Effects of Iron Species on Low Temperature CO Electrolyzers.

Electrochemical energy conversion devices are considered key in reducing CO emissions and significant efforts are being applied to accelerate device development. Unlike other technologies, low temperature electrolyzers have the ability to directly convert CO into a range of value-added chemicals. To make them commercially viable, however, device efficiency and durability must be increased.

Amorphous Calcium Phosphates: Solvent-Controlled Growth and Stabilization through the Epoxide Route.

Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms.

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd-Even Effect of the Organic Spacer.

A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered Co hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one-pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (H ) below ca.

Unveiling the Occurrence of Co(III) in NiCo Layered Electroactive Hydroxides: The Role of Distorted Environments.

Co- and Ni-based layered hydroxides constitute a unique class of two-dimensional inorganic materials with exceptional chemical diversity, physicochemical properties and outstanding performance as supercapacitors and overall water splitting catalysts. Recently, the occurrence of Co(III) in these phases has been proposed as a key factor that enhance their electrochemical performance. However, the origin of this centers and control over its contents remains as an open question.

Mild Homogeneous Synthesis of Gold Nanoparticles through the Epoxide Route: Kinetics, Mechanisms, and Related One-Pot Composites.

A new one-pot homogeneous methodology at room temperature to obtain Au nanoparticles (AuNP) on the basis of the epoxide route is presented. The proposed method takes advantage of the homogenous generation of OH moieties driven by epoxide ring-opening, mediated by chloride nucleophilic attack. Once reached alkaline conditions, the reducing medium allows the quantitative formation of AuNP under well-defined kinetic control.

Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations.

The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects.

On Demand One-Pot Mild Preparation of Layered Double Hydroxides and Their Hybrid Forms: Advances through the Epoxide Route.

Epoxide ring opening driven alkalinization process was explored with the aim of preparing layered double hydroxide (LDH) phases on demand, at room temperature. Employing iodide as nucleophilic agent, the precipitation reaction can be driven under much lower halide concentrations. This scenario favors the selective intercalation of concomitant bulky oxo anions as nitrate or perchlorate in the LDH products, allowing for the one-pot synthesis of an LDH able to delaminate in formamide.

Biopolymeric pellets of polyvinyl alcohol and alginate for the encapsulation of Ib-M6 peptide and its antimicrobial activity against .

The encapsulation of Ib-M6 antibacterial peptide in pellets of polyvinyl alcohol (PVA) and polyvinyl alcohol-alginate (PVA-Alg) matrices was carried out in order to explore its controlled release and activity against K-12. The pellets were obtained by combined ice segregation induced self-assembly (ISISA) and freezing-thawing methods and their microstructure was studied by scanning electron microscopy. Bromothymol blue was used as a model compound to study the transport mechanisms and release from pellets.

Interplay of Coordination Environment and Magnetic Behavior of Layered Co(II) Hydroxichlorides: A DFT+U Study.

In this work we present a systematic computational study of the structural and magnetic properties of a layered family of Co(II) hydroxichlorides, obeying to the general formula Co(OH)Cl (HO) . This solid contains both octahedral and tetrahedral cobalt ions, displaying a complex magnetic order arising from the particular coupling between the two kinds of metallic centers. Here, supercells representing concentrations of 12, 20, and 40% of tetrahedral sites were modeled consistently with the compositions reported experimentally.

Highly Structured Polyvinyl Alcohol Porous Carriers: Tuning Inherent Stability and Release Kinetics in Water.

Polyvinyl alcohol (PVA) porous carriers were prepared by means of ice templating of aqueous solutions containing of 90 kD and/or 16 kD PVA. The carriers were loaded with traces of a colored probe (methyl orange) to screen their release properties, once immersed in water. The carriers prepared from solutions containing 90 kD and 16 kD PVA resulted in intimate polymer mixtures, exhibiting physical properties that stand in between those of the bare 90 kD or 16 kD PVA end members.

