Centro Atómico Constituyentes

The energy spectrum of cosmic rays above $2.5\ifmmode\times\else\texttimes\fi{}{10}^{18}\text{ }\mathrm{eV}$, derived from 20 000 events recorded at the Pierre Auger Observatory, is described. The spectral index $\ensuremath{\gamma}$ of the particle flux, $J\ensuremath{\propto}{E}^{\ensuremath{-}\ensuremath{\gamma}}$, at energies between $4\ifmmode\times\else\texttimes\fi{}{10}^{18}\text{ }\mathrm{eV}$ and $4\ifmmode\times\else\texttimes\fi{}{10}^{19}\text{ }\mathrm{eV}$ is $2.69\ifmmode\pm\else\textpm\fi{}0.02(\mathrm{stat})\ifmmode\pm\else\textpm\fi{}0.06(\mathrm{syst})$, steepening to $4.2\ifmmode\pm\else\textpm\fi{}0.4(\mathrm{stat})\ifmmode\pm\else\textpm\fi{}0.06(\mathrm{syst})$ at higher energies. The hypothesis of a single power law is rejected with a significance greater than 6 standard deviations. The data are consistent with the prediction by Greisen and by Zatsepin and Kuz'min.

This critical review presents and discusses the recent advances in complex hybrid materials that result from the combination of polymers and mesoporous matrices. Ordered mesoporous materials derived from supramolecular templating present high surface area and tailored pore sizes; pore surfaces can be further modified by organic, organometallic or even biologically active functional groups. This permits the creation of hybrid systems with distinct physical properties or chemical functions located in the framework walls, the pore surface, and the pore interior. Bringing polymeric building blocks into the game opens a new dimension: the possibility to create phase separated regions (functional domains) within the pores that can behave as "reactive pockets" of nanoscale size, with highly controlled chemistry and interactions within restricted volumes. The possibilities of combining "hard" and "soft" building blocks to yield these novel nanocomposite materials with tuneable functional domains ordered in space are potentially infinite. New properties are bound to arise from the synergy of both kinds of components, and their spatial location. The main object of this review is to report on new approaches towards functional polymer-inorganic mesostructured hybrids, as well as to discuss the present challenges in this flourishing research field. Indeed, the powerful concepts resulting from the synergy of sol-gel processing, supramolecular templating and polymer chemistry open new opportunities in the design of advanced functional materials: the tailored production of complex matter displaying spatially-addressed chemistry based on the control of chemical topology. Breakthrough applications are expected in the fields of sustainable energy, environment sensing and remediation, biomaterials, pharmaceutical industry and catalysis, among others (221 references).

Photocatalytic activity of anatase cubic-based ordered mesoporous thin films was related to the morphology of the crystalline porous network obtained upon thermal treatment with a specific incremented sequence. The porosity and pore size distribution of these thin films were investigated with a novel Environmental Ellipsometric Porosimetry (EEP) technique. Network crystallinity was assessed by XRD. In parallel, the evolution of the photocatalytic activity was studied through UV-induced photodegradation of methylene blue and lauric acid within the films at the various steps of the temperature treatment. The photoactivity was linked to the porous characteristics of the films and we concluded that the activity is optimal when the porosity is high and completely accessible, and when the nanoparticle and pore size have dimensions of 7.5 and 5.5 nm respectively. Such an optimal system was obtained after a sequential thermal treatment ending with 10 min at 600 °C in air, for which the films adopts an ordered bidirectional grid-like structure.

A novel optical sensor is proposed, based on the normal-incidence excitation of Tamm plasmons at the interface between a multilayer of porous SiO2 and TiO2, acting as a permeable Bragg reflector, and a flat gold film. Transmittance spectra reveal a sharp Tamm mode within the stop-band of the distributed Bragg reflector, the spectral position of which was monitored upon exposure to various solvents, demonstrating the sensitivity of the device to changes of refractive index.

