RESUMO
This work presents the immobilization in situ of commercial lipase from Candida antarctica B (CALB) by the sol-gel technique (xerogel) using silica from rice husk ash (RHA) as a source of silicon. It was used the Ionic Liquid (IL) 1-octyl-3-methylimidazolium bromide (C8MI.Br) as additive. The immobilized derivatives were characterized per SEM, XRD, and per method BET. The enzymatic activity of xerogels was evaluated with different tests, these being the reactional thermal analysis, immobilization yield, and operational and storage stability. The XDR showed that the obtained xerogels have halos in the region between 15 and 35° (2θ) what characterizes it as amorphous materials. The SEM analysis of xerogel shows irregular particles with dimensions less than 20 µm. The immobilized presented an esterification activity (EA) with 263.2 and 213.8 U/g, with and without IL, respectively, higher than the free enzyme (169.6 U/g). The immobilized, with and without IL, presented a significant improvement in the activity performance in relation to free enzyme for the three reactional temperatures (40, 60, and 80 °C) evaluated. The operational stability demonstrated that is possible to use xerogel without ionic liquid for 17 recycles and 21 recycles in IL presence. This methodology allows the preparation of new highly active and selective enzyme catalysts using the rice husk ash as a source of silicon, and the ionic liquid [C8MI]Br as additive. Furthermore, the new materials can provide greater viability in the processes, ensuring longer catalyst life.
Assuntos
Líquidos Iônicos , Oryza , Lipase/metabolismo , Enzimas Imobilizadas/metabolismo , Oryza/metabolismo , Silício , Proteínas Fúngicas/metabolismo , Estabilidade EnzimáticaRESUMO
Sol-gel technique aiming enzymatic immobilization in situ with ionic liquids as additives is poorly studied. In this process, the addition of the enzyme is carried out in the synthesis of the support. The characteristics of ionic liquids, such as low vapor pressure, thermal stability, and non-flammability, make them strong candidates for use as immobilization additives. The objective of the present study was to immobilize the Candida antarctica B lipase by the sol-gel technique using ionic liquids as additives. The optimum points determined for ionic liquids 1-butyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium bromide, and 1 hexadecyl-3-methylimimidazolium were 0.30, 0.27, and 0.22 g/mL of enzyme and 1.60, 1.52, and 1.52% of additive, respectively. The amount of enzyme and ionic liquids used in aerogel immobilization was the same as the optimized values in the xerogel immobilization process (for each ionic liquid). Ionic liquids proved to be good additives in the enzymatic immobilization process. Xerogel, regardless of the ionic liquid, presented a greater number of use cycles and better thermal stability compared to aerogel.
Assuntos
Basidiomycota/enzimologia , Proteínas Fúngicas/química , Líquidos Iônicos/química , Lipase/químicaRESUMO
Arsenic (As) contamination of water is a serious problem in developing countries. In water streams, arsenic can be as As(V) and As(III), the latter being the most toxic species. In this work, an innovative adsorbent based on CaTiO3 nanoparticles (CTO) was prepared by the sol-gel technique for the removal of As(III) from aqueous solution. X-ray diffraction of the CTO nanoparticles powders confirmed the CTO phase. Transmission electron microscopy observations indicated an average particle size of 27 nm, while energy dispersive X-ray spectroscopy analysis showed the presence of Ca, Ti, and O in the expected stoichiometric amounts. The surface specific area measured by Brunauer, Emmett, and Teller (BET) isotherm was 43.9 m2/g, whereas the isoelectric point determined by Zeta Potential measurements was at pH 3.5. Batch adsorption experiments were used to study the effect of pH on the equilibrium adsorption of As(III), using an arsenite solution with 15 mg/L as initial concentration. The highest removal was achieved at pH 3, reaching an efficiency of up to 73%, determined by X-ray fluorescence from the residual As(III) in the solution. Time dependent adsorption experiments at different pHs exhibited a pseudo-second order kinetics with an equilibrium adsorption capacity of 11.12 mg/g at pH 3. Moreover, CTO nanoparticles were regenerated and evaluated for four cycles, decreasing their arsenic removal efficiency by 10% without affecting their chemical structure. X-ray photoelectron spectroscopy analysis of the CTO surface after removal experiments, showed that arsenic was present as As(III) and partially oxidized to As(V).
RESUMO
AIM: Sol-gel is a suitable and advantageous method to synthesize mixed oxide nanomaterials with unique physicochemical and biological properties. MATERIALS & METHODS: In this work, TiO2-SiO2 nanopowders cogeled with platinum acetylacetonate were developed and studied in the perspective of nanomedicine. The physicochemical properties of the Pt/TiO2-SiO2 nanopowders, named NanoRa2-Pt, were evaluated in detail by means of complementary spectroscopic and microscopic tools. The nanopowder's biocatalytic efficiency in wound healing was evaluated in a Type I diabetes animal model. RESULTS: These are TiO2-SiO2 submicron mesoporous particles with variable size and shape containing ultra-small platinum nanoparticles with catalytic properties. CONCLUSION: The use of NanoRa2-Pt catalyzes the natural healing processes with a faster remodeling stage. These sols, which we call nanobiocatalysts, belong to an emerging and very promising research field known as catalytic nanomedicine.
Assuntos
Nanopartículas/química , Platina/química , Dióxido de Silício/química , Titânio/química , Cicatrização/efeitos dos fármacos , Animais , Catálise , Complicações do Diabetes/tratamento farmacológico , Complicações do Diabetes/fisiopatologia , Diabetes Mellitus Tipo 1/complicações , Diabetes Mellitus Tipo 1/tratamento farmacológico , Humanos , Masculino , Nanopartículas Metálicas/química , Nanomedicina , Porosidade , Ratos , Ratos Wistar , Propriedades de SuperfícieRESUMO
Nanostructured porous silica coatings were synthesized on titanium by the combined sol-gel and evaporation-induced self-assembly process. The silica-coating structures were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and nitrogen sorptometry. The effect of the nanoporous surface on apatite formation in simulated body fluid, protein adsorption, osteoblast cell adhesion behavior, and osteogenic differentiation of human bone marrow mesenchymal stem cells (hBMSCs) is reported. Silica coatings with highly ordered sub-10 nm porosity accelerate early osteoblast adhesive response, a favorable cell response that is attributed to an indirect effect due to the high protein adsorption observed on the large-specific surface area of the nanoporous coating but is also probably due to direct mechanical stimulus from the nanostructured topography. The nanoporous silica coatings, particularly those doped with calcium and phosphate, also promote the osteogenic differentiation of hBMSCs with spontaneous mineral nodule formation in basal conditions. The bioactive surface properties exhibited by the nanostructured porous silica coatings make these materials a promising alternative to improve the osseointegration properties of titanium dental implants and could have future impact on the nanoscale design of implant surfaces.