Sol–Gel Coordination Chemistry: Building Catalysts from the Bottom-Up

The development of synthetic routes for the tailoring of efficient silica-based heterogeneous catalysts functionalized with coordination complexes or metallic nanoparticles has become a important goal in chemistry. Most of these techniques have been based on postsynthetic treatments of preformed silicas. Nevertheless, there is an emerging approach, so-called sol–gel coordination chemistry, based on co-condensation during the sol–gel preparation of the hybrid material of the corresponding complex or nanoparticle modified with terminal trialkoxysilane groups with a silica source (such as tetraethoxysilane) and in the presence of an adequate surfactant. This method leads to the production of new mesoporous metal complex-silica materials, with the metallic functionality incorporated homogeneously into the structure of the hybrid material, improving the stability of the coordination complex (which is protected by the silica network) and reducing the leaching of the active phase. This technique also offers the actual possibility of functionalizing silica or other metal oxides for a wider range of applications, such as photonics, sensing, and biochemical functions.

Metal-complex ionosilicas: Cationic mesoporus silica with Ni(II) and Cu(II) complexes in their framework

Metal-complex ionosilicas with cationic complexes into the mesoporous silica framework were prepared using anionic surfactants. The electrostatic interaction between the anionic surfactant and the cationic metal complexes incorporated in the silica framework allows for the fine tuning of the mesoporous structure. The gentle procedure of synthesis developed and mild ion-exchange extraction of the surfactant, allowed a cleaner route for the immobilization of homogeneous cationic catalysts in mesoporous silica, while protecting the structural and chemical integrity of the metal complexes.

Microwave-assisted catalysis by iron oxide nanoparticles on MCM-41: Effect of the support morphology

Catalytically active heterogeneous catalysts have been prepared via microwave deposition of iron oxide nanoparticles (0.5–1.2 wt%) on MCM-41 type silica materials with different morphologies (particles, helical and spheres). This methodology leads to iron oxide nanoparticles composed by a mixture of FeO and Fe2O3 species, being the Fe(II)/Fe(III) peak ratio near to 1.11 by XPS. DRUV spectroscopy indicates the presence of tetrahedral coordinated Fe3+ in the silica framework of the three catalysts as well as some extraframework iron species in the catalysts with particle and sphere-like morphologies. The loading of the nanoparticles does neither affect the mesopore arrangement nor the textural properties of the silica supports, as indicated by SAXS and nitrogen adsorption/desorption isotherms. A detailed investigation of the morphology of the supports in various microwave-assisted catalyzed processes shows that helical mesostructures provide optimum catalytic activities and improved reusabilities in the microwave-assisted redox (selective oxidation of benzyl alcohol) catalyzed process probably due to a combination of lower particle size and higher acidity in comparison with the supports with particle and sphere morphology.

Handling of Uncertainty in Life Cycle Inventory by Correlated Multivariate Lognormal Distributions: Application to the Design of Supply Chain Networks

Poster presented in the 24th European Symposium on Computer Aided Process Engineering (ESCAPE 24), Budapest, Hungary, June 15-18, 2014.

Estimation Models for Nonuniformly Sampled Signals–Application to Multiple Delay Estimation

This letter presents a method to model propagation channels for estimation, in which the sampling scheme can be arbitrary. Additionally, the method yields accurate models, with a size that converges to the channel duration, measured in Nyquist periods. It can be viewed as an improvement on the usual discretization based on regular sampling at the Nyquist rate. The method is introduced in the context of multiple delay estimation using the MUSIC estimator, and is assessed through a numerical example.

SeismicWaveTool: Continuous and discrete wavelet analysis and filtering for multichannel seismic data

A MATLAB-based computer code has been developed for the simultaneous wavelet analysis and filtering of multichannel seismic data. The considered time–frequency transforms include the continuous wavelet transform, the discrete wavelet transform and the discrete wavelet packet transform. The developed approaches provide a fast and precise time–frequency examination of the seismograms at different frequency bands. Moreover, filtering methods for noise, transients or even baseline removal, are implemented. The primary motivation is to support seismologists with a user-friendly and fast program for the wavelet analysis, providing practical and understandable results.

