Synthesis of glycerol carbonate from glycerol and dimethyl carbonate by transesterification: Catalyst screening and reaction optimization

The synthesis of glycerol carbonate from glycerol and dimethyl carbonate by transesterification is reported. Firstly, a catalyst screening has been performed by studying the influence of different basic and acid homogeneous and heterogeneous catalysts on reaction results. Catalytic activity is extremely low for acidic catalysts indicating that reaction rate is very slow. On the contrary, high conversions and yields are obtained for basic catalysts. Catalytic activity increases with catalyst basic strength. The best heterogeneous catalyst is CaO. Calcination of CaO increases dramatically its activity due to calcium hydroxide removal from its surface. A reaction optimization study has been carried out with CaO as catalyst by using a factorial design of experiments leading to operation conditions for achieving a 100% conversion and a >95% yield at 1.5 h reaction time: 95 °C, catalyst/glycerol molar ratio = 0.06 and dimethyl carbonate/glycerol molar ratio = 3.5. Carbonate glycerol can be easily isolated by filtering the catalyst out and evaporating the filtrate at vacuum. Leaching of catalyst in reaction medium was lower than 0.34%. Catalyst recycling leads to a quick decrease in both conversions and yields probably due to a combination of catalyst deactivation by CaO exposure to air between catalytic runs, and a decrease in the catalyst surface area available for reaction due to particle agglomeration.     

Rheological and electrical percolation thresholds of carbon nanotube/polymer nanocomposites

Percolation thresholds of multiwalled carbon nanotube/polystyrene (MWCNT/PS) nanocomposites (NC) were determined by rheology and electrical conductivity. The percolation threshold found by electrical conductivity was 0.5% carbon nanotubes (CNT) and that by mechanical spectroscopy and relaxation measurements was 0.9% CNT. These results together with those reported in the literature show several types of percolation thresholds, depending on the average filler–filler (CNT and/or aggregates) distance in a polymer matrix. A distance close to polymer gyration radius corresponds to a “soft” rheological threshold (P_{C rheo}^soft). Close contacts between fillers giving rise to a conductive path corresponds to an electrical threshold (P_{C elec}). At high filler concentration, fillers form a network, corresponding to a “rigid” rheological threshold (P_{C rheo}^rigid). These thresholds depend on the filler content and follow the order: P_{C elec}^soft < P_{C elec} < P_{C rheo}^rigid. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Photocatalytic enamel/TiO2 coatings developed by electrophoretic deposition for methyl orange decomposition

The aim of this study was to obtain photocatalytic coatings, capable to decompose organic pollutants, through Electrophoretic Deposition (EPD) of enamels containing respectively 0%, 5%, 10%, 15% (in wt%) of TiO₂ onto carbon steel substrates. High quality and homogeneous coatings were obtained by applying 12.5?V during 10?s, as the best EPD conditions. The layers were subsequently heat treated at 740?°C for 10?min, in order to obtain dense glazes.Rietveld refinement of XRD patterns and Raman results show that, after the heat treatment at 740?°C, TiO₂ mostly exists as anatase, responsible of the photocatalytic effect. Semi-quantitative chemical analysis indicate segregation of TiO₂ on the coatings surface, reaching saturation in the sample with 10?wt% TiO₂. FEG-SEM observations reveal rod-like and spherical Ti-rich phases along the cross section of the coatings; some Ti was also dissolved into the enamel. 3D topographical mapping shows that, by adding TiO₂, surface roughness increases significantly.Photocatalytic tests were carried out using a 2?×?10^?5 M aqueous solution of Methyl Orange (MO) as an organic pollutant. By comparing the decomposition rate of MO achieved with the pure enamel (0% of TiO₂) and with the sample with 10% of TiO₂, it was shown that the addition of 10% of TiO₂ results in 90% photocatalytic efficiency.Moreover, the permeation of organic compounds and their UV degradation were studied by measuring the water contact angle onto the enamel surface directly after dipping into oleic acid and after various UV irradiation times. The longer the UV irradiation time, the lower the contact angle, down to a minimum of 14.54° after 8?h of UV irradiation. This means, the compound was initially adsorbed on the enamel/TiO₂ coating surface (10?wt% TiO₂) but was efficiently decomposed upon UV irradiation.     