Our main goal was to investigate if robust chemical fingerprints could be developed for three Argentinean red wines based on organic, inorganic, and isotopic patterns, in relation to the regional soil composition. Soils and wines from three regions (Mendoza, San Juan, and Córdoba) and three varieties (Cabernet Sauvignon, Malbec, and Syrah) were collected. The phenolic profile was determined by HPLC-MS/MS and multielemental composition by ICP-MS; (87)Sr/(86)Sr and δ(13)C were determined by TIMS and IRMS, respectively. Chemometrics allowed robust differentiation between regions, wine varieties, and the same variety from different regions. Among phenolic compounds, resveratrol concentration was the most useful marker for wine differentiation, whereas Mg, K/Rb, Ca/Sr, and (87)Sr/(86)Sr were the main inorganic and isotopic parameters selected. Generalized Procrustes analysis (GPA) using two studied matrices (wine and soil) shows consensus between them and clear differences between studied areas. Finally, we applied a canonical correlation analysis, demonstrating significant correlation (r = 0.99; p < 0.001) between soil and wine composition. To our knowledge this is the first report combining independent variables, constructing a fingerprint including elemental composition, isotopic, and polyphenol patterns to differentiate wines, matching part of this fingerprint with the soil provenance.

The surface detector array of the Pierre Auger Observatory is sensitive to Earth-skimming tau neutrinos that interact in Earth's crust. Tau leptons from ${\ensuremath{\nu}}_{\ensuremath{\tau}}$ charged-current interactions can emerge and decay in the atmosphere to produce a nearly horizontal shower with a significant electromagnetic component. The data collected between 1 January 2004 and 31 August 2007 are used to place an upper limit on the diffuse flux of ${\ensuremath{\nu}}_{\ensuremath{\tau}}$ at EeV energies. Assuming an ${E}_{\ensuremath{\nu}}^{\ensuremath{-}2}$ differential energy spectrum the limit set at 90% C.L. is ${E}_{\ensuremath{\nu}}^{2}d{N}_{{\ensuremath{\nu}}_{\ensuremath{\tau}}}/d{E}_{\ensuremath{\nu}}&lt;1.3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}\text{ }\text{ }\mathrm{GeV}\text{ }{\mathrm{cm}}^{\ensuremath{-}2}\text{ }{\mathrm{s}}^{\ensuremath{-}1}\text{ }{\mathrm{sr}}^{\ensuremath{-}1}$ in the energy range $2\ifmmode\times\else\texttimes\fi{}{10}^{17}\text{ }\text{ }\mathrm{eV}&lt;{E}_{\ensuremath{\nu}}&lt;2\ifmmode\times\else\texttimes\fi{}{10}^{19}\text{ }\text{ }\mathrm{eV}$.

We report processing of a thin film by chemical solution deposition of a microporous ZIF-8 nanoparticle dispersion. By using the drain and capillary regimes involved in the dip-coating process, we tuned the thickness of the films from 40 nm to 1 μm and controlled the packing of the nanoparticles on the substrate. The high optical quality thin films show a dual hierarchical porous structure from the micropores of the framework and the mesoporous interparticular voids. Moreover, vapor sorption properties of the microporous ZIF-8 based thin films have been evaluated by ellipsometric porosimetry. The hydrophobic films show alcohol, THF and hydrocarbon adsorption. Experiments for isopropanol/water separation have been carried out and the selective adsorption of the alcohol versus the water makes these thin films good candidates for vapor sensors.

