High-Pressure Synthesis of ß-Ir4B5 and Determination of the Compressibility of Various Iridium Borides.

A new iridium boride, ß-Ir4B5, was synthesized under high-pressure/high-temperature conditions of 10.5 GPa and 1500 °C in a multianvil press with a Walker-type module. The new modification ß-Ir4B5 crystallizes in a new structure type in the orthorhombic space group Pnma (no. 62) with the lattice parameters a = 10.772(2) Å, b = 2.844(1) Å, and c = 6.052(2) Å with R1 = 0.0286, wR2 = 0.0642 (all data), and Z = 2. The structure was determined by single-crystal X-ray and neutron powder diffraction on samples enriched in 11B. The compound is built up by an alternating stacking of boron and iridium layers with the sequence ABA'B'. Additionally, microcalorimetry, hardness, and compressibility measurements of the binary iridium borides α-Ir4B5, ß-Ir4B5, Ir5B4, hexagonal Ir4B3- x and orthorhombic Ir4B3- x were carried out and theoretical investigations based on density function theory (DFT) were employed to complement a comprehensive evaluation of structure-property relations. The incorporation of boron into the structures does not enhance the compressibility but leads to a significant reduction of the bulk moduli and elastic constants in comparison to elemental iridium.

Effect of phosphate on the particle size of ferric oxyhydroxides anchored onto activated carbon: As(V) removal from water.

The surface area of iron oxyhydroxides is a key factor when removing As from water. However, research related to this matter shows that this issue has not been explored in detail. The use of capping agents is a viable method to synthesize ferric oxyhydroxide nanoparticles; however, this method to our knowledge has not been applied for the anchorage of iron oxyhydroxide nanoparticles on activated carbon (AC). In the present work, the addition of PO(4) (as a capping agent) in forced hydrolysis of FeCl(3) in AC was investigated. Results revealed that the surface area of modified materials reached a maximum of about 900 m(2)/g with a molar ratio PO(4)/Fe of 0.1. Moreover, microscopy studies indicate a size range of iron nanoparticles from 2 to 300 nm, where the smallest particles are attained with the highest concentration of PO(4). The surface charge distribution of modified samples became less positive; however, the As removal increased, indicating that electrostatic interaction is not the controlling sorption mechanism. Modified samples showed a 40% increase on As(V) adsorption capacity when using a molar ratio PO(4)/Fe of 1.5. The proposed method allowed anchoring of iron oxyhydroxides nanoparticles on AC, which have a high As(V) adsorption capacity (5 mg/g).

Dual function of EDTA with silver nanoparticles for root canal treatment-A novel modification.

The chelating and antimicrobial capacity of a novel modification of 17% EDTA with silver nanoparticles (AgNPs) (EDTA-AgNPs) was evaluated in-vitro for root canal treatment (RCT). The EDTA-AgNPs solution was characterized by UV-Vis spectroscopy, ζ-potential and high-resolution transmission electron microscopy (HRTEM). Antimicrobial capacity was evaluated against Candida albicans and Staphylococcus aureus in planktonic and biofilm cells by broth macrodilution (24 h) and XTT assays, (1, 10 and 30 min) respectively. The chelating capacity of EDTA-AgNPs was assessed indirectly (smear layer removal) and directly (demineralizing effect) in bovine dentin at two silver concentrations, 16 and 512 µg/ml at 1 and 10 minutes of exposure time. Smear layer removal was evaluated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The demineralizing effect was determined by atomic absorption spectroscopy (AAS), microhardness test (MH) and X-ray diffractometer (XRD). Synthesized AgNPs were quasi-spherical in shape with an average size of 13.09 ± 8.05 nm. 17% EDTA-AgNPs was effective to inhibit C. albicans and S. aureus in planktonic and biofilm cultures. The smear layer removal and demineralizing effect were similar between 17% EDTA-AgNPs and 17% EDTA treatments. The 17% EDTA-AgNPs solution proved to be an effective antimicrobial agent, and has a similar chelating capacity to 17% EDTA alone. These in-vitro studies strongly suggest that EDTA-AgNPs could be used for effective smear layer removal, having an antimicrobial effect at the same time during RCT.

Nanoscale influence on photoluminescence and third order nonlinear susceptibility exhibited by ion-implanted Pt nanoparticles in silica.

