Reusable composite membranes for highly efficient chromium removal from real water matrixes.

Natural or industrial hexavalent chromium water pollution continues to be a worldwide unresolved threat. Today, there is intense research on new active and cost-effective sorbents for Cr(VI), but most still exhibit a critical limitation: their powdered nature makes their recovery from water cost and energy consuming. In this work, Al(OH)3, MIL-88-B(Fe), and UiO-66-NH2 Cr(VI) sorbents were immobilized into a poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymeric substrate to develop an easily reactivable and reusable water filtering technology. The immobilization of the sorbents into the PVDF-HFP porous matrix modified the macro and meso-porous structure of the polymeric matrix, tuning in parallel its wettability. Although a partial blocking of the Cr(VI) adsorptive capacity was observed for of Al(OH)3 and MIL-88-B(Fe) when immobilized into composite membranes, PVDF-HFP/UiO-66-NH2 filter (i) exceeded the full capacity of the non-immobilized sorbent to trap Cr(VI), (ii) could be reactivated and reusable, and (iii) it was fully functional when applied in real water effluents.

Multifunctional hybrid membranes for photocatalytic and adsorptive removal of water contaminants of emerging concern.

This work focuses on the combination of multifunctional photocatalytic and adsorbent materials in a unique polymeric membrane. For this purpose, Au/TiO2 and Y2(CO3)3 nanoparticles were immobilised onto a poly (vinylidene fluoride-hexafluoropropylene), (PVDF-HFP) membrane, and the physical-chemical characterisation of these materials was performed, as well as pollutant removal efficiency. An efficient TiO2 functionalisation with gold nanoparticles was achieved, endowing these particles with the capability to absorb visible radiation absorption. A favourable porous structure was obtained for the membranes, with an average pore size of 4 µm, and the nanoparticles immobilisation did not alter the chemical properties of the polymeric membrane. The produced hybrid materials, including both the Au/TiO2 and Y2(CO3)3 nanoparticles, presented an efficiency of 57% in the degradation of norfloxacin (5 mg/L) under ultraviolet radiation for 120 min, 80% under visible radiation for 300 min, and 58% in arsenic adsorption for 240 min. These membranes represent a new multifunctional platform for removing several pollutants, which may allow their incorporation in more efficient and less energy-consuming water treatment processes favouring its application, even in low energy resources countries.

Crystal morphology control of synthetic giniite for enhanced photo-Fenton activity against the emerging pollutant metronidazole.

Metronidazole (MNZ) is a recalcitrant antibiotic with toxic and carcinogenic effects in aquatic environments. In this work, Fe5(PO4)4(OH)3·2H2O (giniite) particles were synthesised with three different alkaline cations (Li+, Na+ and K+) and used as Fenton catalysts for MNZ removal. It is shown that the addition of different cations during the hydrothermal synthesis process promote different morphologies from asterisk-like to flower-like and branches-like, maintaining the crystalline structure of pure giniite. The photo-Fenton activity of these particles was then evaluated through the degradation of MNZ under sunlight radiation for 9 h. The results indicate that the alkaline cation has a predominant role in the photo-Fenton efficiency, as demonstrated by the superior degradation efficiencies of Na@giniite particles (91.2% and 72.5% with giniite concentration of 0.2 g L-1 and 0.07 g L-1, respectively), related with its high surface area (10.7 m2 g-1). Thus, it is demonstrated the suitability of Na@giniite particles as Fenton catalyst for MNZ removal from water.

Photocatalytic and antimicrobial multifunctional nanocomposite membranes for emerging pollutants water treatment applications.

Emerging pollutants represent a new global problem for water quality. As these compounds get into the environment, they cause severe threats to aquatic environments and human health and are typically resistant to conventional wastewater treatments. In this work, TiO2 nanoparticles surface was functionalized with silver (Ag) nanoparticles, and solvent cast and electrospun membranes of poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) were prepared with different concentrations of TiO2 and Ag-TiO2 to produce a multifunctional material. The photocatalytic activity of the nanocomposites was evaluated through the degradation of norfloxacin under ultraviolet (UV) and visible radiation. It is shown that nanocomposites with Ag-TiO2 show the highest degradation efficiencies: 64.2% under UV and 80.7% under visible radiation, for 90 and 300 min, respectively. Furthermore, the recyclability of the membranes has also been demonstrated. Finally, it is shown the antimicrobial activity of the nanocomposite membranes, demonstrating the suitability of the Ag-TiO2/PVDF-HFP nanocomposites as multifunctional photocatalytic and antimicrobial membranes for water remediation applications.

