António Portugal

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.

Characterisation of the surface of a cellulosic multi-purpose office paper by inverse gas chromatography

The surface of multi-purpose cellulosic office paper has been analysed by inverse gas chromatography (IGC). The parameters determined were the dispersive component of the surface free energy, the enthalpy of adsorption and the entropy of adsorption of polar and apolar probes, the Lewis acidity constant, Ka, and the Lewis basicity constant, Kb. It can be concluded that the dispersive component of the surface free energy, γsd decreases with temperature, in the range 50–90°C. The temperature coefficient of γsd, dγsd/dT, is −0.35 mJm −2K−1. The values of Ka and Kb were determined to be 0.11±0.011 and 0.94±0.211, respectively. The predominant surface basicity agrees with expectation, bearing in mind the presence of calcium carbonate, and of a styrene-acrylic copolymer, in the surface sizing formulation. It is thought that during the drying stages following the surface sizing treatment, the starch used as the binder migrates to the interior of the surface sizing layer and then to the paper bulk itself. This migration contributes to a decrease in the hydrophilicity of the surface, and also results in the surface showing only slight Lewis.

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.

Effects of nickel hyperaccumulation in Alyssum pintodasilvae on model arthropods representatives of two trophic levels

An experimental assessment of the defence hypothesis of nickel (Ni) hyperaccumulation in Alyssum was lacking. Also, to date no study had investigated the effects of hyperaccumulator litter on a detritivore species. We performed several experiments with model arthropods representatives of two trophic levels: Tribolium castaneum (herbivore) and Porcellio dilatatus (detritivore). In no-choice trials using artificial food disks with different Ni concentrations, T. castaneum fed significantly less as Ni concentration increased and totally rejected disks with the highest Ni concentration. In choice tests, insects preferred disks without Ni. In the no-choice experiment, mortality was low and did not differ significantly among treatments. Hence, this suggested a deterrent effect of high Ni diet. Experiments with P. dilatatus showed that isopods fed A. pintodasilvae litter showed significantly greater mortality (83%) than isopods fed litter from the non-hyperaccumulator species Iberis procumbens (8%), Micromeria juliana (no mortality) or Alnus glutinosa (no mortality). Also, isopods consumed significantly greater amounts of litter from the non-hyperaccumulator plant species. The behaviour of isopods fed A. pintodasilvae litter suggested an antifeedant effect of Ni, possibly due to post-ingestive toxic effects. Our results support the view that Ni defends the Portuguese serpentine hyperaccumulator A. pintodasilvae against herbivores, indicating that Ni can account both for feeding deterrence and toxic effects. The effects of hyperaccumulator litter on the detritivore P. dilatatus suggest that the activity of these important organisms may be significantly impaired with potential consequences on the decomposition processes.

New Propellant Component, Part II. Study of a PSAN/DNAM/HTPB Based Formulation

A study of DNAM as a candidate ingredient for propellant formulations is reported. A formulation including DNAM and based on Phase Stabilized Ammonium Nitrate (PSAN) and Hydroxy-Terminated-Poly Butadiene (HTPB) was selected for the study. This includes thermoanalytical measurements on the mixtures of solid components and propellant samples. Performance is assessed by burning rate measurements. A new small-scale shock sensitivity test developed for studying the propellant under consideration is described. A good potential for DNAM was found for this formulation as revealed by the performance and low vulnerability of the PSAN/DNAM/HTPB composition.

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).

Thermal decomposition of solid mixtures of 2-oxy-4,6-dinitramine-s-triazine (DNAM) and phase stabilized ammonium nitrate (PSAN)

Abstract The thermal decomposition of solid mixtures of 2-oxy-4,6-dinitramine- s -triazine (DNAM) and phase stabilized ammonium nitrate (PSAN) at different mass ratios has been studied. Simultaneous thermal analysis (DSC/TG) and thermomicroscopy have been used. It was found that PSAN promotes the lowering of the decomposition temperature of DNAM. The beginning of this process occurs when both components are in the solid state irrespective of the composition. However, the composition appears as the main factor determining the process progression once initiated. These observations are interpreted in the light of known properties of both DNAM and PSAN. Non-isothermal kinetic analysis, restricted to the early stage of the decomposition process, has been performed for the particular DNAM/PSAN ratios of 50/50 and 60/40. The complexity of the process is evidenced by the impossibility of being described by a kinetic model function other than an empirical one (Sestak–Berggren). Noticeable differences in the apparent Arrhenius parameters were found, indicating remarkable changes in the process over the composition range of the kinetic analysis.

New Propellant Component, Part I. Study of 4,6-Dinitroamino-1,3,5-Triazine-2(1 H)-One (DNAM)

This paper reports a study of the synthesis and characterization of 4,6-dinitroamino-1,3,5-triazine-2(1 H)-one (DNAM) carried out under the perspective of looking for new ingredients in propellant formulations. Emphasis is given to the characterization of DNAM. The following attributes were identified: low sensitivity to impact and friction, thermal stability over a wide temperature range, energetic nature, high density, and interesting particle size distribution. In Part 2 a preliminary evaluation of DNAM capabilities in a propellant formulation will be presented.