Luísa Durães

Application of hydrophobic silica based aerogels and xerogels for removal of toxic organic compounds from aqueous solutions

This work is devoted to the application of hydrophobic silica based aerogels and xerogels for the removal of three toxic organic compounds from aqueous solutions. These materials were tested and characterized regarding their morphology, particle size distribution, surface area and porous structure. The equilibrium tests were carried out at different adsorbate concentrations and the experimental data were correlated by means of Langmuir and Freundlich isotherms. The equilibrium data were well described by Langmuir and Freundlich in most cases. The maximum adsorption capacity by Langmuir model was observed for the adsorption of benzene onto aerogel (192.31 mg/g), though the most promising results were obtained for toluene adsorption due to the greater adsorption energy involved. Comparing these results with other reported results, the hydrophobic silica based aerogels/xerogels were found to exhibit a remarkable performance for the removal of benzene and toluene. In addition, the regeneration of previously saturated aerogel/toluene was also investigated by using an ozonation process. The adsorption/regeneration tests with ozone oxidation showed that the aerogel might be regenerated, nevertheless the materials lost their hydrophobicity and thus different methods should be evaluated in forthcoming investigations.

Synthesis of mechanically reinforced silica aerogels via surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization

Mechanically reinforced polymer–silica aerogels have been successfully prepared by using surface-initiated reversible addition-fragmentation chain transfer polymerization. With this approach, well-defined polystyrene (PSt) and poly(butyl acrylate) (PBA) with low polydispersities grew on the silica surface and improved the mechanical strength in relation to native aerogels. Moreover, it allowed establishing a structure–property relationship between the grafted polymer molecular weight and physical properties of the hybrid aerogels, thereby enabling the preparation of composites with tailored properties. The aerogel composites here obtained exhibited a low density of 0.13–0.17 g cm−3, high thermal insulation performance of 0.03–0.04 W m−1 K−1 and a high specific surface area of 350–780 m2 g−1, with approximately one order of magnitude improvement in the compression strength over the non-reinforced aerogels.

Synthesis and biomedical applications of aerogels: Possibilities and challenges

Aerogels are an exceptional group of nanoporous materials with outstanding physicochemical properties. Due to their unique physical, chemical, and mechanical properties, aerogels are recognized as promising candidates for diverse applications including, thermal insulation, catalysis, environmental cleaning up, chemical sensors, acoustic transducers, energy storage devices, metal casting molds and water repellant coatings. Here, we have provided a comprehensive overview on the synthesis, processing and drying methods of the mostly investigated types of aerogels used in the biological and biomedical contexts, including silica aerogels, silica-polymer composites, polymeric and biopolymer aerogels. In addition, the very recent challenges on these aerogels with regard to their applicability in biomedical field as well as for personalized medicine applications are considered and explained in detail.

Study of the suitability of silica based xerogels synthesized using ethyltrimethoxysilane and/or methyltrimethoxysilane precursors for aerospace applications

Silica based materials were synthesized using ethyltrimethoxysilane (ETMS) and/or methyltrimethoxysilane (MTMS) precursors by sol–gel technology, in order to ascertain if their properties are suitable for aerospace applications. When ETMS was used alone and in equimolar ETMS/MTMS mixtures, no gel formation took place and a resin-like precipitate was observed. After drying, a compact tablet was formed. When mixtures of 25% ETMS/75% MTMS and MTMS alone were used, gel formation occurred and xerogels were produced upon drying. Chemical and structural characterization of the obtained materials was performed using Elemental Analysis, FTIR, XRD and SEM. Bulk density, specific surface area, contact angle and the thermal behavior were also evaluated. For materials from ETMS, the chemical structure grows preferentially in one direction and, in the case of MTMS the growth follows a 3D pattern. The use of ETMS precursor leads to a significant increase in the product density, accompanied by a decrease in the specific surface area. It also leads to a decrease in the thermal stability limit of the synthesized materials. Then, ETMS precursor is less appropriate than MTMS precursor for space applications. However, ETMS co-precursor in mixtures with MTMS contributes to the increase in the hydrophobic character of the synthesized materials.

