Catalytic Epoxidation and Sulfoxidation Activity of a Dioxomolybdenum(VI) Complex Bearing a Chiral Tetradentate Oxazoline Ligand

A dioxomolybdenum(vi) complex bearing a tetradentate anionic N,O oxazoline ligand with four stereocenters has been studied as a catalyst in the liquid-phase epoxidation of 17 different aliphatic and aromatic olefins (including prochiral, racemate or pure enantiomers) using tert-butyl hydroperoxide as the oxidant. Epoxide selectivities of up to 100% and variable epoxide yields (3–100% within 24 h) were obtained. Although the complex generally exhibited low or no chiral induction ability, diastereoselectivity was significant in some cases (in the reaction of limonene, for example). Kinetic studies and recycling tests with the substrates cis-cyclooctene and trans-β-methylstyrene showed that the catalyst is stable and reusable, and recycling is facilitated by immobilization of the complex in a room temperature ionic liquid. Preliminary results show that the complex may have a broad substrate scope, not only for olefin epoxidation, but also for the dehydrogenation of alcohols to carbonyl compounds and the sulfoxidation of sulfides to sulfoxides.     

Fate of LCFA in the co-digestion of cow manure, food waste and discontinuous addition of oil

Different concentrations of oily waste were added in a discontinuous mode and recurrently to anaerobic continuous stirred tank reactors fed with cow manure and food waste. Four continuous stirred tank reactors were run in parallel. A control reactor (R1) received no additional oil and R2, R3 and R4 received increasing concentrations of oil in two different experimental approaches. First, the lipids composition was forced to change suddenly, in three moments, without changing the total chemical oxygen demand (COD) fed to the reactors. The only long chain fatty acid (LCFA) detected onto the R1 solid matrix was palmitic acid (C16:0). Nevertheless in the solid matrix of R2, R3 and R4 C16:0 and stearic acid were detected. For occasional increase in the oil concentration up to 7.7 gCOD_oil/L_reactor (55% Oil_COD/Total_COD) no statistical differences were detected between the reactors, in terms of methane production, effluent soluble COD, effluent volatile fatty acids and total and volatile solids removal. Therefore this experiment allowed to conclude that cow manure–food waste co-digestion presents sufficient buffer capacity to endure solid-associated LCFA concentration up to 20–25 gCOD-LCFA/kgTS.In a second experiment higher concentrations of oil were added, raising occasionally the concentration in the reactors to 9, 12, 15 and 18 gCOD_oil/L_reactor. All pulses had a positive effect in methane production, with the exception of the highest oil pulse concentration, that persistently impaired the reactor performance. This experiment demonstrates that threshold values for LCFA and C16:0 accumulation onto the solid matrix, of about 180–220 gCOD-LCFA/kgTS and 120–150 gCOD-C16:0/kgTS, should not be surpassed in order to prevent persistent reactor failure, as occurs in some full scale co-digestion plants.     

Soft Nanopatterning on Light‐Emitting Inorganic–Organic Composites

In this work we demonstrate the nanopatterning of nanocomposites made by luminescent zinc oxide nanoparticles and light‐emitting conjugated polymers by means of soft molding lithography. Vertical nanofluidics is exploited to overcome the polymer transport difficulties intrinsic in materials incorporating nanocrystals, and the rheology, fluorescence, absolute quantum yield, and emission directionality of the nanostructured composites are investigated. We study the effect of patterned gratings on the directionality of light emitted from the nanocomposites, finding evidence of the enhancement of forward emitted light, due to the printed wavelength‐scale periodicity. These results open new possibilities for the realization of nanopatterned devices based on hybrid organic‐inorganic systems.     

Quantification of anhydrous ethanol and detection of adulterants in commercial Brazilian gasoline by Raman spectroscopy

Raman spectroscopy can be used to evaluate the quality of fuels in a remote, rapid, and nondestructive manner without the need for reagents. In this study, Raman was used to quantify anhydrous ethanol in commercial gasoline and to detect peaks due to compounds commonly used for the adulteration of commercial gasoline. Samples of commercial gasoline were collected from fuel stations in the region of Santos, SP, Brazil. Samples of naphtha from the refinery, pure ethanol, and ethanol diluted in distilled water at concentrations close to the range used in the gasoline were also obtained and characterized. Raman spectra were collected using a dispersive Raman spectrometer (830?nm, 2?cm^?1 resolution in the 400–1800?cm^?1 spectral range). As expected, the spectra of commercial gasoline showed pronounced peaks of naphtha and ethanol. By using the peak intensities of the ethanol diluted in water, the ethanol concentration was found to be in the range of 27%?±?1% in most of the samples; some samples presented ethanol concentrations as high as 28.8%, suggesting adulteration. Some samples presented peaks at 766, 798, and 995?cm^?1 with higher intensities, suggesting the presence of an adulterant with organic characteristics, such as solvents with aromatic rings. Raman spectroscopy has been shown to be effective in determining the adulteration of commercial gasoline, which may contribute to rapid quality control of fuels at the point of sale.     

