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A new curcuminoid molecule (3) has been designed and synthesized, containing a central -(CH2)2-COOH chain at the α carbon of the keto-enol moiety in the structure. The carboxylic acid group is added to react with exposed amino groups on silica oxide nanoparticles (nSiO2), forming an amide bond to attach the curcuminoid moiety to the nSiO2 covalently. The Kaiser test quantifies the functionalization degree, yielding 222 µmol of curcuminoid per gram of nanoparticles. The synthesized hybrid nanosystem, nSiO2-NHCO-CCM, displays significant emission properties, with a maximum emission at 538 nm in dichloromethane, similar to curcuminoid 1 (without the central chain), which emits at 565 nm in the same solvent. Solvent-induced spectral effects on the absorption and emission bands of the new hybrid nanosystem are confirmed, similar to those observed for the free curcuminoid (1). The new nanosystem is evaluated in the presence of kerosene in water, showing an emission band at 525 nm as a detection response. The ability of nSiO2-NHCO-CCM to change its fluorescence when interacting with kerosene in water is notable, as it overcomes the limitation caused by the insolubility of free curcuminoid 1 in water, allowing for the exploitation of its properties when connected to the water-stable nanosystem for future detection studies.
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NO2 is one of the main greenhouse gases, which is mainly generated by the combustion of fossil fuels. In addition to its contribution to global warming, this gas is also directly dangerous to humans. The present work reports the structural and gas sensing properties of the CaCu3Ti4O12 compound prepared by the sol-gel technique. Rietveld refinement confirmed the formation of the pseudo-cubic CaCu3Ti4O12 compound, with less than 4 wt% of the secondary phases. The microstructural and elemental composition analysis were carried out using scanning electron microscopy and X-ray energy dispersive spectroscopy, respectively, while the elemental oxidation states of the samples were determined by X-ray photoelectron spectroscopy. The gas sensing response of the samples was performed for different concentrations of NO2, H2, CO, C2H2 and C2H4 at temperatures between 100 and 300 °C. The materials exhibited selectivity for NO2, showing a greater sensor signal at 250 °C, which was correlated with the highest concentration of nitrite and nitrate species on the CCTO surface using DRIFT spectroscopy.
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In the present work, we report the use of bacterial cells for the production of CdS/CdSe Core/Shell quantum dots (QDs), a complex nanostructure specially designed to improve their performance as photosensitizer in photovoltaic devices. The method requires the incorporation of L-cysteine, CdCl2 and Na2SeO3 to Escherichia coli cultures and allows a tight control of QDs properties. The obtained CdS/CdSe QDs were photophysically and structurally characterized. When compared to CdS QDs, the classical shift in the UV-visible spectra of Core/Shell nanostructures was observed in CdS/CdSe QDs. The nanosize, structure, and composition of Core/Shell QDs were confirmed by TEM and EDS analysis. QDs presented a size of approximately 12 nm (CdS) and 17 nm (CdS/CdSe) as determined by dynamic light scattering (DLS), whereas the fourier transform infrared (FTIR) spectra allowed to distinguish the presence of different biomolecules bound to both types of nanoparticles. An increased photostability was observed in CdS/CdSe nanoparticles when compared to CdS QDs. Finally, biosynthesized CdS/CdSe Core/Shell QDs were used as photosensitizers for quantum dots sensitized solar cells (QDSSCs) and their photovoltaic parameters determined. As expected, the efficiency of solar cells sensitized with biological CdS/CdSe QDs increased almost 2.5 times when compared to cells sensitized with CdS QDs. This work is the first report of biological synthesis of CdS/CdSe Core/Shell QDs using bacterial cells and represents a significant contribution to the development of green and low-cost photovoltaic technologies.
RESUMO
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).
