Degradation of pharmaceutical compound pentoxifylline in water by non-thermal plasma treatment

The decomposition of a model pharmaceutical compound, pentoxifylline, in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration, operated in pulsed regime, at atmospheric pressure and room temperature. The solution was made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. Oxygen was introduced with a flow rate of 600 sccm. After 60 min plasma treatment 92.5% removal of pentoxifylline was achieved and the corresponding decomposition yield was 16 g/kWh. It was found that pentoxifylline degradation depended on the initial concentration of the compound, being faster for lower concentrations. Faster decomposition of pentoxifylline could be also achieved by increasing the pulse repetition rate, and implicitly the power introduced in the discharge, however, this had little effect on the decomposition yield. The degradation products were investigated by liquid chromatography-mass spectrometry technique (LC-MS). The evolution of the intermediates during plasma treatment showed a fast increase in the first 30 min, followed by a slower decrease, so that these products are almost completely removed after 120 min treatment time.     

Metal Triflates Incorporated in Mesoporous Catalysts for Green Synthesis of Fine Chemicals

Strong Lewis acid SnTf-MCM-41 and SnTf-UVM-7 catalysts with unimodal and bimodal pore systems were prepared in a two-step synthesis in which the triflic acid (Tf) was incorporated into previously synthesized mesoporous tin-containing silicas. The Sn incorporation inside the pore walls was carried out through the Atrane method. The SnTf-UVM-7 catalysts were prepared by aggregating nanometric mesoporous particles defining a hierarchic textural-type additional pore system. Catalysts with different Si/Sn ratios in the range 21.8–50.8 for SnTf-MCM-41 and 18.4 for SnTf-UVM-7 were found to be efficient catalysts for the acylation of aromatics and heteroaromatics. Under microwave irradiation the reaction was possible even with acetic acid. The selectivity to the desired product (o-hydroxyacetophenone for phenol) or the unfavored three-substituted five ring heterocycles was dramatically increased under these conditions. The process is green, environmentally safe, and heterogeneous.     

Degradation of antibiotics in water by non-thermal plasma treatment

The decomposition of three β-lactam antibiotics (amoxicillin, oxacillin and ampicillin) in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration. Solutions of concentration 100 mg/L were made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. The electrical discharge was operated in pulsed regime, at room temperature and atmospheric pressure, in oxygen. Amoxicillin was degraded after 10 min plasma treatment, while the other two antibiotics required about 30 min for decomposition. The evolution of the degradation process was continuously followed using liquid chromatography-mass spectrometry (LC-MS), total organic carbon (TOC) and chemical oxygen demand (COD) analyses.     

Acylation of sulfonamines using silica grafted 1-butyl-3-(3-triethoxysilylpropyl)-4,5-dihydroimidazolium ionic liquids as catalysts

Heterogeneous immobilized ionic liquid catalysts were prepared via grafting of 1,3-dimethyl-3-(3-triethoxysilylpropyl)-imidazolium tetrafluoroborate or bis{(trifluoromethyl)sulfonyl} imide ([NTf₂]⁻) on silica supports with different surfaces and pore size. In addition to the adsorption–desorption isotherms of nitrogen at −196 °C, the catalysts were characterized by TG-DTA, XPS, DRIFTS, DR-UV–vis, NMR, and XRD techniques. The catalytic behavior was checked in the acylation of three different sulfonamines: benzenesulfonamine, p-nitrobenzenesulfonamine, and p-methoxybenzene-sulfonamine with acetic acid, acetic anhydride and maleic anhydride. These tests confirmed the acid Lewis properties of these catalysts.     

First In Situ Raman Study of Vanadium Oxide Based SO2 Oxidation Supported Molten Salt Catalysts

In situ Raman spectroscopy at temperatures up to 500°C is used for the first time to identify vanadium species on the surface of a vanadium oxide based supported molten salt catalyst during SO₂ oxidation. Vanadia/silica catalysts impregnated with Cs₂SO₄ were exposed to various SO₂/O₂/SO₃ atmospheres and in situ Raman spectra were obtained and compared to Raman spectra of unsupported model V₂O₅–Cs₂SO₄ and V₂O₅–Cs₂S₂O₇ molten salts. The data indicate that (1) the V^V complex V^VO₂(SO₄)₂ ^3– (with characteristic bands at 1034 cm^–1 due to (V=O) and 940 cm^–1 due to sulfate) and Cs₂SO₄ dominate the catalyst surface after calcination; (2) upon admission of SO₃/O₂ the excess sulfate is converted to pyrosulfate and the V^V dimer (V^VO)₂O(SO₄)₄ ^4– (with characteristic bands at 1046 cm^–1 due to (V=O), 830 cm^–1 due to bridging S–O along S–O–V and 770 cm^–1 due to V–O–V) is formed and (3) admission of SO₂ causes reduction of V^V to V^IV (with the (V=O) shifting to 1024 cm^–1) and to V^IV precipitation below 420°C.     