Thermal and dynamic mechanical behavior of epoxy composites reinforced with post-consumed yerba mate

Yerba mate (YM) is widely consumed in Latin American countries, and its residues can be used as bio-resources such as reinforced in epoxy composites. The present work aims to produce epoxy resin composites and evaluate the influence of post-consumed YM as reinforcement. The concentrations of YM used were 5, 10, and 20% (wt/wt). Chemical, thermal, morphological, and dynamic mechanical behaviors were explored. The YM incorporation did not influence chemically on the epoxy structure and a pull-out phenomenon was observed as YM content increased. The YM at lower concentrations (5 and 10%) led to higher values of activation energies calculated from model-free isoconversional methods. On the other hand, the composite e/YM 20 wt% improved all dynamic-mechanical properties. YM proved to be a suitable and cheap reinforcement for epoxy resin.     

A visible-light and infrared video database for performance evaluation of video/image fusion methods

Multidimensional Systems and Signal Processing - In general, the fusion of visible-light and infrared images produces a composite representation where both data are pictured in a single image. The...     

Solution blow spun titania nanofibers from solutions of high inorganic/organic precursor ratio

In this work titania nanofibers were produced from different precursor solutions by solution blow spinning. Hydrophilic polyvinylpyrrolidone, hydrophobic poly(vinyl acetate) and amorphous and semi-crystalline poly(lactic acid) polymers were used with green-solvents and titanium isopropoxide as the inorganic precursor. Hybrid nanofibers with high inorganic loading content were successfully produced from all precursor solutions. The fibers were calcined at different annealing temperatures for evaluation of phase transitions. The minimum temperature to obtain pure titania fiber was found to be 500 °C, as assessed by thermal characterization. Anatase was the unique polymorph formed at this annealing temperature. This is of paramount importance due to its photocatalytic character. Calcination at high temperatures showed that rutile slightly appeared at 600 °C for the polyvinylpyrrolidone-based system and showed a strong peak at 700 °C for all systems, co-existing with anatase as minor phase. The use of amorphous and semicrystalline poly(lactic acid) polymers did not influence the anatase crystal size and phase conversion. This was found to be dependent on the annealing temperature and medium acidity, as currently found in powder synthesis.     

Nanocomposite powders of hydroxyapatite-graphene oxide for biological applications

The repair of bone fractures is a clinical challenge for patients with impaired healing, such as osteoporosis. Currently, different strategies have been developed to design new biomaterials, enhancing their interactions with biological systems and conducting the cellular behavior in the desired direction to help fracture healing. In the present work, hydroxyapatite-graphene oxide (HA-GO) nanocomposites were produced and the morphological and physicochemical influences of the addition of 0.5 wt%, 1.0 wt% and 1.5 wt% of GO to HA were observed. FEG-SEM and TEM analyses of HA-GO nanocomposites showed HA nanoparticles adhered to the surface of the GO sheets, suggesting an effective method to form nanostructured graphene-based biomaterials. As confirmation, physicochemical analyses by Raman, FTIR and TGA demonstrated a strong affinity between HA and GO, according to the increase of concentration from 0.5 wt% to 1.5 wt% GO in the HA-GO nanocomposites. Also, in order to evaluate the HA-GO nanocomposites behavior under biological microenvironment, in vitro bioactivity and indirect cytotoxicity tests were performed. FEG-SEM analyses confirmed the positive results for the bioactivity properties of HA-GO nanocomposite and indirect cytotoxicity demonstrated that even with a decrease in the hDPSCs viability and proliferation, when increasing to 1.5 wt% of GO concentration, high level of cell viability was exhibited by HA-GO nanocomposites. These biological results suggested the 0.5 wt% HA-GO nanocomposite as a potential bioactive bone graft and a promising biomaterial for bone tissue regeneration, when compared to the pure HA.     

Time-temperature behavior of carbon/epoxy laminates under creep loading

Mechanics of Time-Dependent Materials - The time-temperature creep behavior of advanced composite laminates is herein determined through a comprehensive set of experiments and analytical modeling....