A systematic study has been carried out to investigate photoluminescence and third order nonlinear ultraviolet properties exhibited by platinum nanoparticles nucleated in a high-purity silica matrix. The modification in the characteristic photoluminescence spectra of the nanocomposites, ranging between 400 and 600 nm, was obtained with the assistance of a thermal annealing process that changed the average size of the platinum nanoparticles. The influence of temperature, between 200 °C-1100 °C, during the thermal treatment of the nanostructures was analyzed. UV-vis spectroscopy studies corroborated changes in the optical absorption resonances of the ion-implanted samples after annealing, which could then be correlated with the average size of the nanoparticles. The estimated average size was also corroborated by transmision electron microscopy. For temperatures below 600 °C the system is mainly composed of ultra-small photoluminescent platinum nanoparticles. Larger platinum nanoparticles were formed at higher annealing temperatures but photoluminescence quenching was observed as the typical plasmonics response of larger metal nanoparticles started to emerge. The photoluminescence emission for samples with a particle size of less than 2 nm is enhanced approximately 12 fold with respect to the samples with a particle size in the range of 3-7 nm. Differences in the resulting photoluminescence spectra were revealed by substituting the participation of argon, hydrogen or nitrogen, as environmental gases for thermal annealing. A weak PL emission, featuring 1.5 nW at a laser excitation power of 800 µW, related to larger platinum nanoparticles was observed. New emission peaks emerging from the larger platinum nanoparticles were associated with possible hydrogen adsorption on the nanoparticles' surface. Third order nonlinear ultraviolet measurements were conducted using a time-resolved two-wave mixing method with self-diffraction at 355 nm wavelength. The observed self-diffraction decay time is less than 25 ps, regardless of the average size of the nanoparticles studied. The evolution of the self-diffracted intensities derived from temperature was also linked to the mean size of the nanoparticles in the samples. Comparative two-wave mixing evaluations also validated a modification in third order nonlinear susceptibility exhibited by annealed samples. An important role of the localized surface plasmon resonance phenomena associated with the platinum nanoparticles for photoluminescence and optical nonlinearities was identified. A proposed hypothetical electronic mechanism that may explain the exceptional optical transitions related to low-dimensional platinum systems is discussed.

Arsenic contamination in irrigation water, agricultural soil and maize crop from an abandoned smelter site in Matehuala, Mexico.

Mobility of Arsenic (As) from metallurgical wastes in Matehuala, Mexico has been accounted for ultra-high concentration of As in water (4.8-158mg/L) that is used for recreational purposes as well as cultivation of maize. In this study, we (i) measured As concentrations in soils irrigated with this water, (ii) investigated the geochemical controls of available As, and (iii) measured bioaccumulation of As in maize. Water, soil, and maize plant samples were collected from 3 different plots to determine As in environmental matrices as well as water soluble As in soils. Soil mineralogy was determined by X-ray diffraction analysis. Bioaccumulation of As in maize plants was estimated from the bioconcentration and translocation factors. We recorded As built-up in agricultural soils to the extent of 172mg/kg, and noted that this As is highly soluble in water (30% on average). Maize crops presented high bioaccumulation, up to 2.5 times of bioconcentration and 45% of translocation. Furthermore, we found that water extractable As was higher in soils rich in calcite, while it was lower in soils containing high levels of gypsum, but As bioconcentration showed opposite trend. Results from this study show that irrigation with As rich water represents a significant risk to the population consuming contaminated crops.

Surface properties of Ni-Pt/SiO2 catalysts for N2O decomposition and reduction by H2.

The surface properties of bimetallic Ni-Pt/SiO2 catalysts with variable Ni/Ni + Pt atomic ratio (0.75, 0.50, and 0.25) were studied using N2O decomposition and N2O reduction by hydrogen reactions as probes. Catalysts were prepared by incipient wetness impregnation of the silica support with aqueous solutions of the metal precursors to a total metal loading of 2 wt %. For both model reactions, Pt/SiO2 catalyst was substantially more active than Ni/SiO2 catalyst. Mean particle size by TEM was about the same (in the range 6-8 nm) for all catalysts and truly bimetallic particles (more than 95%) were evidenced by EDS in the Ni-Pt/SiO2 catalysts. CO adsorption on the bimetallic catalysts showed differences in the linear CO absorption band as a function of the Ni/Pt atomic ratio. Bimetallic Ni-Pt/SiO2 catalysts showed, for the N2O decomposition, a catalytic behavior that points out an ensemble-size sensitive behavior for Ni-rich compositions. For the N2O + H2 reaction, the bimetallic catalysts were very active at low temperature. The following activity order at 300 K was observed: Ni75Pt25 > Ni25Pt75 approximately Ni50Pt50 > Pt. TOF values for these catalysts increased 2-5 times compared to the most active reference catalyst (Pt/SiO2). The enhancement of the activity in the Ni75Pt25 bimetallic catalysts is explained in terms of the presence of mixed Ni-Pt ensembles.

