Manuel Augusto Gomes de Oliveira Azenha

Abstract The objective of this work was the exploration of low calcination temperature ranges (< 350 degrees C) to obtain molecularly imprinted microspheres (MIM) with a high crystallinity as anatase, in cooperation of an acidic pretreatment aiming at the preservation of the hollow shape and also of the selective binding sites. It was confirmed the possibility of obtaining bilirubin-imprinted crystalline TiO2 microspheres (highly crystalline anatase, as confirmed by XRD) exhibiting higher photocatalytic efficiency associated especially with the hollow shape and calcination at lower temperatures (200 degrees C or 250 degrees C). It was with the calcination temperature of 250 degrees C that the highest photocatalytic efficiency was obtained, under UV irradiation, associated with the highest adsorption selectivity (alpha(K) = 19) and degradation selectivity (alpha(k) = 2.7) observed for the degradation of the template against a closely related analogue compound.

Abstract Optosensing chitosan-based membranes have been applied for the detection of heavy metals, especially in drinking water. The novelty of this study is based on the use of sulphated polysaccharides, in such optosensing membranes, aiming at an improved analytical performance. The sulphated polysaccharides, such as ulvan, fucoidan and chondroitin sulfate, were extracted from by-products and wastes of marine-related activities. The membranes were developed for the analysis of aluminum. The variation in the visible absorbance of the sensor membranes after the contact between the chromophore and the aluminum cation was studied. The membranes containing sulphated polysaccharides showed improved signals when compared to the chitosan-only membrane. As for the detection limits for the membranes containing ulvan, fucoidan and chondroitin sulfate, 0.17 mg L-1, 0.21 mg L-1 and 0.36 mg L-1 were obtained, respectively. The values were much lower than that obtained for the chitosan-only membrane, 0.52 mg L-1, which shows the improvement obtained from the sulphated polysaccharides. The results were obtained with the presence of CTAB in analysis solution, which forms a ternary complex with the aluminum cation and the chromophore. This resulted in an hyperchromic and batochromic shift in the absorption band. When in the presence of this surfactant, the membranes showed lower detection limits and higher selectivity.

Abstract The possibility of generating organically modified hollow TiO2 microspheres via a simple sol-gel synthesis was demonstrated for the first time in this work. A mixture of titania precursors, including an organically modified precursor, was used to obtain methyl-modified hollow TiO2 microspheres selective for bilirubin by the molecular imprinting technique (Methyl-HTM-MIM). Methyl-HTM-MIM were prepared by a sol-gel method using titanium (IV) isopropoxide (TTIP), and methyltitanium triisopropoxide (MTTIP) as precursors. Two ratios of titania precursors were tested (1/6 and 1/30 mol(MTTIP)/mol(TTIP)). With the characterization results obtained by the SEM and ATR-FTIR techniques, it was possible to establish that only the 1/30 mol(MTTIP)/mol(TTIP) ratio allowed for the preparation of hollow spheres with a reasonably homogeneous methylated-TiO2 shell. It was possible to obtain a certain degree of organization of the hybrid network, which increased with calcination temperatures. By adjusting isothermal adsorption models, imprinting parameters were determined, indicating that the new methylated microspheres presented greater selectivity for bilirubin than the totally inorganic hollow TiO2 microspheres. The effectiveness of the molecular imprinting technique was proven for the first time in an organically modified titania material, with imprinting factor values greater than 1.4, corresponding to a significant increase in the maximum adsorption capacity of the template represented by the molecularly imprinted microspheres. In summary, the results obtained with the new methyl-HTM-MIM open the possibility of exploring the application of these microspheres for selective sorption (separation or sensing, for example) or perhaps even for selective photocatalysis, particularly for the degradation of organic compounds.

Abstract Currently, salinity and heat are two critical threats to crop production and food security which are being aggravated by the global climatic instability. In this scenario, it is imperative to understand plant responses to simultaneous exposure to different stressors and the cross-talk between underlying functional mechanisms. Thus, in this study, the physiological and biochemical responses of tomato plants (Solanum lycopersicum L.) to the combination of salinity (100 mM NaCl) and heat (42 degrees C; 4 h/day) stress were evaluated. After 21 days of co-exposure, the accumulation of Na+ in plant tissues was superior when salt-treated plants were also exposed to high temperatures compared to the individual saline treatment, leading to the depletion of other nutrients and a harsher negative effect on plant growth. Despite that, neither oxidative damage nor a major accumulation of reactive oxygen species took place under stress conditions, mostly due to the accumulation of antioxidant (AOX) metabolites alongside the activation of several AOX enzymes. Nonetheless, the plausible allocation of resources towards the defense pathways related to oxidative and osmotic stress, along with severe Na toxicity, heavily compromised the ability of plants to grow properly when the combination of salinity and heat was imposed.

Abstract Aluminum (Al) toxicity limits crops growth and production in acidic soils. Compared to roots, less is known about the toxic effects of Al in leaves. Al subcellular compartmentalization is also largely unknown. Using rye (Secale cereale L.) Beira (more tolerant) and RioDeva (more sensitive to Al) genotypes, we evaluated the patterns of Al accumulation in leaf cell organelles and the photosynthetic and metabolic changes to cope with Al toxicity. The tolerant genotype accumulated less Al in all organelles, except the vacuoles. This suggests that Al compartmentalization plays a role in Al tolerance of Beira genotype. PSII efficiency, stomatal conductance, pigment biosynthesis, and photosynthesis metabolism were less affected in the tolerant genotype. In the Calvin cycle, carboxylation was compromised by Al exposure in the tolerant genotype. Other Calvin cycle-related enzymes, phoshoglycerate kinase (PGK), glyceraldehyde 3-phosphate dehydrogenase (GAPDH), triose-phosphate isomerase (TPI), and fructose 1,6-bisphosphatase (FBPase) activities decreased in the sensitive line after 48 h of Al exposure. Consequentially, carbohydrate and organic acid metabolism were affected in a genotype-specific manner, where sugar levels increased only in the tolerant genotype. In conclusion, Al transport to the leaf and compartmentalization in the vacuoles tolerant genotype's leaf cells provide complementary mechanisms of Al tolerance, protecting the photosynthetic apparatus and thereby sustaining growth.