Linear low-density polyethylene colored with a nanoclay-based pigment: Morphology and mechanical, thermal, and colorimetric properties

In this study, a novel kind of hybrid pigment based on nanoclays and dyes was synthesized and characterized. These nanoclay-based pigments (NCPs) were prepared at the laboratory with sodium montmorillonite nanoclay (NC) and methylene blue (MB). The cation-exchange capacity of NC exchanged with MB was varied to obtain a wide color gamut. The synthesized nanopigments were thoroughly characterized. The NCPs were melt-mixed with linear low-density polyethylene (PE) with an internal mixer. Furthermore, samples with conventional colorants were prepared in the same way. Then, the properties (mechanical, thermal, and colorimetric) of the mixtures were assessed. The PE–NCP samples developed better color properties than those containing conventional colorants and used as references, and their other properties were maintained or improved, even at lower contents of dye compared to that with the conventional colorants.

Reproducibility comparison among multiangle spectrophotometers

New color-measuring instruments known as multiangle spectrophotometers have been recently created to measure and characterize the goniochromism of special-effect pigments in many materials with a particular visual appearance (metallic, interference, pearlescent, sparkle, or glitter). These devices measure the gonioapparent color from the spectral relative reflectance factor and the L*a*b* values of the sample with different illumination and observation angles. These angles usually coincide with requirements marked in American Society for Testing and Materials (ASTM) and Deutsches Institut Für Normung standards relating to the gonioapparent color, but the results of comparisons between these instruments are still inconclusive. Therefore, the main purpose of this study is to compare several multiangle spectrophotometers at a reproducibility level according to ASTM E2214-08 guidelines. In particular, we compared two X-Rite multi-gonio spectrophotometers (MA98 and MA68II), a Datacolor multi-gonio spectrophotometer (FX10), and a BYK multi-gonio spectrophotometer (BYK-mac). These instruments share only five common measurement geometries: 45° × −30° (as 15°), 45° × −20° (as 25°), 45° × 0° (as 45°), 45° × 30° (as 75°), 45° × 65° (as 110°). Specific statistical studies were used for the reproducibility comparison, including a Hotelling test and a statistical intercomparison test to determine the confidence interval of the partial color differences ΔL*, Δa*, Δb*, and the total color difference ΔE*ab. This was conducted using a database collection of 88 metallic and pearlescent samples that were measured 20 times without the replacement of all the instruments. The final findings show that in most measurement geometries, the reproducibility differences between pairs of instruments are statistically significant, although in general, there is a better reproducibility level at certain common geometries for newer instruments (MA98 and BYK-mac). This means that these differences are due to systematic or bias errors (angle tolerances for each geometry, photometric scales, white standards, etc.), but not exclusively to random errors. However, neither of the statistical tests used is valid to discriminate and quantify the detected bias errors in this comparison between instruments.

Familias de curvas elípticas adecuadas para Criptografía Basada en la Identidad

La Criptografía Basada en la Identidad hace uso de curvas elípticas que satisfacen ciertas condiciones (pairingfriendly curves), en particular, el grado de inmersión de dichas curvas debe ser pequeño. En este trabajo se obtienen familias explicitas de curvas elípticas idóneas para este escenario. Dicha criptografía está basada en el cálculo de emparejamientos sobre curvas, cálculo factible gracias al algoritmo de Miller. Proponemos una versión más eficiente que la clásica de este algoritmo usando la representación de un número en forma no adyacente (NAF).

Conversion of a digital camera into a non-contact colorimeter for use in stone cultural heritage: The application case to Spanish granites

In this study, a digital CMOS camera was calibrated for use as a non-contact colorimeter for measuring the color of granite artworks. The low chroma values of the granite, which yield similar stimulation of the three color channels of the camera, proved to be the most challenging aspect of the task. The appropriate parameters for converting the device-dependent RGB color space into a device-independent color space were established. For this purpose, the color of a large number of Munsell samples (corresponding to the previously defined color gamut of granite) was measured with a digital camera and with a spectrophotometer (reference instrument). The color data were then compared using the CIELAB color formulae. The best correlations between measurements were obtained when the camera works to 10-bits and the spectrophotometric measures in SCI mode. Finally, the calibrated instrument was used successfully to measure the color of six commercial varieties of Spanish granite.