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The type of metal oxide affects the activity and selectivity of Fe2O3â»SiO2â»MeO2â»Pt (Me = Ti, Sn, Ce) catalysts on the hydrogenation of cinnamaldehyde. The double shell structure design is thought to protect the magnetic Fe2O3 cores, and also act as a platform for depositing a second shell of TiO2, SnO2 or CeO2 metal oxide. To obtain a homogeneous metallic dispersion, the incorporation of 5 wt % of Pt was carried out over Fe2O3â»SiO2â»MeO2 (Me = Ti, Sn, Ce) structures modified with (3-aminopropyl)triethoxysilane by successive impregnation-reduction cycles. The full characterization by HR-TEM, STEM-EDX, XRD, N2 adsorption isotherm at -196 °C, TPR-H2 and VSM of the catalysts indicates that homogeneous core-shell structures with controlled nano-sized magnetic cores, multi-shells and metallic Pt were obtained. The nature of the metal oxide affects the Pt nanoparticle sizes where the mean Pt diameter is in the order: â»TiO2â»Pt > â»SnO2â»Pt > â»CeO2â»Pt. Among the catalysts studied, â»CeO2â»Pt had the best catalytic performance, reaching the maximum of conversion at 240 min. of reaction without producing hydrocinnamaldehyde (HCAL). It also showed a plot volcano type for the production of cinnamic alcohol (COL), with 3-phenyl-1-propanol (HCOL) as a main product. The â»SnO2â»Pt catalyst showed a poor catalytic performance attributable to the Pt clusters' occlusion in the irregular surface of the â»SnO2. Finally, the â»TiO2â»Pt catalyst showed a continuous production of COL with a 100% conversion and 65% selectivity at 600 min of reaction.
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The relative dislocation density of aluminum and copper samples is quantitatively measured using linear Resonant Ultrasound Spectroscopy (RUS). For each metallic group, four samples were prepared with different thermomechanical treatments in order to induce changes in their dislocation densities. The RUS results are compared with Nonlinear Resonant Ultrasound Spectroscopy (NRUS) as well as Second Harmonic Generation (SHG) measurements. NRUS has a higher sensitivity by a factor of two to six and SHG by 14â»62%. The latter technique is, however, faster and simpler. As a main result, we obtain a quantitative relation between the changes in the nonlinear parameters and the dislocation density variations, which in a first approximation is a linear relation between these differences. We also present a simple theoretical expression that explains the better sensitivity to dislocation content of the nonlinear parameters with respect to the linear ones. X-Ray diffraction measurements, although intrusive and less accurate, support the acoustics results.
RESUMO
Recently, we reported the production of Cadmium sulfide (CdS) fluorescent semiconductor nanoparticles (quantum dots, QDs) by acidophilic bacteria of the Acidithiobacillus genus. Here, we report that the addition of inorganic phosphate to Acidithiobacillus thiooxidans ATCC 19703 cultures favors the biosynthesis of CdS QDs at acidic conditions (pH 3.5). The effect of pH, phosphate and cadmium concentrations on QDs biosynthesis was studied by using Response Surface Methodology (RSM), a multivariate technique for analytical optimization scarcely used in microbiological studies to date. To address how phosphate affects intracellular biosynthesis of CdS QDs, the effect of inorganic phosphate on bacterial cadmium-uptake was evaluated. By measuring intracellular levels of cadmium we determined that phosphate influences the capacity of cells to incorporate this metal. A relation between cadmium tolerance and phosphate concentrations was also determined, suggesting that phosphate participates in the adaptation of bacteria to toxic levels of this metal. In addition, QDs-biosynthesis was also favored by the degradation of intracellular polyphosphates. Altogether, our results indicate that phosphate contributes to A. thiooxidans CdS QDs biosynthesis by influencing cadmium uptake and cadmium tolerance. These QDs may also be acting as a nucleation point for QDs formation at acidic pH. This is the first study reporting the effect of phosphates on QDs biosynthesis and describes a new cadmium-response pathway present in A. thiooxidans and most probably in other bacterial species.