Ce -Gd Mixed Oxides as Hosts for Er -Based Upconversion Phosphors.

A family of Er and Er -Yb based nanophosphors, hosted in monophasic oxidic Ce -Gd binary solid solutions, was prepared. The samples were formulated with a constant Er content as the activator, with the eventual addition of Yb as a sensitizer. The amorphous Ce Gd Er (OH)CO ⋅H O and Ce Gd Er Yb (OH)CO ⋅H O precursors were prepared by following the urea method to obtain monodispersed spheres of tunable size ranging from 30 to 450 nm.

Extremely efficient crystallization of HKUST-1 and Keggin-loaded related phases through the epoxide route.

Highly crystalline HKUST-1 and COK-16-like phases were obtained based on a mild in situ alkalinization one-pot epoxide driven method. A slurry composed of finely ground trimesic acid, HBTC, dispersed in a CuCl aqueous solution quantitatively developed well crystallized HKUST-1 after the addition of propylene oxide. The use of solid HBTC ensures a low concentration of free linker, favoring crystalline growth over the precipitation of amorphous or metastable impurities.

Rich stochastic dynamics of co-doped Er:Yb fluorescence upconversion nanoparticles in the presence of thermal, non-conservative, harmonic and optical forces.

The stochastic dynamics of individual co-doped Er:Yb upconversion nanoparticles (UCNP) were investigated from experiments and simulations. The UCNP were characterized by high-resolution scanning electron microscopy, dynamic light scattering, and zeta potential measurements. Single UCNP measurements were performed by fluorescence upconversion micro-spectroscopy and optical trapping.

The magnetic structure of β-cobalt hydroxide and the effect of spin-orientation.

Synchrotron X-ray and neutron diffraction experiments at various temperatures, down to 3 K, along with ab initio calculations, are carried out to elucidate the magnetic order of layered β-cobalt-hydroxide. This combination of techniques allows for the unambiguous assignment of the magnetic structure of this material. Our results confirm that below the Néel temperature high-spin cobalt centers are ferromagnetically coupled within a layer, and antiferromagnetically coupled across layers (magnetic propagation vector k = (0,0,½)), in agreement with the indirect interpretation based on magnetic susceptibility measurements.

Microorganism mediated biosynthesis of metal chalcogenides; a powerful tool to transform toxic effluents into functional nanomaterials.

Cadmium contained in soil and water can be taken up by certain crops and aquatic organisms and accumulate in the food-chain, thus removal of Cd from mining or industrial effluents - i.e. Ni-Cd batteries, electroplating, pigments, fertilizers - becomes mandatory for human health.

Ca(ii) and Ce(iii) homogeneous alginate hydrogels from the parent alginic acid precursor: a structural study.

Alginate hydrogels are suitable for the encapsulation of biomolecules and microorganisms for the building of bioactive materials. Several alternatives to the conventional alginate formulation are being studied for a broad range of biotechnological applications; among them the crosslinking of alginate by lanthanide cations, Ln(iii), envisages expanded biomedical applications. The performance of these functional materials is highly related to the microstructure of the alginate matrix, which in turn is affected by the conditions of synthesis.

Feasibility of using a translucid inorganic hydrogel to build a biosensor using immobilized algal cells.

Anthropic activities generate contaminants, as pesticides and other pollutants, in the aquatic environment which present a real threat to ecosystems and human health. Thus, monitoring tools become essential for water managers to detect these chemicals before the occurrence of adverse effects. In this aim, algal cell biosensors, based on photosystem II activity measurement, have been designed for several years in previous studies.

Silica@proton-alginate microreactors: a versatile platform for cell encapsulation.