Photocatalytic reusable membranes for the effective degradation of tartrazine with a solar photoreactor.

Recalcitrant dyes present in effluents constitute a major environmental concern due to their hazardous properties that may cause deleterious effects on aquatic organisms. Tartrazine is a widely-used dye, and it is known to be resistant to biological and chemical degradation processes and by its carcinogenic and mutagenic nature. This study presents the use of TiO2 (P25) nanoparticles immobilized into a poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)) membrane to assess the photocatalytic degradation of this dye in a solar photoreactor. The nanocomposite morphological properties were analyzed, confirming an interconnected porous microstructure and the homogeneous distribution of the TiO2 nanoparticles within the membrane pores. It is shown that the nanocomposite with 8wt% TiO2 exhibits a remarkable sunlight photocatalytic activity over five hours, with 78% of the pollutant being degraded. It was also demonstrated that the degradation follows pseudo-first-order kinetics model at low initial tartrazine concentration. Finally, the effective reusability of the produced nanocomposite was also assessed.

Processing and size range separation of pristine and magnetic poly(l-lactic acid) based microspheres for biomedical applications.

Biodegradable poly(l-lactic acid) (PLLA) and PLLA/CoFe2O4 magnetic microspheres with average sizes ranging between 0.16-3.9µm and 0.8-2.2µm, respectively, were obtained by an oil-in-water emulsion method using poly(vinyl alcohol) (PVA) solution as the emulsifier agent. The separation of the microspheres in different size ranges was then performed by centrifugation and the colloidal stability assessed at different pH values. Neat PLLA spheres are more stable in alkaline environments when compared to magnetic microspheres, both types being stable for pHs higher than 4, resulting in a colloidal suspension. On the other hand, in acidic environments the microspheres tend to form aggregates. The neat PLLA microspheres show a degree of crystallinity of 40% whereas the composite ones are nearly amorphous (17%). Finally, the biocompatibility was assessed by cell viability studies with MC3T3-E1 pre-osteoblast cells.

Differential expression of genes involved in the degeneration and regeneration pathways in mouse models for muscular dystrophies.

The genetically determined muscular dystrophies are caused by mutations in genes coding for muscle proteins. Differences in the phenotypes are mainly the age of onset and velocity of progression. Muscle weakness is the consequence of myofiber degeneration due to an imbalance between successive cycles of degeneration/regeneration. While muscle fibers are lost, a replacement of the degraded muscle fibers by adipose and connective tissues occurs. Major investigation points are to elicit the involved pathophysiological mechanisms to elucidate how each mutation can lead to a specific degenerative process and how the regeneration is stimulated in each case. To answer these questions, we used four mouse models with different mutations causing muscular dystrophies, Dmd (mdx), SJL/J, Large (myd) and Lama2 (dy2J) /J, and compared the histological changes of regeneration and fibrosis to the expression of genes involved in those processes. For regeneration, the MyoD, Myf5 and myogenin genes related to the proliferation and differentiation of satellite cells were studied, while for degeneration, the TGF-ß1 and Pro-collagen 1α2 genes, involved in the fibrotic cascade, were analyzed. The result suggests that TGF-ß1 gene is activated in the dystrophic process in all the stages of degeneration, while the activation of the expression of the pro-collagen gene possibly occurs in mildest stages of this process. We also observed that each pathophysiological mechanism acted differently in the activation of regeneration, with distinctions in the induction of proliferation of satellite cells, but with no alterations in stimulation to differentiation. Dysfunction of satellite cells can, therefore, be an important additional mechanism of pathogenesis in the dystrophic muscle.

