Ethanol steam reforming over Ni/La–Al2O3 catalysts: Influence of lanthanum loading

Hydrogen production from ethanol reforming over nickel catalysts supported on lanthanum loaded Al₂O₃ substrates was studied. Activity results revealed the enhancement in the reforming stability of the Ni catalysts with the increase in the lanthanum loading on Al₂O₃ substrates. Catalytic behavior of Ni/La–Al₂O₃ catalysts in the ethanol steam reforming was found to be the contribution of the activity of the La–Al₂O₃ supports for the ethanol dehydration reaction and the activity of the nickel metallic phase that catalyzes both dehydrogenation and CC bond rupture. Physicochemical characterization of catalysts revealed that acidity, nickel dispersion and nickel-support interaction depend on the La-loading on Al₂O₃. The better reforming stability of catalysts with the increase in La content was explained in terms of the ability of nickel surface and/or La–Ni interactions to prevent the formation of carbon filaments.     

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends. II: Polypropylene‐(ethylene‐propylene) heterophasic copolymer [PP‐EP]/EVA systems

Morphological characteristics and mechanical properties of PP‐EP/EVA blends were studied and compared to those of PP/EVA previously reported. For the PPEP/EVA blends, interfacial interactions in amorphous zones, which were associated with shifts in T_g, were well defined compared to those of PP/EVA blends, although the nature of crystalline zones was similar for both systems. At EVA concentrations up to 20%, the elongation at break and impact strength slightly increased in both systems. However, PP‐EP/EVA displayed higher values of these properties compared with PP/EVA. At high EVA concentrations (above 20%), the indicated properties were enhanced in both polymeric systems, and the same proportional behavior was maintained. The decrease in tensile strength of PP‐EP/EVA was not as marked as in PP/EVA with the addition of EVA, and it remained below PP/EVA at high EVA concentrations. The improvement in properties of PP‐EP/EVA was attributed to favorable interactions between the ethylene groups contained in both copolymers. These interactions rendered a high degree of compatibility between the PP‐EP and EVA components.     

Indoloazepinone‐Constrained Oligomers as Cell‐Penetrating and Blood–Brain‐Barrier‐Permeating Compounds

Non‐cationic and amphipathic indoloazepinone‐constrained (Aia) oligomers have been synthesized as new vectors for intracellular delivery. The conformational preferences of the [l ‐Aia‐Xxx]_n oligomers were investigated by circular dichroism (CD) and NMR spectroscopy. Whereas Boc‐[l ‐Aia‐Gly]_2,4‐OBn oligomers 12 and 13 and Boc‐[l ‐Aia‐β³‐h‐l ‐Ala]_2,4‐OBn oligomers 16 and 17 were totally or partially disordered, Boc‐[l ‐Aia‐l ‐Ala]₂‐OBn ( 14 ) induced a typical turn stabilized by C₅‐ and C₇‐membered H‐bond pseudo‐cycles and aromatic interactions. Boc‐[l ‐Aia‐l ‐Ala]₄‐OBn ( 15 ) exhibited a unique structure with remarkable T‐shaped π‐stacking interactions involving the indole rings of the four l ‐Aia residues forming a dense hydrophobic cluster. All of the proposed FITC‐6‐Ahx‐[l ‐Aia‐Xxx]₄‐NH₂ oligomers 19 – 23 , with the exception of FITC‐6‐Ahx‐[l ‐Aia‐Gly]₄‐NH₂ ( 18 ), were internalized by MDA‐MB‐231 cells with higher efficiency than the positive references penetratin and Arg₈. In parallel, the compounds of this series were successfully explored in an in vitro blood–brain barrier (BBB) permeation assay. Although no passive diffusion permeability was observed for any of the tested Ac‐[l ‐Aia‐Xxx]₄‐NH₂ oligomers in the PAMPA model, Ac‐[l ‐Aia‐l ‐Arg]₄‐NH₂ ( 26 ) showed significant permeation in the in vitro cell‐based human model of the BBB, suggesting an active mechanism of cell penetration.     