This review presents and discusses recent advances in the emerging field of "gated nanochemistry", outlining the substantial progress made so far. The development of hybrid mesoporous silica with complex tailored pore nanoarchitectures bridges the gap between molecular materials and the requirements of nanodevices for controlled nanoscale chemistry. In the last decade, membranes, particles and thin film porous architectures have been designed, synthesized and selectively modified by molecular, polymeric, organometallic or biologically active groups. The exquisite manipulation of mesopore morphology and interconnection combined with molecular or supramolecular functionalities, and the intrinsic biological compatibility of silica have made these materials a potential platform for selective sensing and drug delivery. The wide répertoire of these hard-soft architectures permit us to envisage sophisticated intelligent nano-systems that respond to a variety of external stimuli such as pH, redox potential, molecule concentration, temperature, or light. Transduction of these stimuli into a predefined response implies exploiting spatial and physico-chemical effects such as charge distribution, steric constraints, equilibria displacements, or local changes in ionic concentration, just to name a few examples. As expected, this "positional mesochemistry" can be only attained through the concerted control of assembly, surface tailoring and, confinement conditions, thus giving birth to a new class of stimuli-responsive materials with modulable transport properties. As a guiding framework the emerging field of "gated nanochemistry" offers methodologies and tools for building up stimuli-sensitive porous architectures equipped with switchable entities whose transport properties can be triggered at will. The gated nanoscopic hybrid materials discussed here not only herald a new era in the integrative design of "smart" drug delivery systems, but also give the reader a perspective of the promising future in the development of mesoporous platforms that can control mass transport on command through the combination of flexible supramolecular routes, with implications on health, environment and energy.

We present experimental evidence on the physical origin of a magnetic dead layer (MDL) in manganite nanoparticles. The studied nanoparticles constitute the wall of La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3 manganite nanotubes. Magnetic properties analysis and high resolution transmission electron microscopy show a shell of approximately 2 nm thickness with different properties from the core. In this shell the atoms are in a noncrystalline array that perfectly explains the 50% reduction of the magnetization compared to the bulk. Moreover, we present experimental evidence that the internal magnetic structure of the MDL is constituted by small ferromagnetic clusters in a frustrated configuration.

We prepared synthetic hydroxyapatite [HAP; Ca5(PO4)(3-x)(CO3)x(OH)(1+x) (x = 0.3)] and then investigated this material's ability to remove trivalent antimony [Sb(III)] from water. The HAP was characterized by X-ray diffraction analysis, scanning electron microscopy, X-ray energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy. The sorption of Sb(III) to HAP was measured over an Sb(III) concentration range of 0.05-50 mg L(-1), at constant ionic strength (I = 0.01 mol dm(-3)) in equilibrated aqueous suspensions (34 g dm(-3)) for 5 < pH < 8 in vessels that were closed to the atmosphere. Under these conditions, we found that HAP particles were enriched in Ca after incongruent dissolution of the solid. More than 95% of the Sb(III) in solution adsorbed to the solid-phase HAP in <30 min. The equilibrium distribution of Sb(III) (solid vs liquid phase) was characterized by a Langmuir model with gamma(max) = 6.7 +/- 0.1 x 10(-8) mol m(-2) (1.4 +/- 0.2 x 10(-4) mol dm(-3) g(-1)) and K(ads) = 1.5 +/- 0.2 x 10(3) dm3 mol(-1). As Sb adsorption occurred, the pH of the isoelectric point (pH(iep)) of the HAP suspensions declined from 7.7 to 6.9. This finding supports the idea that the negative surface potential of the HAP increased due to the adsorption of Sb as a charged species. The decline in pH(iep) during Sb adsorption plus the thermodynamic description of the Sb(III)-HAP-H2O system suggest likely surface reactions for the interaction of Sb with HAP. We discuss the efficiency of Sb removal from water by HAP in the context of phosphate enrichment.