As an alternative approach to the well known Ca(ii)-alginate encapsulation process within silica hydrogels, proton-driven alginate gelation was investigated in order to establish its capacity as a culture carrier, both isolated and embedded in an inorganic matrix. Control over the velocity of the proton-gelation front allows the formation of a hydrogel shell while the core remains liquid, allowing bacteria and microalgae to survive the strongly acidic encapsulation process. Once inside the inorganic host, synthesized by a sol-gel process, the capsules spontaneously redissolve without the aid of external complexing agents.

Hierarchical bioglass scaffolds: introducing the "milky way" for templated bioceramics.

Free standing hierarchical bioglass scaffolds were prepared by the ISISA (ice-segregation-induced self-assembly) method. Commercial low-cost precursors such as Ludox® HS-40 and cow milk were employed as the source of SiO and biominerals (Ca(ii), P(v), Na(i) and K(i)), respectively. Then, in a single macroscopic piece, three levels of porosity coexist due to the simultaneous templating effect of ice (macropores), milk (50-200 nm mesopores) and the voids left between preformed Ludox® nano building blocks (2-5 nm mesopores).

Co-encapsulation and microalgae in silica matrices, a stepping stone toward a portable microcosm.

We report on the first silica encapsulation of a metazoan (), with a high initial viability (96% of the population remained active 48 h after encapsulation). Moreover, the co-encapsulation of this crustacean and microalgae () was achieved, creating inside a silica monolith, the smallest microcosm developed to present. This artificial ecosystem in a greatly diminished scale isolated inside a silica nanoporous matrix could have applications in environmental monitoring, allowing ecotoxicity studies to be carried out in portable devices for on-line and pollution level assessment.

Halide exchange on Mg(II)-Al(III) layered double hydroxides: exploring affinities and electrostatic predictive models.

The crystalline chloride form of layered double hydroxide (LDH) with the formula Mg0.75Al0.25(OH)2Cl0.

Rhodamine B doped silica encapsulation matrices for the protection of photosynthetic organisms.

An advanced encapsulation matrix that efficiently protects microalgae from harmful UV light without causing toxicity to the entrapped culture is developed based on the electrostatic adsorption of the dye Rhodamine B on silica preformed particles during sol-gel synthesis. The three microalgae (Chlorella vulgaris, Pseudokirchneriella subcapitata and Chlamydomonas reinhardtii) were previously immobilized in alginate following the Two-step procedure. Once entrapped in the silica gel, Rhodamine B act as an inner cut-off filter, protecting the encapsulated organisms from UV radiation.

New method for the simultaneous determination of diffusion and adsorption of dyes in silica hydrogels.

The fine tuning of porosity in sol gel based devices makes possible the design of novel applications in which the transport of molecules through the oxide gel plays a crucial role. In this work we develop a new method for the simultaneous analysis of diffusion and adsorption of small diffusing probes, as anionic and cationic dyes, through silica mesoporous hydrogels synthesized by sol-gel. The novelty of the work resides in the simplicity of acquisition of the experimental data (by means of a desk scanner) and further mathematical modeling, which is in line with high throughput screening procedures, enabling rapid and simultaneous determination of relevant diffusion and adsorption parameters.

Sol-gel silica platforms for microalgae-based optical biosensors.

An advanced hybrid biosensing platform with improved optical quality is developed based on the acidic encapsulation of microalgi in silica matrices synthesized by TAFR (tetraethoxysilane derived alcohol free route). The three microalgi (Chlorella vulgaris, Pseudokirchneriella subcapitata and Chlamydomonas reinhardtii) were previously immobilized in alginate following the two-step procedure. Tuning the alginate protecting function with the aid of Tris-HCl buffer, the sol-gel synthesis was conducted at pH 4.

One pot synthesis of Mg2Al(OH)6Cl·1.5H2O layered double hydroxides: the epoxide route.

Pure Mg2Al(OH)6Cl·1.5H2O layered double hydroxide (LDH) has been synthesized at room temperature by a one-pot method, homogeneously driven by chloride-assisted glycidol rupture (epoxide route). Well-defined nanoplatelet texture was achieved and the LDH crystallization mechanism discussed.