Pedro B. Tavares

Designing Novel Hybrid Materials by One-Pot Co-condensation: From Hydrophobic Mesoporous Silica Nanoparticles to Superamphiphobic Cotton Textiles

This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic.

Size and surface effects on the magnetic properties of NiO nanoparticles

NiO nanoparticles (NPs) were prepared by a sol-gel process using the citrate route. The sol-gel parameters were tuned to obtain samples with different average particle sizes, ranging from 12 to 70 nm. Magnetic characterization revealed an increase in the blocking temperature with the diameter of the NPs and an increase in the effective magnetic anisotropy (K(eff)) with decreasing particle size. The magnetic moment per particle was calculated for all samples using the susceptibility value at T = 300 K. The number of uncompensated spins per NP was found to be proportional to n (n(S)≡ total number of spins), indicating that they are randomly distributed on the NP surface. For small diameters (<30 nm) the surface anisotropy constant was estimated, using, for NiO NPs, a recent model describing the evolution of K(eff) with particle size. Hysteretic loops performed at low temperatures after field cooling displayed loop shifts (∼6.5 kOe in the field axis and ∼0.18 emu g(-1) vertically), coercive field enhancement (H(C)≈ 4.8 kOe) and training effects for the smaller NPs. The sample with NPs of larger diameters presented magnetic properties close to those of bulk NiO.

Redox properties and VOC oxidation activity of Cu catalysts supported on Ce1−xSmxOδ mixed oxides

A series of Cu catalysts supported on Ce1-xSmxOδ mixed oxides with different molar contents (x=0, 0.25, 0.5, 0.75 and 1), was prepared by wet impregnation and evaluated for volatile organic compounds (VOC) abatement, employing ethyl acetate as model molecule. An extensive characterization study was undertaken in order to correlate the morphological, structural and surface properties of catalysts with their oxidation activity. The optimum performance was obtained with Cu/CeO2 catalyst, which offers complete conversion of ethyl acetate into CO2 at temperatures as low as 260°C. The catalytic performance of Cu/Ce1-xSmxOδ was interpreted on the basis of characterization studies, showing that incorporation of samarium in ceria has a detrimental effect on the textural characteristics and reducibility of catalysts. Moreover, high Sm/Ce atomic ratios (from 1 to 3) resulted in a more reduced copper species, compared to CeO2-rich supports, suggesting the inability of these species to take part in the redox mechanism of VOC abatement. Sm/Ce surface atomic ratios are always much higher than the nominal ratios indicating an impoverishment of catalyst surface in cerium oxide, which is detrimental for VOC activity.

Nanostructured iron oxide catalysts with gold for the oxidation of carbon monoxide

A commercial iron oxide support is compared with Fe2O3 samples prepared by decomposition of iron nitrate, at 300 °C and 500 °C and heating times varying from 30 min to 96 h in N2. Different methods were used for gold deposition, namely double impregnation (DIM), liquid phase reductive deposition (LPRD) and ultrasonication (US). Samples were characterised by N2 adsorption at −196 °C, high-resolution transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and temperature programmed reduction. CO oxidation was used as a test reaction to compare the catalytic activities. The best results were obtained for the sample produced by decomposition of nitrate at 300 °C for 1 h, which showed the largest surface area and highest amount of hydroxylated iron species. Increasing the calcination time and/or the temperature produced less active samples. Although LPRD materials showed the smallest gold nanoparticle sizes (1–12 nm), the best catalytic results were obtained for the DIM materials. This is most likely related to the oxidation state of gold (Au+) found in the DIM catalysts, in contrast with LPRD and US materials, where metallic gold (Au0) is present. Other samples showed lower activities. Nevertheless, all samples prepared by DIM had better catalytic activity than the Au/Fe2O3 World Gold Council reference catalyst.

Facile one-pot synthesis of Pt nanoparticles /SBA-15: an active and stable material for catalytic applications

Pt/SBA-15 with an enhanced surface area but unchanged pore diameter (compared to pure SBA-15) and a Pt average particle size of ∼9 nm shows a high and stable activity for both gas-phase CO oxidation and liquid-phase cyclooctadiene hydrogenation. No intrinsic change in the structure of the catalyst occurs after several reaction cycles, suggesting that the Pt/SBA-15 presented here is an active and stable catalyst.

