José M. Rojo

Thermal decomposition of hydrotalcites. An infrared and nuclear magnetic resonance spectroscopic study

Calcined hydrotalcites have been used extensively as catalysts for base-catalysed reactions. The calcination procedure in critical in determining the behaviour of the final material. The characteristics of the hydrotalcite, following the different stages of calcination, have been studied by means of thermogravimetric (TG), X-ray diffraction (XRD), IR, 1H and 27Al NMR techniques. We have shown that dehydroxylation begins within layers and then in a second stage occurs between adjacent layers, causing collapse of the structure. This process is accompanied by a change from octahedral to tetrahedral coordination of the aluminium. Decarbonation leads to the formation of micropores of radius <1.75 nm. Dehydroxylation and decarbonation are reversible processes, and their rates depend on the calcination temperature.

Induced changes in ceria by thermal treatments under vacuum or hydrogen

The reduction of CeO2 either under vacuum or hydrogen at temperatures between 295 and 773 K has been investigated by gravimetric methods and IR, 1H-NMR, and ESR spectroscopies. Thermal treatments of the samples under vacuum produce mainly the progressive dehydroxylation of the samples and a weak surface reduction. However, treatments under hydrogen modify substantially this behavior. The gravimetric results show two well-differentiated processes: a fast weight gain due to incorporation of H2 in the oxide bulk, followed by an important weight loss due to lattice oxygen extraction. Infrared data indicate that H2-treatments at temperatures below 673 K do not significantly change the surface concentration of hydroxyl groups, but they induce an important decrease above that temperature. The magnetic resonance spectra confirm the hydrogen incorporation in the oxide, mainly in the bulk, when the sample is heated under H2 in the 373–773 K range.

Transcriptional regulation of th2 differentiation by inducible costimulator.

Helper T (Th) cell differentiation is accompanied by complex transcriptional changes. Although costimulatory receptors are important in Th differentiation, the underlying mechanisms are poorly understood. Here we examine the transcriptional mechanisms by which ICOS regulates Th2 differentiation and selective IL-4 expression by effector T cells. We found impaired expression of c-Maf transcription factor functionally associated with the IL-4 defect in ICOS(-/-) cells. c-Maf expression in effector cells was regulated by IL-4 levels during Th differentiation. ICOS costimulation potentiated the T cell receptor (TcR)-mediated initial IL-4 production, possibly through the enhancement of NFATc1 expression. These data indicate that ICOS, by enhancing TcR signals at an early stage of T cell activation, regulates IL-4 transcription and T cell function in effector cells.

Block-Copolymer assisted synthesis of hierarchical carbon monoliths suitable as supercapacitor electrodes

Three dimensional (3D) hierarchical porous (micro-, meso- and macro-porous) carbon monoliths (HCMs) have recently been proposed as promising supercapacitor electrodes. In this work, we have further explored the use of block-copolymers as templates for the preparation of HCMs via condensation of resorcinol and formaldehyde (RF) and subsequent carbonization. The resulting HCMs exhibited a textured morphology consisting of a bicontinuous macroporous carbon network built of interconnected microporous carbon colloids, as demonstrated by nitrogen adsorption/desorption isotherms, mercury porosimetry and electron microscopy, in both scanning and transmission mode. Such a texture favored the performance of HCMs as supercapacitor electrodes, reaching remarkable values of capacitance of up to 198 F g−1 (normalized by mass) and 34.5 μF cm−2 (normalized by BET surface area). The first electrolyte infiltration into the micropore (prior capacitance measurements) was demonstrated to play a crucial role in the achievement of large capacitance values.

Single-Walled Carbon Nanotubes as Electrodes in Supercapacitors

7 pages.-- PACS: 82.47.Uv; 82.45.Fk; 85.35.Kt; 68.43.Mn; 82.45.Yz; 82.45.Gj; 81.40.Gh; 78.30.Na

The New Oxygen-Deficient Fluorite Bi3NbO7: Synthesis, Electrical Behavior and Structural Approach

A new single phase of composition Bi{sub 3}NbO{sub 7} has been isolated in the binary system Bi{sub 2}O{sub 3}-Nb{sub 2}O{sub 5}. X-ray single crystal diffraction studies have shown that Bi{sub 3}NbO{sub 7} crystallizes in the cubic system, space group Fm{bar 3}m, with unit-cell parameter a = 5.4788(9) {angstrom}. The structure has been determined, and the final reliability index is R = 0.027. Bi{sub 3}NbO{sub 7} exhibits a defect fluorite-type structure with 12.5% of anion vacancies and appears to show a disorder in both anionic and cationic lattices. The study by electron diffraction and high resolution electron microscopy has shown the presence of an incommensurate cubic lattice. Bi{sub 3}NbO{sub 7} shows good behavior as an ionic conductor up to 875 C without any phase transition as deduced from impedance measurements.