Astrophysical parameters and orbital solution of the peculiar X-ray transient IGR J00370+6122

Context. BD + 60° 73 is the optical counterpart of the X-ray source IGR J00370+6122, a probable accretion-powered X-ray pulsar. The X-ray light curve of this binary system shows clear periodicity at 15.7 d, which has been interpreted as repeated outbursts around the periastron of an eccentric orbit. Aims. We aim to characterise the binary system IGR J00370+6122 by deriving its orbital and physical parameters. Methods. We obtained high-resolution spectra of BD + 60° 73 at different epochs. We used the fastwind code to generate a stellar atmosphere model to fit the observed spectrum and obtain physical magnitudes. The synthetic spectrum was used as a template for cross-correlation with the observed spectra to measure radial velocities. The radial velocity curve provided an orbital solution for the system. We also analysed the RXTE/ASM and Swift/BAT light curves to confirm the stability of the periodicity. Results. BD + 60° 73 is a BN0.7 Ib low-luminosity supergiant located at a distance ~3.1 kpc, in the Cas OB4 association. We derive Teff = 24 000 K and log gc = 3.0, and chemical abundances consistent with a moderately high level of evolution. The spectroscopic and evolutionary masses are consistent at the 1-σ level with a mass M∗ ≈ 15 M⊙. The recurrence time of the X-ray flares is the orbital period of the system. The neutron star is in a high-eccentricity (e = 0.56 ± 0.07) orbit, and the X-ray emission is strongly peaked around orbital phase φ = 0.2, though the observations are consistent with some level of X-ray activity happening at all orbital phases. Conclusions. The X-ray behaviour of IGR J00370+6122 is reminiscent of “intermediate” supergiant X-ray transients, though its peak luminosity is rather low. The orbit is somewhat wider than those of classical persistent supergiant X-ray binaries, which when combined with the low luminosity of the mass donor, explains the low X-ray luminosity. IGR J00370+6122 will very likely evolve towards a persistent supergiant system, highlighting the evolutionary connection between different classes of wind-accreting X-ray sources.

VdBH 222: a starburst cluster in the inner Milky Way

Context. It has been suggested that the compact open cluster VdBH 222 is a young massive distant object. Aims. We set out to characterise VdBH 222 using a comprehensive set of multi-wavelength observations. Methods. We obtained multi-band optical (UBVR) and near-infrared (JHKS) photometry of the cluster field, as well as multi-object and long-slit optical spectroscopy for a large sample of stars in the field. We applied classical photometric analysis, as well as more sophisticated methods using the CHORIZOS code, to determine the reddening to the cluster. We then plotted dereddened HR diagrams and determined cluster parameters via isochrone fitting. Results. We have identified a large population of luminous supergiants confirmed as cluster members via radial velocity measurements. We find nine red supergiants (plus one other candidate) and two yellow supergiants. We also identify a large population of OB stars. Ten of them are bright enough to be blue supergiants. The cluster lies behind ≈7.5 mag of extinction for the preferred value of RV = 2.9. Isochrone fitting allows for a narrow range of ages between 12 and 16 Ma. The cluster radial velocity is compatible with distances of ~6 and ~10 kpc. The shorter distance is inconsistent with the age range and Galactic structure. The longer distance implies an age ≈ 12 Ma and a location not far from the position where some Galactic models place the far end of the Galactic bar. Conclusions. VdBH 222 is a young massive cluster with a likely mass >20 000 M⊙. Its population of massive evolved stars is comparable to that of large associations, such as Per OB1. Its location in the inner Galaxy, presumably close to the end of the Galactic bar, adds to the increasing evidence for vigorous star formation in the inner regions of the Milky Way.