Comparative photocatalytic behavior of Ta catalysts prepared by d.c.-sputtering, sol–gel and grafting in acetone degradation

Ta-doped photocatalysts were prepared using three different techniques: reactive d.c.-magnetron sputtering, sol–gel and grafting of tantalum on MCM-41 and TiO₂. The composition of the catalysts prepared by reactive d.c.-magnetron sputtering consisted in tantalum and titania, while that of sol–gel and grafted catalysts of Ta–titania–silica mixed oxides. The characterization of these catalysts was carried out using the adsorption-desorption isotherms of N₂ at 77 K, X-ray diffraction (XRD) patterns, small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), XPS, TEM, and ²⁹Si- and ¹⁸¹Ta-CP/MAS NMR spectra. The behavior of these photocatalysts was checked in acetone degradation. The photocatalytic tests indicate that, depending on the preparation conditions and tantalum content, an enhancement of the activity occurs as compared with pure titania. Sol–gel and Ta-grafted MCM and TiO₂ catalysts exhibited a rather poor activity, which was correlated with the lack of crystallinity of titania.     

Iron, cobalt or nickel substituted MCM-41 molecular sieves for oxidation of hydrocarbons

A series of mesoporous Fe-MCM-41, Co-MCM-41 and Ni-MCM-41 catalysts with different quantity of the metal incorporated in the framework were synthesized and characterized (as-synthesized samples and those after reaction) by X-ray diffraction pattern (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) techniques. The effect of the incorporated metal on the MCM-41 surface hydroxyl groups has been evidenced. The catalytic activity and selectivity of these catalysts in liquid phase oxidation of 1-hexene, styrene and benzene with hydrogen peroxide were studied. The structure and morphology of the catalysts before and after reaction were also compared. The results show a high activity and selectivity of catalysts having higher Co content to benzaldehyde from styrene or phenol from benzene, and a low activity of all prepared catalysts in the oxidation of the 1-hexene. The activity and efficiency of H₂O₂ increases with the metal content and depend on the reaction parameters such as temperature, molar ratio of the reactants and the solvent, and the nature of the reactor.     

Alkylation of Phenols and Naphthols on Silica-Immobilized Triflate Derivatives

Immobilized triflate derivatives (La(OTf)₃, AgOTf, tert-butyldimethylsilyltrifluoro-methanesulfonate), and triflic acid were found to be effective in the alkylation of phenol and naphthols with tert-butanol. The acidic strength and type of acidity (Lewis or Brønsted) are key factors controlling the conversion and product distribution.     

Bifunctional Nanoscopic Catalysts for the One-Pot Synthesis of (±)-Menthol from Citral

Active and selective bifunctional Me(Ir, Pd)/beta zeolite and doped nanoscopic hydroxylated fluorides (0.1?% Pd (or Pt)/AlF₃) catalysts were developed for the one-pot synthesis of menthols from citral. In the case of fluoride catalysts, the strong electron-withdrawing effect of the dominating fluoride environment depletes the metal surface from electrons and hence, favours the hydrogenation of the C=C bond to citronellal on both Pd and Pt-based catalysts.     

Heterogeneous Raney Nickel and Cobalt Catalysts for Racemization and Dynamic Kinetic Resolution of Amines

Raney metals were studied as heterogeneous catalysts for racemization and dynamic kinetic resolution (DKR) of chiral amines, as an alternative to metals like palladium or ruthenium. Both Raney nickel and cobalt were able to selectively racemize various chiral amines with high selectivity. In the racemization of benzylic primary amines, the minor formation of side products, e.g., secondary amines, can be suppressed by varying the hydrogen pressure. In the racemization of aliphatic amines over Raney catalysts, the selectivity is very high, with the enantiomeric amine as the sole product. DKR of racemic aliphatic amines can be performed with immobilized Candida antarctica lipase B and Raney nickel in one pot; for 2‐hexylamine, a yield of 95 % of the acetylated amide was achieved, with 97 % ee. Attention is devoted to the compatibility of the enzyme and the metal catalyst during the DKR. For benzylic primary amines, a two‐pot process is proposed in which the liquid is alternatingly shuttled between two vessels containing the solid racemization catalyst and the biocatalyst. After 4 such cycles, the amide of (R)‐1‐phenylethylamine was obtained with 94 % yield and more than 90 % ee.