2-thiouracil and three benzouracils suggest that uracil exists mainly as three tautomers in gas phase: one major structure that corresponds to the classical structure of uracil (pyrimidine-2,4(1H,3H)-dione) bearing two carbonyls and two NH moieties, and two minor enolic forms (4-hydroxypyrimidin-2(1H)-one and 2-hydroxypyrimidin-4(1H)-one). Such tautomeric distribution is supported by theoretical calculations, which show that they are the three most stable tautomers.