In this work we compare and characterize the behavior of Langevin and dissipative particle dynamics (DPD) thermostats in a broad range of nonequilibrium simulations of polymeric systems. Polymer brushes in relative sliding motion, polymeric liquids in Poiseuille and Couette flows, and brush-melt interfaces are used as model systems to analyze the efficiency and limitations of different Langevin and DPD thermostat implementations. Widely used coarse-grained bead-spring models under good and poor solvent conditions are employed to assess the effects of the thermostats. We considered equilibrium, transient, and steady state examples for testing the ability of the thermostats to maintain constant temperature and to reproduce the underlying physical phenomena in nonequilibrium situations. The common practice of switching off the Langevin thermostat in the flow direction is also critically revisited. The efficiency of different weight functions for the DPD thermostat is quantitatively analyzed as a function of the solvent quality and the nonequilibrium situation.

Silver nanoparticle assemblies are embedded within mesoporous oxide thin films by an in situ mild reduction leading to nanoparticle-mesoporous oxide thin-film composites (NP@MOTF). A quantitative method based on X-ray reflectivity is developed and validated with energy dispersive spectroscopy in order to assess pore filling. The use of dilute formaldehyde solutions leads to control over the formation of silver nanoparticles within mesoporous titania films. Inclusion of silver nanoparticles in mesoporous silica requires more drastic conditions. This difference in reactivity can be exploited to selectively synthesize nanoparticles in a predetermined layer of a multilayered mesoporous stack leading to complex 1D-ordered multilayers with precise spatial location of nanometric objects. The metal oxide nanocomposites synthesized have potential applications in catalysis, optical devices, surface-enhanced Raman scattering, and metal enhancement fluorescence.

The objective of this research was to investigate the development of a reliable fingerprint from elemental and isotopic signatures of Argentinean honey to assess its geographical provenance. Honey, soil, and water from three regions (Córdoba, Buenos Aires, and Entre Rı́os) were collected. The multielemental composition was determined by ICP-MS. δ(13)C was measured by isotopic ratio mass spectrometry, whereas the (87)Sr/(86)Sr ratio was determined using thermal ionization mass spectrometry. The data were analyzed by chemometrics looking for the association between the elements, stable isotopes, and honey samples from the three studied areas. Honey samples were differentiated by classification trees and discriminant analysis using a combination of eight key variables (Rb, K/Rb, B, U, (87)Sr/(86)Sr, Na, La, and Zn) presenting differences among the studied regions. The application of canonical correlation analysis and generalized procrustes analysis showed 91.5% consensus between soil, water, and honey samples, in addition to clear differences between studied areas. To the authors' knowledge, this is the first report demonstrating the correspondence between soil, water, and honey samples using different statistical methods, showing that elemental and isotopic honey compositions are related to soil and water characteristics of the site of origin.

In this research work, DEXTRAN- and polyethylene glycol (PEG)-coated iron-oxide superparamagnetic nanoparticles were synthetized and their cytotoxicity and biodistribution assessed. Well-crystalline hydrophobic Fe3 O4 SPIONs were formed by a thermal decomposition process with d = 18 nm and σ = 2 nm; finally, the character of SPIONs was changed to hydrophilic by a post-synthesis procedure with the functionalization of the SPIONs with PEG or DEXTRAN. The nanoparticles present high saturation magnetization and superparamagnetic behavior at room temperature, and the hydrodynamic diameters of DEXTRAN- and PEG-coated SPIONs were measured as 170 and 120 nm, respectively. PEG- and DEXTRAN-coated SPIONs have a Specific Power Absorption SPA of 320 and 400 W/g, respectively, in an ac magnetic field with amplitude of 13 kA/m and frequency of 256 kHz. In vitro studies using VERO and MDCK cell lineages were performed to study the cytotoxicity and cell uptake of the SPIONs. For both cell lineages, PEG- and DEXTRAN-coated nanoparticles presented high cell viability for concentrations as high as 200 μg/mL. In vivo studies were conducted using BALB/c mice inoculating the SPIONs intravenously and exposing them to the presence of an external magnet located over the tumour. It was observed that the amount of PEG-coated SPIONs in the tumor increased by up to 160% when using the external permanent magnetic as opposed to those animals that were not exposed to the external magnetic field.

