An overview on alumina-silica-based aerogels.

Silica aerogels are remarkable materials with excellent physicochemical properties, such as high porosity and surface area, along with low density and thermal conductivity. In addition to their outstanding properties, these materials are quite interesting due to the possibility to change their chemistry according to intended applications. However, they also show some disadvantages, like low mechanical strength and poor dimensional stability under high temperatures (above 600 °C). Although these aerogels are frequently used as thermal insulators, for high temperature environments some of their properties need to be improved. The mixing with other ceramic thermally resistant phases is a viable approach. Thus, this work presents an overview on alumina-silica-based aerogels, describing their synthesis, processing and properties. The improvement on their properties will be discussed as a function of the amount of refractory phase (alumina) in the silica matrix. The introduction of the alumina phase makes them stable until 1200-1400 °C, maintaining low values of thermal conductivity at very high temperature (below 81 mW m-1 K-1). Finally, a brief survey on the most promising applications of these materials is presented, with several examples. In catalysis, alumina-silica aerogels have shown equivalent performance when compared to reference catalysts. In the field of thermal insulation, these materials show great potential, especially in high temperatures environments, due to their thermal dimensional stability and inherent low thermal conductivity. As adsorbents, higher stability and adsorption capacity were obtained with the incorporation of the alumina phase in silica aerogels, and these materials can be reused for repeated adsorption/desorption cycles. Indeed, a significant improvement of the aerogel performance by the synergetic effect of combining silica and alumina phases is usually obtained, supporting the expectation of the extension of their fields of application.

Optimization of Polyamide Pulp-Reinforced Silica Aerogel Composites for Thermal Protection Systems.

The present work describes for the first time the preparation of silica-based aerogel composites containing tetraethoxysilane (TEOS) and vinyltrimethoxysilane (VTMS) reinforced with Kevlar® pulp. The developed system was extensively investigated, regarding its physical, morphological, thermal and mechanical features. The obtained bulk density values were satisfactory, down to 208 kg·m-3, and very good thermal properties were achieved-namely a thermal conductivity as low as 26 mW·m-1·K-1 (Hot Disk®) and thermal stability up to 550 °C. The introduction of VTMS offers a better dispersion of the polyamide fibers, as well as a higher hydrophobicity and thermal stability of the composites. The aerogels were also able to withstand five compression-decompression cycles without significant change of their size or microstructure. A design of experiment (DOE) was performed to assess the influence of different synthesis parameters, including silica co-precursors ratio, pulp amount and the solvent/Si molar ratio on the nanocomposite properties. The data obtained from the DOE allowed us to understand the significance of each parameter, offering reliable guidelines for the adjustment of the experimental procedure in order to achieve the optimum properties of the studied aerogel composites.

A biocompatible redox MRI probe based on a Mn(ii)/Mn(iii) porphyrin.

For the development of redox responsive MRI probes based on the MnIII/MnII couple, stable complexation of both reduced and oxidized forms of the metal ion and appropriate tuning of the redox potential in the biologically relevant range are key elements. The water soluble fluorinated Mn-porphyrin derivative Mn-3 satisfies both requirements. In aqueous solutions, it can reversibly switch between MnIII/MnII oxidation states. In the presence of ascorbic acid or ß-mercaptoethanol, the MnIII form undergoes reduction, which is slowly but fully reversed in the presence of air oxygen. A UV-Vis kinetic study of MnIII/MnII reduction under oxygen-free conditions yielded second-order rate constants, k2, of 46.1 M-1 s-1 and 13.8 M-1 s-1 for the reaction with ascorbic acid and ß-mercaptoethanol, respectively. This could correspond, in the absence of oxygen, to a half-life of a few minutes in blood plasma and a few seconds in circulating immune cells where ascorbic acid reaches 20-40 µM and a few mM concentrations, respectively. In contrast to expectations based on the redox potential, reduction with glutathione or cysteine does not occur. It is prevented by the coordination of the glutathione carboxylate group(s) to MnIII in the axial position, as was evidenced by NMR data. Therefore, MnIII-3 acts as an ascorbate specific turn-on MRI probe, which in turn can be re-oxidized by oxygen. The relaxivity increase from the oxidized to the reduced form is considerably improved at medium frequencies (up to 80 MHz) with respect to the previously studied Mn-TPPS4 analogues; at 20 MHz, it amounts to 150%. No in vitro cytotoxicity is detectable for Mn-3 in the typical MRI concentration range. Finally, 19F NMR resonances of MnIII-3 are relatively sharp which could open further opportunities to exploit such complexes as paramagnetic 19F NMR probes.