Impact of Defects on Pyrazolate Based Metal Organic Frameworks

The high strength of the metal-pyrazolate coordination bond allows the deliberate introduction of defects on pyrazolate based metal-organic frameworks without affecting the integrity of the porous crystalline network. Yet the presence of defects has a major impact on the properties of these systems which include higher pore accessibility and increased interactions with guest molecules, higher ion/electronic mobility and enhanced catalytic properties. In this review selected examples of the impact of the presence of defects in the capture of environmentally relevant gases, ion and electronic conductivity and catalytic properties of defective pyrazolate based metal organic frameworks are given.     

Fluorine containing self‐crosslinking acrylic latexes with reduced flammability and their application as polymer binders for heterogeneous cation‐exchange membranes

In this study, self‐crosslinking core–shell latexes comprising copolymerized perfluorethyl groups and a novel flame retardant based on phosphazene derivative were prepared by the semi‐continuous non‐seeded emulsion polymerization of 2,2,2‐trifluorethyl methacrylate, methyl methacrylate, butyl acrylate, methacrylic acid, and hexaallylamino‐cyclo‐triphosphazene as main monomers. For interfacial crosslinking, diacetone acrylamide was copolymerized into the shell layer of latex particles to provide sites for subsequent reaction with adipic acid dihydrazide. The heterogeneous cation‐exchange membranes were obtained by dispersing commercial strong acid cation‐exchange resin powder in the latex binder and casting the mixture followed by keto‐hydrazide crosslinking reaction. It was found that the increased concentration of fluorine atoms and phosphazene units in the macromolecular structure of interfacially crosslinked emulsion polymers resulted in a significant enhancement of their flame resistance and shape stability in aqueous environment. Moreover, the easily prepared heterogeneous cation‐exchange membranes based on latexes with higher amounts of fluorine and phosphazene units were shown to exhibit satisfactory physicochemical and electrochemical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45467.     

Highly Stable Colloidal “Giant” Quantum Dots Sensitized Solar Cells

Colloidal quantum dots (QDs) are widely studied due to their promising optoelectronic properties. This study explores the application of specially designed and synthesized “giant” core/shell CdSe/(CdS)_x QDs with variable CdS shell thickness, while keeping the core size at 1.65 nm, as a highly efficient and stable light harvester for QD sensitized solar cells (QDSCs). The comparative study demonstrates that the photovoltaic performance of QDSCs can be significantly enhanced by optimizing the CdS shell thickness. The highest photoconversion efficiency (PCE) of 3.01% is obtained at optimum CdS shell thickness ≈1.96 nm. To further improve the PCE and fully highlight the effect of core/shell QDs interface engineering, a CdSe_x S_1?x interfacial alloyed layer is introduced between CdSe core and CdS shell. The resulting alloyed CdSe/(CdSe_x S_1?x )₅/(CdS)₁ core/shell QD‐based QDSCs yield a maximum PCE of 6.86%, thanks to favorable stepwise electronic band alignment and improved electron transfer rate with the incorporation of CdSe_x S_1?x interfacial layer with respect to CdSe/(CdS)₆ core/shell. In addition, QDSCs based on “giant” core/CdS‐shell or alloyed core/shell QDs exhibit excellent long‐term stability with respect to bare CdSe‐based QDSCs. The giant core/shell QDs interface engineering methodology offers a new path to improve PCE and the long‐term stability of liquid junction QDSCs.     