A quasi-elastic aquifer deformational behavior: Madrid aquifer case study

The purpose of this paper is to analyze the quasi-elastic deformational behavior that has been induced by groundwater withdrawal of the Tertiary detrital aquifer of Madrid (Spain). The spatial and temporal evolution of ground surface displacement was estimated by processing two datasets of radar satellite images (SAR) using Persistent Scatterer Interferometry (PSI). The first SAR dataset was acquired between April 1992 and November 2000 by ERS-1 and ERS-2 satellites, and the second one by the ENVISAT satellite between August 2002 and September 2010. The spatial distribution of PSI measurements reveals that the magnitude of the displacement increases gradually towards the center of the well field area, where approximately 80 mm of maximum cumulated displacement is registered. The correlation analysis made between displacement and piezometric time series provides a correlation coefficient greater than 85% for all the wells. The elastic and inelastic components of measured displacements were separated, observing that the elastic component is, on average, more than 4 times the inelastic component for the studied period. Moreover, the hysteresis loops on the stress–strain plots indicate that the response is in the elastic range. These results demonstrate the quasi-elastic behavior of the aquifer. During the aquifer recovery phase ground surface uplift almost recovers from the subsidence experienced during the preceding extraction phase. Taking into account this unique aquifer system, a one dimensional elastic model was calibrated in the period 1997–2000. Subsequently, the model was used to predict the ground surface movements during the period 1992–2010. Modeled displacements were validated with PSI displacement measurements, exhibiting an error of 13% on average, related with the inelastic component of deformation occurring as a long-term trend in low permeability fine-grained units. This result further demonstrates the quasi-elastic deformational behavior of this unique aquifer system.

La palmera datilera y la palmera canaria en la medicina tradicional de España

En la actualidad son muy pocos los usos vigentes. Aunque los dátiles son la materia utilizada con mayor frecuencia, también se han empleado la savia, el polen y el cogollo tierno o palmito. Los dátiles de Phoenix dactylifera se utilizaron como analgésico y para tratar la anemia y trastornos digestivos, o para fortalecer las encías, en el tratamiento de la disfunción eréctil y como afrodisiacos, para facilitar el parto y calmar los dolores postparto, y tratar el prolapso de la matriz o para el exceso de flujo menstrual. También se utilizaron como diuréticos, para la disuria y en trastornos de la vejiga. El uso que más claramente ha persistido es el tratamiento de diversos problemas respiratorios. En uso externo se utilizaron para tratar problemas de la piel, heridas, hemorragias y hemorroides. De la palmera de Canarias (Phoenix canariensis), especialmente en la isla de la Gomera, la savia cruda o guarapo, su concentrado o miel de palma y los resultantes de su fermentación (vino de palma) se consumen como alimento y también se utilizan como diurético, remedio de trastornos génitourinarios, digestivo, para infecciones de la cavidad bucal, expectorante, antitusígeno y para las irritaciones de garganta. En el Toledo de Al-Andalus las espatas de P. dactylifera se utilizaron, hace casi mil años, en el tratamiento de la debilidad, los dolores, nefritis, las enfermedades de la vejiga, trastornos hepáticos (también como preventivo), diarrea, trastornos digestivos, dolores en el abdomen y en el estómago, excesivo sangrado menstrual, úlceras en la piel y sarna, dolores articulares y trastornos cardiacos. La fitoterapia racional debería prestar atención a este recurso, considerar la evidencia científica disponible (farmacológica e incluso clínica) e incorporarlo a nuestro repertorio terapéutico.

Consequences of Kondo exchange on quantum spins

When individual quantum spins are placed in close proximity to conducting substrates, the localized spin is coupled to the nearby itinerant conduction electrons via Kondo exchange. In the strong coupling limit this can result in the Kondo effect — the formation of a correlated, many body singlet state — and a resulting renormalization of the density of states near the Fermi energy. However, even when Kondo screening does not occur, Kondo exchange can give rise to a wide variety of other phenomena. In addition to the well known renormalization of the g factor and the finite spin decoherence and relaxation times, Kondo exchange has recently been found to give rise to a newly discovered effect: the renormalization of the single ion magnetic anisotropy. Here we put these apparently different phenomena on equal footing by treating the effect of Kondo exchange perturbatively. In this formalism, the central quantity is ρJ, the product of the density of states at the Fermi energy ρ and the Kondo exchange constant J. We show that perturbation theory correctly describes the experimentally observed exchange induced shifts of the single spin excitation energies, demonstrating that Kondo exchange can be used to tune the effective magnetic anisotropy of a single spin.