Ação do óleo essencial de Syzygium aromaticum (L.) Merr. & L.M.Perry sobre as hifas de alguns fungos fitopatogênicos / Action of Syzygium aromaticum (L.) Merr. & L.M.Perry essential oil on the hyphae of some phytopathogenic fungi

Atualmente o uso de métodos alternativos para o controle de doenças e pragas na agricultura, visando minimizar os danos ao meio ambiente e à saúde pública é uma prática reconhecida e necessária. Este trabalho objetivou investigar a ação do óleo essencial de Syzygium aromaticum (L.) Merr. & L.M.Perry sobre o crescimento micelial in vitro dos fungos fitopatogênicos Rhizoctonia solani, Fusarium solani, Fusarium oxysporum e Macrophomina phaseolina. A análise por cromatografia gasosa acoplada com espectrometria de massa possibilitou a identificação de eugenol (83,6 por cento), acetato de eugenila (11,6 por cento) e cariofileno (4,2 por cento). A avaliação microscópica dos micélios dos fungos evidenciou diversas alterações morfológicas, como a presença de vacúolos, desorganização dos conteúdos celulares, diminuição na nitidez da parede celular, intensa fragmentação e menor turgência das hifas. O óleo essencial de cravo apresentou atividade fungicida na concentração de 0,15 por cento sobre o crescimento de R. solani, F. oxysporum e F. solani, entretanto não demonstrou essa atividade sobre M. phaseolina. Esses resultados indicam perspectivas favoráveis para posterior uso do óleo de cravo no controle desses fitopatógenos na agricultura.

Currently, the use of alternative methods to control diseases and pests in agriculture has been a recognized and necessary practice to minimize damages to the environment and public health. This study aimed to investigate the action of clove [Syzygium aromaticum (L.) Merr. & L.M.Perry] essential oil on the in vitro mycelial growth of the phytopathogenic fungi Rhizoctonia solani, Fusarium solani, Fusarium oxysporum and Macrophomina phaseolina. Analysis by gas chromatography-mass spectrometry allowed the identification of eugenol (83.6 percent), eugenyl acetate (11.6 percent) and caryophyllene (4.2 percent). Microscopic evaluation of mycelia showed several morphological changes such as presence of vacuoles, cell content disorganization, decreased cell wall clearness, intense fragmentation and lower turgescence of hyphae. Clove essential oil showed fungicidal activity at 0.15 percent on the growth of R. solani, F. oxysporum and F. solani, but not for M. phaseolina. These results indicate favorable perspectives for future use of clove essential oil to control these phytopathogens in agriculture.

Intravenous injections of PAF-acether induce platelet aggregation in rats.

The mechanism of rat thrombocytopenia induced by i.v. injections of platelet-activating factor (PAF-acether) was investigated. Platelet counts performed after diluting the blood samples in 1% formalin in saline showed that PAF-acether (6 micrograms/kg i.v.) induced a significant thrombocytopenia in rats, which peaked within 1 h, followed by a drastic increase of platelet counts at 4 h and a return to basal levels at 24 h. At this time, it was not possible to induce thrombocytopenia with a second challenge with PAF-acether, indicating a clear state of desensitization which disappeared within five days after the first injection of PAF-acether. The pretreatment with the specific PAF-acether receptor antagonist, BN 52021 (2.5-15 mg/kg), 48740 RP (6-25 mg/kg) and WEB 2086 (0.25-1 mg/kg) blocked the thrombocytopenia dose dependently. The lipoxygenase inhibitor nordihydroguaiaretic acid, at 25-100 mg/kg, was also effective against the thrombocytopenia induced by PAF-acether, reinforcing the potential involvement of arachidonic acid derivatives in this process. Adrenal hormones may modulate this process, since adrenalectomized animals responded to PAF-acether with exacerbated thrombocytopenia. No reduction in the platelet counts was noted when the blood was diluted in formalin-free saline, indicating that unstable aggregates were formed in vivo, which tended to resolve in vitro. Our results suggest that the thrombocytopenia induced in rats by PAF results from a reversible process of intravascular platelet aggregation, probably following the secretion of platelet-activating substances released by a first-hit blood cell.