The rs5743836 polymorphism in TLR9 confers a population-based increased risk of non-Hodgkin lymphoma

Non-Hodgkin lymphoma (NHL) has been associated with immunological defects, chronic inflammatory and autoimmune conditions. Given the link between immune dysfunction and NHL, genetic variants in toll-like receptors (TLRs) have been regarded as potential predictive factors of susceptibility to NHL. Adequate anti-tumoral responses are known to depend on TLR9 function, such that the use of its synthetic ligand is being targeted as a therapeutic strategy. We investigated the association between the functional rs5743836 polymorphism in the TLR9 promoter and risk for B-cell NHL and its major subtypes in three independent case–control association studies from Portugal (1160 controls, 797 patients), Italy (468 controls, 494 patients) and the US (972 controls, 868 patients). We found that the rs5743836 polymorphism was significantly overtransmitted in both Portuguese (odds ratio (OR), 1.85; P=7.3E−9) and Italian (OR, 1.84; P=6.0E−5) and not in the US cohort of NHL patients. Moreover, the increased transcriptional activity of TLR9 in mononuclear cells from patients harboring rs5743836 further supports a functional effect of this polymorphism on NHL susceptibility in a population-dependent manner.

Gold nanoparticles supported on magnesium oxide for CO oxidation

Au was loaded (1 wt%) on a commercial MgO support by three different methods: double impregnation, liquid-phase reductive deposition and ultrasonication. Samples were characterised by adsorption of N2 at -96°C, temperature-programmed reduction, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction. Upon loading with Au, MgO changed into Mg(OH)2 (the hydroxide was most likely formed by reaction with water, in which the gold precursor was dissolved). The size range for gold nanoparticles was 2-12 nm for the DIM method and 3-15 nm for LPRD and US. The average size of gold particles was 5.4 nm for DIM and larger than 6.5 for the other methods. CO oxidation was used as a test reaction to compare the catalytic activity. The best results were obtained with the DIM method, followed by LPRD and US. This can be explained in terms of the nanoparticle size, well known to determine the catalytic activity of gold catalysts.

Anisotropic electrical transport in epitaxial La2/3Ca1/3MnO3 thin films

Epitaxial thin films of La0.62±0.05Ca0.33±0.02MnO3−δ were grown by laser ablation on SrTiO3. On (100) substrates the films grow with the larger c axis perpendicular to the plane. The films deposited on (110) SrTiO3 grow with both the c (long) axis and a (or b, short) axis in the plane of the film. The electrical resistivity (ρ) and the magnetoresistance (Δρ/ρ) show crystalline anisotropy. The resistivity ratio between the a and c axis is constant (0.8) from 10 K up to 120 K and decreases to 0.77 between 125 and 225 K, shows a small peak anomaly at Tc (257 K), and is almost constant in the paramagnetic phase. This temperature dependence is associated with anisotropic local lattice distortions. The magnetoresistance anisotropy (Δρ/ρ∥−Δρ/ρ⊥) with the applied field in the plane of the film, is small at low temperatures, peaks close to Tc, and is slightly larger for measurements along the a axis. The contributions of domain rotation and magnetocrystalline anisotropy to the anisotropic magnetoresistance associa...

Treatment of crystallized-fruit wastewater by UV-A LED photo-Fenton and coagulation-flocculation.

This work reports the treatment of crystallized-fruit effluents, characterized by a very low biodegradability (BOD5/COD <0.19), through the application of a UV-A LED photo-Fenton process. Firstly, a Box-Behnken design of Response Surface Methodology was applied to achieve the optimal conditions for the UV-A LED photo-Fenton process, trying to maximize the efficiency by saving chemicals and time. Under the optimal conditions ([H2O2] = 5459 mg/L; [Fe(3+)] = 286 mg/L; time >180 min), a COD removal of 45, 64 and 74% was achieved after 360 min, using an irradiance of 23, 70 and 85 W/m(2) respectively. Then a combination of UV-A LED photo-Fenton with coagulation-flocculation-decantation attained a higher COD removal (80%), as well as almost total removal of turbidity (99%) and total suspended solids (95%). Subsequent biodegradability of treated effluents increased, allowing the application of a biological treatment step after the photochemical/CFD with 85 W/m(2).

Anomalous low-field magnetization in La2/3Ca1/3MnO3 near the critical point: Stable clusters?

The magnetic behavior of bulk La2/3Ca1/3MnO3 (TC=267 K) at low fields in the paramagnetic phase was studied. Near TC(T−TC<30 K) we find a sequence of steplike features in the effective Curie constant C(T)=M(T−TC)/H at well defined temperatures and intermediate plateaus, accompanied by temperature hysteresis. On approaching TC, the C values at each plateau follow a geometrical progression, with the effective spin S doubled at each step. The first plateau gives S=5.5, corresponding to a cluster of three Mn3+ ions sharing one extra hole. This suggests that close to TC short range magnetic order at low fields develops hierarchically through a series of most stable cluster states.