Ultrastructural analysis of Candida albicans when exposed to silver nanoparticles.

Candida albicans is the most common fungal pathogen in humans, and recently some studies have reported the antifungal activity of silver nanoparticles (AgNPs) against some Candida species. However, ultrastructural analyses on the interaction of AgNPs with these microorganisms have not been reported. In this work we evaluated the effect of AgNPs on C. albicans, and the minimum inhibitory concentration (MIC) was found to have a fungicidal effect. The IC50 was also determined, and the use of AgNPs with fluconazole (FLC), a fungistatic drug, reduced cell proliferation. In order to understand how AgNPs interact with living cells, the ultrastructural distribution of AgNPs in this fungus was determined. Transmission electron microscopy (TEM) analysis revealed a high accumulation of AgNPs outside the cells but also smaller nanoparticles (NPs) localized throughout the cytoplasm. Energy dispersive spectroscopy (EDS) analysis confirmed the presence of intracellular silver. From our results it is assumed that AgNPs used in this study do not penetrate the cell, but instead release silver ions that infiltrate into the cell leading to the formation of NPs through reduction by organic compounds present in the cell wall and cytoplasm.

Arsenic mobility controlled by solid calcium arsenates: a case study in Mexico showcasing a potentially widespread environmental problem.

An As-contaminated perched aquifer under an urban area affected by mining was studied over a year to determine the contamination source species and the mechanism of As mobilization. Results show that the dissolution of calcium arsenates in residues disposed on an inactive smelter has caused high levels of As pollution in the adjoining downgradient 6-km perched aquifer, reaching up to 158 mg/L of dissolved As, and releasing a total of ca. 7.5 tons of As in a year. Furthermore, free calcium ion availability was found to control As mobility in the aquifer through the diagenetic precipitation of calcium arsenates (Ca5H2(AsO4)4·cH2O) preventing further mobilization of As. Results shown here represent a model for understanding a highly underreported mechanism of retention of arsenate species likely to dominate in calcium-rich environments, such as those in calcareous sediments and soils, where the commonly reported mechanism of adsorption to iron(III) oxyhydroxides is not the dominant process.

SERS properties of different sized and shaped gold nanoparticles biosynthesized under different environmental conditions by Neurospora crassa extract.

Surface-enhanced Raman scattering (SERS) is a surface-sensitive technique that enhances Raman scattering by molecules adsorbed on rough metal surfaces. It is known that metal nanoparticles, especially gold and silver nanoparticles, exhibit great SERS properties, which make them very attractive for the development of biosensors and biocatalysts. On the other hand, the development of ecofriendly methods for the synthesis of metallic nanostructures has become the focus of research in several countries, and many microorganisms and plants have already been used to biosynthesize metallic nanostructures. However, the majority of these are pathogenic to plants or humans. Here, we report gold nanoparticles with good SERS properties, biosynthesized by Neurospora crassa extract under different environmental conditions, increasing Raman signals up to 40 times using methylene blue as a target molecule. Incubation of tetrachloroauric acid solution with the fungal extract at 60°C and a pH value of a) 3, b) 5.5, and c) 10 resulted in the formation of gold nanoparticles of a) different shapes like triangles, hexagons, pentagons etc. in a broad size range of about 10-200 nm, b) mostly quasi-spheres with some different shapes in a main size range of 6-23 nm, and c) only quasi-spheres of 3-12 nm. Analyses included TEM, HRTEM, and EDS in order to corroborate the shape and the elemental character of the gold nanoparticles, respectively. The results presented here show that these 'green' synthesized gold nanoparticles might have potential applicability in the field of biological sensing.

Production of platinum nanoparticles and nanoaggregates using Neurospora crassa.

Fungal biomass and fungal extract of the nonpathogenic fungus Neurospora crassa were successfully used as reducing agents for the biosynthesis of platinum nanoparticles (PtNPs). The experiment was carried out by exposing the fungal biomass or the fungal extract to a 0.001 M precursor solution of hexachloroplatinic(IV) acid (H2PtCl6). A change of color of the biomass from pale yellow to dark brown was the first indication of possible formation of PtNPs by the fungus. Subsequent analyses confirmed the intracellular biosynthesis of single PtNPs (4-35 nm in diameter) and spherical nanoaggregates (20-110 nm in diameter). Using the fungal extract, similar results were obtained, producing rounded nanoaggregates of Pt single crystals in the range of 17-76 nm.