Synthesizing nanocrystalline LiMn2O4 by a combustion route

Nanocrystalline samples of lithium manganese oxide with cubic spinel structure have been prepared by combustion of reaction mixtures containing Li(I) and Mn(II) nitrates that operate as oxidisers, and sucrose that acts as fuel. The samples were characterised by X-ray diffraction, transmission electron microscopy, thermal analysis, and impedance and electrochemical measurements. The effect of the fuel content on the purity and morphology of the products was analysed. The samples as prepared showed small amounts of Mn2O3 and Mn3O4 as impurities, depending on the amount of sucrose used in the synthesis. Annealing at 700 °C led to single-phase cubic spinels. In these phases, the smallest average particle size (ca. 30 nm) corresponded to the sample obtained with a hyperstoichiometric amount of fuel. This sample showed the Li1.05Mn1.95O4 composition as deduced from the thermal and electrochemical data. No variation in conductivity associated with the cubic⇔orthorhombic phase transition was observed. The electrochemical behaviour as positive electrode showed good cyclability at high current densities (reversible capacity of 73 mAh g−1 at 2.46 mA cm−2).

T-cell receptor.

The T-cell antigen receptor complex (TCR/CD3) is a cell surface structure that defines the T lymphocyte lineage, where it fulfills two basic functions, namely antigen recognition and triggering of signals needed to mount adequate responses to foreign aggression and/or to undergo differentiation. Knowing the precise structure of the complex in terms of its components and their relative arrangement and interactions before and after antigen recognition is essential to understand how ligand binding transforms into functionally relevant T-cell responses. These include not only full responses to foreign peptide antigens by mature T-cells, but also other phenomena like modulation ofT-cell activation with altered peptide ligands, positive and negative selection ofthymocytes, alloreactivity and autoimmune reactions. A wealth of new data has accumulated in recent years on the structure of TCR/antigen complexes and CD3 polypeptides and on the stoichiometry of the TCR/CD3 complex and intersubunit interactions. In this review, we discuss how these data fit into a meaningful model of the TCR/CD3 function.

Nanosize LiNiyMn2 −yO4(0 < y≤ 0.5) spinels synthesized by a sucrose-aided combustion method. Characterization and electrochemical performance

Nanosize crystalline cathode materials of LiNiyMn2 − yO4 (0 < y ≤ 0.5) composition and spinel-type structure have been obtained by a single-step sucrose-aided self-combustion method. The as-prepared samples contained some amorphous organic impurities that were removed after a short period of heating at 500 °C. The pure single-phase spinels have been characterized by X-ray diffraction, transmission electron microscopy, chemical analysis, and nitrogen sorption isotherms. The samples consist of particles (ca. 24 nm size) that are aggregated in clusters (ca. 1 µm size) in which mesopores (10–80 nm size) appear among the particles. Additional heating at 800° and 1000 °C produces a slight increase in the cubic lattice parameter and a pronounced increase in particle size (>100 nm). Electrical conductivity decreases as the Ni content increases in accordance with an electron hopping mechanism between Mn3+ and Mn4+ ions. The 500 °C- and 800 °C-heated LiNi0.5Mn1.5O4 samples show good electrochemical behaviour at 4.7 V as cathode materials. The capacity (132.7 mA h g−1) found is close to the nominal capacity (146.7 mA h g−1) and remains constant for current densities in the range C/24–2C (where C = 2.6 mA cm−2). At higher current densities (2C–10C) the capacity decreases progressively. The cyclability at the C current density is ca. 99.7% for both samples.

PPO15-PEO22-PPO15block copolymer assisted synthesis of monolithic macro- and microporous carbon aerogels exhibiting high conductivity and remarkable capacitance

Ultralightweight (specific gravity 5 × 10−2) and highly conductive (2.5 S/cm) monolithic carbon aerogels exhibiting a three-dimensionally continuous micro- and macroporous structure have been prepared through a PPO-PEO-PPO block copolymer assisted route. The resulting carbon aerogels were highly suitable as electrodes of electric double layer capacitors, with remarkable values of capacitance of up to 225 F/g (normalized by mass) and 31 µF/cm2 (normalized by BET surface area).