High Antimicrobial Activity and Low Human Cell Cytotoxicity of Core–Shell Magnetic Nanoparticles Functionalized with an Antimicrobial Peptide

Superparamagnetic iron oxide nanoparticles (SPIONs) functionalized with antimicrobial agents are promising infection-targeted therapeutic platforms when coupled with external magnetic stimuli. These antimicrobial nanoparticles (NPs) may offer advantages in fighting intracellular pathogens as well as biomaterial-associated infections. This requires the development of NPs with high antimicrobial activity without interfering with the biology of mammalian cells. Here, we report the preparation of biocompatible antimicrobial SPION@gold core-shell NPs based on covalent immobilization of the antimicrobial peptide (AMP) cecropin melittin (CM) (the conjugate is named AMP-NP). The minimal inhibitory concentration (MIC) of the AMP-NP for Escherichia coli was 0.4 μg/mL, 10-times lower than the MIC of soluble CM. The antimicrobial activity of CM depends on the length of the spacer between the CM and the NP. AMP-NPs are taken up by endothelial (between 60 and 170 pg of NPs per cell) and macrophage (between 18 and 36 pg of NPs per cell) cells and accumulate preferentially in endolysosomes. These NPs have no significant cytotoxic and pro-inflammatory activities for concentrations up to 200 μg/mL (at least 100 times higher than the MIC of soluble CM). Our results in membrane models suggest that the selectivity of AMP-NPs for bacteria and not eukaryotic membranes is due to their membrane compositions. The AMP-NPs developed here open new opportunities for infection-site targeting.

Tailored Silica Based Xerogels and Aerogels for Insulation in Space Environments

In this work, the sol-gel technology is used to produce silica based xerogels and aerogels suitable for insulation applications in Space. The properties of the obtained materials are tailored varying the precursor – Methyltrimethoxysilane (MTMS) or Methyltriethoxysilane (MTES), and the solvent – methanol or ethanol. A two-step acid-base catalyzed synthesis is used, being the obtained gels dried at atmospheric pressure, in the case of xerogels, and in supercritical conditions, for aerogels. Density and thermal conductivity must be made as low as possible for the sought application and only highly porous materials can fulfill this requirement. The obtained xerogels and aerogels, either with MTMS or MTES, show very promising properties for thermal insulation in Space, when methanol is used as solvent. The more suitable materials are obtained with MTMS and exhibit very low density (80-100 kg/m3), very high surface area (~ 400 m2/g) and small pore size (~ 30-40 Å). They also show moderate flexibility and a remarkable hydrophobic character (~ 150º).

Heavy metals in Iberian soils: Removal by current adsorbents/amendments and prospective for aerogels

Heavy metals are dangerous pollutants that in spite of occurring naturally are released in major amounts to the environment due to anthropogenic activities. After being released in the environment, the heavy metals end up in the soils where they accumulate as they do not degrade, adversely affecting the biota. Because of the dynamic equilibria between soil constituents, the heavy metals may be present in different phases such as the solid phase (immobilized contaminants) or dissolved in soil solution. The latter form is the most dangerous because the ions are mobile, can leach and be absorbed by living organisms. Different methods for the decontamination of polluted soils have been proposed and they make use of two different approaches: mobilizing the heavy metals, which allows their removal from soil, or immobilization that maintains the metal concentrations in soils but keeps them in an inert form due to mechanisms like precipitation, complexation or adsorption. Mobilization of the heavy metals is known to cause leaching and increase plant uptake, so this treatment can cause greater problems. Aerogels are incredible nanostructured, lightweight materials with high surface area and tailorable surface chemistry. Their application in environmental cleaning has been increasing in recent years and very promising results have been obtained. The functionalization of the aerogels can give them the ability to interact with heavy metals, retaining the latter via strong adsorptive interactions. Thus, this review surveys the existing literature for remediation of soils using an immobilization approach, i.e. with soil amendments that increase the soil sorption/retention capacity for heavy metals. The considered framework was a set of heavy metals with relevance in polluted Iberian soils, namely Cd, Cr, Cu, Ni, Pb and Zn. Moreover, other adsorbents, especially aerogels, have been used for the removal of these contaminants from aqueous media; because groundwater and soil solution have dynamic equilibria with the soil solid phase, these works allowed to draw conclusions and perspectives for the use of aerogels not only as adsorbents in aqueous media but also as amendments for the remediation of heavy metal polluted soils.