Molecular and Electrophysiological Role of Diabetes-Associated Circulating Inflammatory Factors in Cardiac Arrhythmia Remodeling in a Metabolic-Induced Model of Type 2 Diabetic Rat

Background: Diabetic patients have prolonged cardiac repolarization and higher risk of arrhythmia. Besides, diabetes activates the innate immune system, resulting in higher levels of plasmatic cytokines, which are described to prolong ventricular repolarization. Methods: We characterize a metabolic model of type 2 diabetes (T2D) with prolonged cardiac repolarization. Sprague-Dawley rats were fed on a high-fat diet (45% Kcal from fat) for 6 weeks, and a low dose of streptozotozin intraperitoneally injected at week 2. Body weight and fasting blood glucose were measured and electrocardiograms of conscious animals were recorded weekly. Plasmatic lipid profile, insulin, cytokines, and arrhythmia susceptibility were determined at the end of the experimental period. Outward K⁺ currents and action potentials were recorded in isolated ventricular myocytes by patch-clamp. Results: T2D animals showed insulin resistance, hyperglycemia, and elevated levels of plasma cholesterol, triglycerides, TNFα, and IL-1b. They also developed bradycardia and prolonged QTc-interval duration that resulted in increased susceptibility to severe ventricular tachycardia under cardiac challenge. Action potential duration (APD) was prolonged in control cardiomyocytes incubated 24 h with plasma isolated from diabetic rats. However, adding TNFα and IL-1b receptor blockers to the serum of diabetic animals prevented the increased APD. Conclusions: The elevation of the circulating levels of TNFα and IL-1b are responsible for impaired ventricular repolarization and higher susceptibility to cardiac arrhythmia in our metabolic model of T2D.     

Lumped-intermediates analysis in the photooxidation of Rhodamine 6G in the H<Subscript>2</Subscript>O<Subscript>2</Subscript>/UV system

The combination of H₂O₂ with UV radiation was applied to study the degradation of Rhodamine 6G dye (Rh-6G). The lumped kinetic model proposed in this work is a reaction-system scheme to describe the degradation of dye using lumps of intermediate compounds grouped by their chemical and colorimetric behavior. Rate constants obtained by application of the model were shown to predict the progress of dye oxidation. The effects of pH and oxidant dosage on these rate constants were also analyzed. Finally, photodecoloration was studied considering the absorption at 528 nm (the maximum absorption wavelength of the dye) as the sum of all compounds absorbing at this wavelength: Rhodamine itself and the colored intermediates produced.     

An integral planning model that includes production,selling price,cash flow management and flexible capacity

Many authors consider that production and marketing decisions should be integrated. In this paper, we discuss an aggregate planning problem that includes production, selling price, cash management and flexible capacity (by means of hiring and firing and with the possibility of unlimited production subcontracting). The demand is considered to be a nonlinear function of the product selling price. The problem, which is modelled as a mixed integer linear program, can be solved using standard optimisation software. The results of a computational experiment and a numerical example are shown to illustrate the performance of the proposed model and obtain some managerial insights.     