Trace metals in the marine bivalve Macoma balthica in the westerschelde estuary, The Nertherlands. Part 3: Variability of the role of cytosol in metal uptake by the clams

Tellinid clams Macoma balthica were sampled every 2 months for 2.5 years at two locations from the Westerschelde estuary (The Netherlands) and submitted to in vitro short-term exposure to Cd, Cu and Zn. Total and heat-stable cytosolic metal concentrations have been measured before and after exposure to study the effects of the sampling season on metal uptake by the bivalve. We observed much higher uptakes of Cd and, to a lesser extent, Cu in winter than in summer, while Zn appears to be constantly regulated. These phenomena are amplified in the cytosol, especially for Cd, a non-essential element, for which the concentrations after exposure can reach 35–45 μg·g⁻¹ (dry wt.) in winter, but only a maximum of 0.5 μg·g⁻¹ in summer, all natural values being between 0.01 and 0.1 μg·g⁻¹ on average. The contents (μg) of the various elements, either at the total or at the cytosolic level, are not constant, hence showing that the seasonal body weight fluctuation of the clams (dilution or concentration effect) is not the only parameter responsible for the metal uptake variability. Furthermore, we have shown that the proportion of cytosolic metal is not constant, but increases with the absolute cytosolic concentration up to 35–40. Therefore, the cytosolic phase of the cells plays a growing role in Cd, Cu and Zn storage as long as their total concentration increases.     

Denitrification en continu a l'aide de microorganismes immobilises sur des supports solides

In this paper, we describe a study of biological denitrification by immobilized cells. Nitrates are reduced in sterile solutions by Pseudomonas aeruginosa immobilized in a fixed bed reactor, and in synthetic waste water by mixed cultures immobilized into a fluidized bed reactor.The fixed bed reactor is a Plexiglas column filled with corn stovers (Table 1). It is 0.05 m in diameter and 0.55 in height, its volume being approx. 11. The fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Reactor and carrier are sterilized with ethylene-oxide. After sterilization 1 l. of a growing batch culture of Pseudomonas aeruginosa is introduced aseptically and the reactor is then fed continuously (45 ml h⁻¹) with fresh medium (N---NO₃ = 40 mg l⁻¹) until the first steady state is reached.Nitrates and nitrites are determinated by means of a colorimetric method.Reactor efficiency remains constant for over 40 days. Nitrates and nitrites concentrations are measured inside the reactor for flow varying from 2 to 16 ml min⁻¹ (Fig. 2). Reductions of nitrates and nitrites seem to be two first-order reactions (Fig. 3 and Table 2) and constant rate increases with flow rate (Fig. 4). Until nitrate concentration reaches 960 mg/l⁻¹ (N---NO₃) degradation is correct (Figs 5 and 6), beyond nitrites, which have been formed, seem to be inhibitor.Using this reactor, 50 mg N---NO₃ have been reduced per hour and per liter of empty reactor, but it may be possible to reduce 140 mg N---NO₃ l⁻¹ h⁻¹ if fresh medium contains 200 mg N---NO₃ l⁻¹.The fluidized bed reactor is a Plexiglas column filled with earthenware. It is 0.05 m in diameter and 3.15 m in height, its volume being approx. 6.201. Fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Figure 7 shows the retention time of the liquid in the reactor in relation to flow. The first steady state has been reached after 2 weeks, and it has not been possible to know half life time of the column.Four experiments were conducted (Table 3) and, for each nitrate, nitrite and methanol concentrations in the reactor were measured (Fig. 8). So, it appears that reduction of nitrates and nitrites are two first-order reactions (Table 4) and that constant rate values, which are higher than in fixed bed reactor, increase with flow.The reactor is more affected by a flow shift than by a nitrate concentration shift in fresh medium, and biomass linked onto carrier is about 76 mg of dry matter g⁻¹ of earthenware.So, our fluidized bed column is able to reduce 560 mg N---NO₃ h⁻¹ l⁻¹ of empty reactor, then retention time of liquid is less than 3 min.     

A phenomenological model for analyzing reciprocating compressors

A new model for hermetic reciprocating compressors is presented. This model is able to predict compressor efficiency and volumetric efficiency in terms of a certain number of parameters (10) representing the main sources of losses inside the compressor. The model provides users with helpful information about the way in which the compressor is designed and working.A statistical fitting procedure based on the Monte Carlo method was developed for its adjustment. The model can predict compressor performance at most points with a maximum deviation of 3%.A possible gas condensation on cold spots inside the cylinder during the last part of the compression stroke was also evaluated.