Development of a biocompatible magnetic nanofluid by incorporating SPIONs in Amazonian oils

Higher quality magnetic nanoparticles are needed for use as magnetic nanoprobe in medical imaging techniques and cancer therapy. Moreover, the phytochemistry benefits of some Amazonian essential oils have sparked great interest for medical treatments. In this work, a magnetic nanoprobe was developed, allying the biocompatibility and superparamagnetism of iron oxide nanoparticles (SPIONs) with benefits associated with Amazonian oils from Copaiba and Andiroba trees. SPIONs were obtained by two thermal decomposition procedures and different amounts of precursors (iron acetylacetonates). Their characterization was accomplished by Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy and magnetization. The obtained nanoparticles composition and magnetic properties were not affected by the relative proportion of iron(II) and iron(III) in the precursor system. However, when changing the reducing and stabilizing agents the coating layer shows different compositions/relative weight - the more promising SPIONs have a coating mainly composed by oleylamine and an iron oxide:coating wt% ratio of 55:45. Nanoparticles size distributions were very narrow and centred in the average size of 6-7nm. Cellular assays confirmed the biocompatibility of SPIONs and their effective internalization in human colon cancer cells. Mössbauer/XRD results indicated maghemite as their main iron oxide phase, but traces of magnetite proved to be present. Magnetization saturations of 57emu/g at 5K and 42emu/g at 300K were achieved. With incorporation of SPIONs into Copaiba and Andiroba essential oils, these values show a 4-fold decrease, but the supermagnetic behaviour is preserved providing the effective formation of a nanofluid.

Truncated tetragonal bipyramidal anatase nanocrystals formed without use of capping agents from the supercritical drying of a TiO2 sol

Titanium dioxide (TiO2) nanoparticles are extremely attractive materials for numerous applications, especially in the anatase form. We have made these shaped, <10 nm anatase nanoparticles (NPs) via the supercritical (SC) drying of a titania sol, made by a “green” aqueous sol–gel nanosynthesis route. The SC drying was carried out in alcohol at 255–260 °C, and no further heating or processing of the NPs was required. The true phase composition (crystalline and amorphous phases) and the microstructure of the NPs was thoroughly characterised by the advanced X-ray methods, such as Rietveld-reference intensity ratio (RIR) and the whole powder pattern modelling (WPPM) technique, and HR-TEM analysis. Furthermore, the NPs were also characterised by Raman, FT-IR and optical spectroscopy. These anatase NPs showed themselves to exhibit a truncated tetragonal bipyramidal shape, exposing the {101} (side) and {001} (top) faces. They had a euhedral crystal habit, with sharply defined and easily recognised faces, and were very homogeneous and monodisperse in both shape and size. The photocatalytic activity (PCA) of the samples was assessed in gas–solid phase by monitoring the degradation of nitrogen oxides (NOx), a major atmospheric pollutant. Results showed that the particular shape of these anatase NPs played a key role in their photocatalytic behaviour. In fact, these truncated tetragonal bipyramidal nanocrystals exhibited an enhanced photocatalytic activity, double that of spherical anatase NPs of a similar size reported previously by the authors. This was attributed to the exposure of mainly the {101} and, to a lesser extent, {001} crystal faces, which are more reactive under photocatalysis for redox reactions.

New equation of state for the detonation products of explosives

A new equation of state (EoS), named HL, supported by a Boltzmann EoS type and based on physical intermolecular potential of gas components, is presented. This EoS, used in THOR code, takes α=13.5 to the exponent of the intermolecular potential and θ=1.4 to the adimensional temperature. It allows the calculation of thermodynamical properties and final compositions of gas and solid species, at adiabatic isobar and isochor combustion conditions (deflagration) and at Chapman-Jouguet detonation regimes, as a function of the initial composition of energetic system. Its validation has been done, initially, correlating the calculations of detonation of gaseous mixtures to experimental results. Predictions of detonation properties of condensed energetic materials give results in good correlation with experimental values. Deviation is more important in nitroaromatic compounds than in nitramines. Predicted values of detonation velocity show similar results independently of H/NO2 and H(CH2)/NO2 ratios of energetic m...