Polymorphism in Non-Fullerene Acceptors Based on Indacenodithienothiophene

Organic solar cells incorporating non-fullerene acceptors (NFAs) have reached remarkable power conversion efficiencies of over 18%. Unlike fullerene derivatives, NFAs tend to crystallize from solutions, resulting in bulk heterojunctions that include a crystalline acceptor phase. This must be considered in any morphology-function models. Here, it is confirmed that high-performing solution-processed indacenodithienothiophene-based NFAs, i.e., ITIC and its derivatives ITIC-M, ITIC-2F, and ITIC-Th, exhibit at least two crystalline forms. In addition to highly ordered polymorphs that form at high temperatures, NFAs arrange into a low-temperature metastable phase that is readily promoted via solution processing and leads to the highest device efficiencies. Intriguingly, the low-temperature forms seem to feature a continuous network that favors charge transport despite of a poorly order along the π–π stacking direction. As the optical absorption of the structurally more disordered low-temperature phase can surpass that of the more ordered polymorphs while displaying comparable—or even higher—charge transport properties, it is argued that such a packing structure is an important feature for reaching highest device efficiencies, thus, providing guidelines for future materials design and crystal engineering activities.     

Elderly user experience to improve a Kinect-based game playability

When it comes to using computers, older people experience many barriers, which are a considerable hurdle to overcome in order to enable them to accept technological aids. Thus, computer interface design and development must support elderly end users by avoiding many usability issues which lead to negative impacts on them. This paper describes the combination of a computer game design for the elderly and its implementation with user experience considerations embedded in the process. In this way, a positive gaming experience is provided to the end user. This game uses the Kinect device, enabling users to interact intuitively with the computer without any intermediary controller, and its main purpose is to promote at the same time cognitive and physical activities for healthy living. Feedback was taken from physiotherapists’ written observations and user experience questionnaires, which allowed the game to be adapted to their needs, obtaining 86.25% satisfaction. The effectiveness of this study opens the door to new developments in ICT that not only improve quality of life but also reduce the existing digital divide for the elderly.     

Toward Rigorous Materials Production: New Approach Methodologies Have Extensive Potential to Improve Current Safety Assessment Practices

Advanced material development, including at the nanoscale, comprises costly and complex challenges coupled to ensuring human and environmental safety. Governmental agencies regulating safety have announced interest toward acceptance of safety data generated under the collective term New Approach Methodologies (NAMs), as such technologies/approaches offer marked potential to progress the integration of safety testing measures during innovation from idea to product launch of nanomaterials. Divided in overall eight main categories, searchable databases for grouping and read across purposes, exposure assessment and modeling, in silico modeling of physicochemical structure and hazard data, in vitro high‐throughput and high‐content screening assays, dose‐response assessments and modeling, analyses of biological processes and toxicity pathways, kinetics and dose extrapolation, consideration of relevant exposure levels and biomarker endpoints typify such useful NAMs. Their application generally agrees with articulated stakeholder needs for improvement of safety testing procedures. They further fit for inclusion and add value in nanomaterials risk assessment tools. Overall 37 of 50 evaluated NAMs and tiered workflows applying NAMs are recommended for considering safer‐by‐design innovation, including guidance to the selection of specific NAMs in the eight categories. An innovation funnel enriched with safety methods is ultimately proposed under the central aim of promoting rigorous nanomaterials innovation.     

Performance of carbon-supported PtPd as catalyst for hydrogen oxidation in the anodes of proton exchange membrane fuel cells

In this work, the replacement of platinum by palladium in carbon-supported catalysts as anodes for hydrogen oxidation reaction (HOR), in proton exchange membrane fuel cells (PEMFCs), has been studied. Anodes with carbon-supported Pt, Pd, and equiatomic Pt:Pd, with various Nafion^® contents, were prepared and tested in H₂|O₂ (air) PEMFCs fed with pure or CO-contaminated hydrogen. An electrochemical study of the prepared anodes has been carried out in situ, in membrane electrode assemblies, by cyclic voltammetry and CO electrooxidation voltammetry. The analyses of the corresponding voltammograms indicate that the anode composition influences the cell performance. Single cell experiments have shown that platinum could be replaced, at least partially, saving cost with still good performance, by palladium in the hydrogen diffusion anodes of PEMFCs. The performance of the PtPd catalyst fed with CO-contaminated H₂ used in this work is comparable to Pt, thus justifying further work varying the CO concentration in the H₂ fuel to assert its CO tolerance and to study the effect of the Pt:Pd atomic ratio.