Engineering the Morphostructural Properties and Drug Loading Degree of Organic-Inorganic Fluorouracil-MgAl LDH Nanohybrids by Rational Control of Hydrothermal Treatment.

Layered double hydroxides (LDHs) or hydrotalcite-like compounds have attracted great attention for the delivery of anticancer drugs due to their 2D structure, exhibiting a high surface-to-volume ratio and a high chemical versatility. The drug is protected between the layers from which it is slowly released, thus increasing the therapeutic effect and minimizing the side effects associated to nonspecific targeting. This work aimed to design LDHs with Mg and Al (molar ratio of 2/1) in brucite-like layers, which retained fluorouracil (5-FU; 5-FU/Al = 1, molar ratio) in the interlayer gallery as the layers grow during the co-precipitation step of the synthesis. To rationally control the physicochemical properties, particularly the size of the crystallites, the aging step following the co-precipitation was performed under carefully controlled conditions by changing the time and temperature (i.e., 25 °C for 16 h, 100 °C for 16 h, and 120 °C for 24 h). The results revealed the achievement of the control of the size of the crystals, which are gathered in three different agglomeration systems, from tight to loose, as well as the loading degree of the drug in the final organic-inorganic hybrid nanomaterials. The role played by the factors and parameters affecting the drug-controlled release was highlighted by assessing the release behavior of 5-FU by changing the pH, solid mass/volume ratio, and ionic strength. The results showed a pH-dependent behavior but not necessarily in a direct proportionality. After a certain limit, the mass of the solid diminishes the rate of release, whereas the ionic strength is essential for the payload discharge.

Using Fly Ash Wastes for the Development of New Building Materials with Improved Compressive Strength.

Fly ash wastes (silica, aluminum and iron-rich materials) could be smartly valorized by their incorporation in concrete formulation, partly replacing the cement. The necessary binding properties can be accomplished by a simple procedure: an alkali activation process, involving partial hydrolysis, followed by gel formation and polycondensation. The correlations between the experimental fly ash processing conditions, particle characteristics (size and morphology) and the compressive strength values of the concrete prepared using this material were investigated by performing a parametric optimization study to deduce the optimal processing set of conditions. The alkali activation procedure included the variation of the NaOH solutions concentration (8-12 M), temperature values (25-65 °C) and the liquid/solid ratio (1-3). The activation led to important modifications of the crystallography of the samples (shown by powder XRD analysis), their morphologies (seen by SEM), particle size distribution and Blaine surface values. The values of the compressive strength of concrete prepared using fly ash derivatives were between 16.8-22.6 MPa. Thus, the processed fly ash qualifies as a proper potential building material, solving disposal-associated problems, as well as saving significant amounts of cement consumed in concrete formulation.

Urea-Assisted Synthesis of Mesoporous TiO2 Photocatalysts for the Efficient Removal of Clofibric Acid from Water.

Mesoporous TiO2 photocatalysts intended for the advanced removal of clofibric acid (CA) from water were synthesized by the sol-gel method in a medium containing cetyl-trimethyl-ammonium bromide (CTAB) and urea, using either ethanol or isopropanol to dilute the TiO2 precursor. The activation of the samples was undertaken at 550, 650 and 750 °C. The XRD revealed that the nature of the solvent resulted in significant differences in the anatase-to-rutile ratios obtained at different temperatures. The specific surface area values were situated between 9 and 43 m2·g-1 and the band gap values were similar for all the samples. The photocatalytic activity of the prepared samples was examined for the degradation of CA, an emergent water contaminant. The photocatalytic tests performed under UV-A irradiation revealed that the photo-reactivity of these materials depends on the calcination temperature. The best results were obtained for the samples calcined at 750 °C, which showed high yields of CA elimination, as well as almost complete mineralization (over 95%) after 180 min of reaction. Good results in terms of catalyst reusability in the reaction were found for the catalyst showing the highest photo-reactivity. Therefore, the samples can be considered good candidates for future water remediation applications.

Tailoring Mesoporous Titania Features by Ultrasound-Assisted Sol-Gel Technique: Effect of Surfactant/Titania Precursor Weight Ratio.

A mesoporous titania structure has been prepared using the ultrasound-assisted sol-gel technique in order to find out a way to tailor its structure. The TiO2 obtained was compared to the same version of titania but synthesized by a conventional sol-gel method with the objective of understanding the effect of ultrasound in the synthesis process. All synthesis experiments were focused on the preparation of a titania photocatalyst. Thus, the anatase photocatalytic active phase of titania was proven by X-ray diffraction. Additionally, the ultrasonation treatment proved to increase the crystallinity of titania samples, being one of the requirements to having good photocatalytic activity for titania. The influence of surfactant/titania precursor weight ratio on the structural (XRD), textural (N2-sorption measurements), morphological (TEM), surface chemistry (FTIR) and optical properties (UVDR) was investigated. It was observed that the crystallite size, specific surface area, band gap energy and even photocatalytic activity was affected by the synergism occurring between cavitation effect and the surfactant/titania precursor weight ratio. The study yielded interesting great results that could be considered for further application of ultrasound to tailor mesoporous titania features via sol-gel soft template synthesis, against conventional sol-gel process.

Zn/La Mixed Oxides Prepared by Coprecipitation: Synthesis, Characterization and Photocatalytic Studies.

Mixed oxides containing zinc and lanthanum were prepared by coprecipitation in alkaline medium, followed by calcination at 400 °C. The initial precipitation product and the calcined form were characterized by Brunauer-Emmett-Teller (BET) method adsorption of nitrogen at -196 °C, Scanning Electron Microscopy/Electron-Probe Microanalysis (SEM/EPM), Ultraviolet-Diffuse Reflectance Spectroscopy (UV-DRS) and Infrared (IR) spectroscopy. The band gap slightly changes from 3.23 eV to 3 eV by calcination. The photocatalytic performance of the solids were investigated in diluted aqueous medium, by using clofibric acid (CA), a stable and toxic molecule used as precursor in some pesticides and drugs, as test compound, possibly found in the wastewaters in low concentrations. The effects of the degradation extent, determined by high performance liquid chromatography (HPLC) and total organic carbon (TOC) measurements, were investigated at different initial concentrations of CA. Within about 60 min the CA degradation is almost total at low concentration values (3 ppm) and reaches over 80% in 180 min for an initial concentration of 50 ppm. Moreover, the CA removal performance of photocatalyst remains excellent after three cycles of use: the removal yield was practically total after 60 min in the first two cycles and reached 95% even in the third cycle.