Influence of composition of MgAl2O4 supported NiCeO2ZrO2 catalysts on coke formation and catalyst stability for dry reforming of methane

Dry reforming of methane was studied over Ni catalysts supported on γAl₂O₃, CeO₂, ZrO₂ and MgAl₂O₄ (670 °C, 1.5 bar, 16–20 l CH₄ ml_catalyst⁻¹ h⁻¹). It is shown that MgAl₂O₄ supported Ni catalysts promoted with both CeO₂ and ZrO₂ are promising catalysts for dry reforming of methane with carbon dioxide. Within a certain composition range, the simultaneous promotion with CeO₂ and ZrO₂ has great influence on the amount of coke and the catalyst service time. XRD analyses indicate that formation of crystalline Ce_xZr_1−xO₂ mixed oxide phases occurs on double promotion. In particular, incorporation of low amounts of Zr in the CeO₂ fluorite structure provides stable dry reforming catalysis. As shown with TPR, promotion leads to a higher reduced state of Ni. SEM, XRD and TPR analyses demonstrate that highly dispersed, doubly promoted Ni catalysts with a strong metal-support interaction are essential for stable dry reforming and suppression of the formation of carbon filaments.     

Processing–formulation–performance relationships of polypropylene/short flax fiber composites

This work is a comprehensive study of the effect of extrusion process parameters and formulation on the properties of polypropylene (PP)/short flax fiber composites. The parameters that were varied during the twin‐screw extrusion process were screw configuration, revolutions per minute (rpm), extrusion temperature, and flow rate. The effect of the feeding zone location of cellulosic fiber was also considered. This study investigates the effect of the formulation, cellulosic fiber content, the presence of a coupling agent, and of a reactive additive on composite performance. The composites were characterized in terms of morphology and microstructure, fiber length, rheological, thermal, and mechanical properties. Sensibility to humidity and recyclability were also considered. When compared with as‐received PP, the tensile strength of injection‐molded parts increased with cellulosic content by up to 40 vol %, and the tensile modulus increased 3.5 times when a combination of coupling and reactive agents was used. Exposed to controlled humidity of 50% during 1 year, these composites exhibited a very low level of humidity uptake around 0.85 wt %. The processability of these materials using a cast film line and the mechanical properties of extruded sheets are also presented. Furthermore, these materials demonstrate a good recyclability using injection molding by keeping the integrality of their mechanical properties after five reprocessing cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41528.     

Esterification and Transesterification of Renewable Chemicals

An overview is given of newly developed Lewis or Brønsted acid and base catalysts for esterification, transesterification and ester interchange reactions. The most relevant applications of these catalysts and reactions in the domain of renewable resources, in particular, oils and fats, are discussed.     

Kinetics of the selective catalytic reduction of NO by NH3 on a Cu-faujasite catalyst

The kinetics of the selective catalytic reduction (SCR) of NO by NH₃ in the presence of O₂ has been studied on a 5.5% Cu-faujasite (Cu-FAU) catalyst. Cu-FAU was composed of cationic and oxocationic Cu species. The SCR was studied in a gas phase-flowing reactor operating at atmospheric pressure. The reaction conditions explored were: 458<T_R<513 K, 2503 (ppm) < 4000, 12 (%) < 4. The kinetic orders were 0.8–1 with respect to NO, 0.5–1 with respect to O₂, and essentially 0 with respect to NH₃. Based on these kinetic partial orders of reactions and elementary chemistry, a wide variety of mechanisms were explored, and different rate laws were derived. The best fit between the measured and calculated rates for the SCR of NO by NH₃ was obtained with a rate law derived from a redox Mars and van Krevelen mechanism. The catalytic cycle is described by a sequence of three reactions: (i) Cu^I is oxidized by O₂ to “Cu^II-oxo”, (ii) “Cu^II-oxo” reacts with NO to yield “Cu^II-N_xO_y”, and (iii) finally “Cu^II-N_xO_y” is reduced by NH₃ to give N₂, H₂O, and the regeneration of Cu^I (closing of the catalytic cycle). The rate constants of the three steps have been determined at 458, 483, and 513 K. It is shown that Cu^I or “Cu^II-oxo” species constitute the rate-determining active center.     

Hyperthermostabilization of Bacillus licheniformis{alpha}-amylase and modulation of its stability over a 50{degrees}C temperature range

Bacillus licheniformis     

Synthesis and in Vitro Characterisation of Ifenprodil‐Based Fluorescein Conjugates as GluN1/GluN2B N‐Methyl‐D‐aspartate Receptor Antagonists

GluN2B‐containing NMDA receptors are involved in many important physiological functions and play a pivotal role in mediating pain as well as in several neurodegenerative disorders. We aimed to develop fluorescent probes to target the GluN2B subunit selectively in order to allow better understanding of the relationships between receptor localisation and physiological importance. Ifenprodil, known as the GluNR2B antagonist of reference, was chosen as the template for the elaboration of probes. We had previously reported a fluorescein conjugate that was shown (by confocal microscopy imaging of DS‐red‐labelled cortical neurons) to bind specifically to GluN2B. To elaborate this probe, we explored the influence of both the nature and the attachment point of the spacer between the fluorophore and the parent compound, ifenprodil. We performed chemical modifications of ifenprodil at the benzylic position and on the phenol ring by introducing secondary amine or amide functions and evaluated alkyl chains from two to 20 bonds either including or not including secondary amide functions as spacers. The previously developed probe was found to display the greatest activity in the inhibition of NMDA‐induced Ca²⁺ influx by calcium imaging experiments on HEK293 cells transfected with the cDNA encoding for GluN1‐1A and GluN2B. Further investigations revealed that this probe had a neuroprotective effect equivalent to that of ifenprodil in a standard test for neurotoxicity. Despite effects of lesser amplitude with these probes relative to ifenprodil, we demonstrated that they displaced [³H]ifenprodil in mouse brain slices in a similar manner.     

Reversibly crosslinked self‐healing PCL‐based networks

Poly(ε‐caprolactone) (PCL)‐based thermoreversible networks with self‐healing properties were prepared through Diels–Alder (DA) and retro‐DA reactions. Bis‐ or Tris‐maleimide compounds and a series of copolymer(caprolactone‐diene) PCL_XF_Y (X: degree of polymerization and Y: furan‐average functionality) with Y between 2.4 and 4.9 were used. The successive sequences of formation and dissociation of polycaprolactone networks via DA and retro‐DA reactions were observed repeatedly by dynamic mechanical analyses (DMA) and their gel‐temperatures determined. The cross‐linking densities, thermal properties, and thermal reversibility of the PCL_XF_Y/multimaleimide polymers have been modulated by the structure and functionalities of the used diene and dienophile moieties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of Polycarbonate and Glycol Modified Poly(ethylene terephthalate) by Addition of Silica‐Nanoparticles Grafted with SAN Copolymer Using “Classical” and ARGET ATRP

This study presents a nanocomposite manufacturing route starting from non‐functionalized nanosilica and SAN surface modification via “grafting from” ATRP up to processing of transparent polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites. Synthesis limitations of low molecular weight graft SAN derived from “classical” ATRP are overcome by employment of the emerging ARGET ATRP. Mechanical investigations of polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites present up to 80% enhancement of creep performance and additionally 70% enhancement against wear abrasion for glycol modified poly(ethylene terephthalate) nanocomposites. Strength and tensile modulus are only moderately influenced by the addition of nanoparticles. Morphological studies confirm that the present modification route is able to create uniform dispersions of single particles and small particle aggregates in polymer matrices.