Organic molecules have been incorporated into the pore system of mesoporous TiO2 and ZrO2 xerogels and thin films. Surface-modifying functions include alkyl, aryl, amino, sulfonate, thiol, and polyol. Phosphate, phosphonate, carboxylate, and polyphenol were used as grafting groups. The incorporation of these functions into the mesoporous network (typically 2−8 μmol/m2) was monitored by crossing FTIR and EDS. In particular, the cases of dihexadecyl phosphate, monododecyl phosphate, 3-nitrophthalic acid, TIRON (disodium 1,2-dihydroxybenzene, 3,5-disulfonate), and thiol-bearing carboxylates are discussed. Uptake experiments suggest that the pore structure plays a key role in the accessibility of the pore system. Leaching experiments in different solvents and conditions were performed to assess the anchoring of the grafted functions. This permits tailoring of the molecule grafting, from firmly anchored functions to groups with controlled lability.

Complex multilayered thin-film architectures are fabricated by sequentially stacking mesoporous and macroporous layers with varying structure and properties. A series of deposition–stabilization steps are used to sequentially deposit the component layers of the films in order to obtain interconnected systems with a precise ordering of accessible cavities, as shown in the figure.

Using molecular simulations, we study the properties of a polymer brush in contact with an explicit solvent under Couette and Poiseuille flow. The solvent is comprised of chemically identical chains. We present evidence that individual, unentangled chains in the dense brush exhibit cyclic, tumbling motion and non-Gaussian fluctuations of the molecular orientations similar to the behaviour of isolated tethered chains in shear flow. The collective molecular motion gives rise to an inversion of hydrodynamic flow direction in the vicinity of the brush-coated surface. Utilising Couette and Poiseuille flow, we investigate to what extend the effect of a brush-coated surface can be described by a Navier slip condition.

We show that ferromagnetic/paramagnetic La${}_{0.75}$Sr${}_{0.25}$MnO${}_{3}$/LaNiO${}_{3}$ multilayers present an unexpected magnetic exchange-bias effect (EBE), observed in field-cooled magnetization loops. The exchange-bias field and the enhancement of the coercivity vanish around 50 K. We demonstrate that the oxidation state of the Ni and Mn cations changes from Mn${}^{3+}$-Ni${}^{3+}$ to Mn${}^{4+}$-Ni${}^{2+}$ in the layers close to the interface probed by x-ray absorption spectroscopy measurements. The variation of the valence states is accompanied by a change in the magnetic behavior of the cations at the La${}_{0.75}$Sr${}_{0.25}$MnO${}_{3}$/LaNiO${}_{3}$ interface, possibly giving rise to the formation of magnetic or magnetically frustrated regions that may pin the ferromagnetic La${}_{0.75}$Sr${}_{0.25}$MnO${}_{3}$ layers and explain the EBE.

We report the synthesis of rare-earth manganese-oxide-based nanotubes. The pore wetting technique was used to obtain structures of nominal composition La0.325Pr0.300Ca0.375MnO3 with 800 nm external diameter, 4000 nm length, and wall thickness below 100 nm exhibiting magnetic and magnetoresistive behavior below 200 K, including nonvolatile memory. Walls are found to be formed by small crystals of approximately 20 nm. Structures obtained using different diameter of pores, as small as 100 nm, have a similar aspect ratio. Results show the realization of nanotubes of manganites exhibiting intrinsic phase separation.

We discover that hcp phases of Fe and Fe(0.9)Ni(0.1) undergo an electronic topological transition at pressures of about 40 GPa. This topological change of the Fermi surface manifests itself through anomalous behavior of the Debye sound velocity, c/a lattice parameter ratio, and Mössbauer center shift observed in our experiments. First-principles simulations within the dynamic mean field approach demonstrate that the transition is induced by many-electron effects. It is absent in one-electron calculations and represents a clear signature of correlation effects in hcp Fe.