Ferromagnetically modified zeolite catalysts for liquid-phase High–Throughput Experimentation

A novel method for the separation of heterogeneous catalysts from liquid-phase reactions in High–Throughput Experimentation (HTE) libraries was developed based on a magnetic recuperation procedure. Ferromagnetic iron nanoparticles were introduced in a set of zeolite structures by means of aqueous impregnation of an iron precursor, followed by reduction in H₂. The obtained magnetic zeolites can be efficiently stirred in the catalytic reaction mixture using conventional magnetic stirring bars and they are automatically separated by depositing on the magnetic bar when the stirring is stopped. Characterization techniques demonstrated that the iron nanoparticles are distributed on the external surface of the zeolites, where the interference with the catalytic active sites is limited. Catalytic tests of a High-Throughput library of 10 wt. % Fe magnetic zeolites, performed using the liquid-phase benzylation of toluene with benzyl alcohol as test reaction, showed that the modified catalysts can be very easily and efficiently separated from the reaction mixture while they retain similar activity and selectivity to that of the unmodified samples.     

Simulation of the layer inversion phenomenon in binary liquid--fluidized beds by DEM–CFD with a drag law for polydisperse systems

Liquid-fluidized beds of particular binary mixtures exhibit the layer inversion phenomenon, a peculiar result of the mechanical equilibrium developing in such multiphase systems. Because of the crucial role of the hydrodynamic interaction, these are ideal test cases for assessing fluid-particle models in multi-particle CFD simulations. In the present work the layer inversion phenomenon is reproduced via Discrete Element Method (DEM) simulations, in which the drag force model for polydisperse systems described in Cello et al. (2010) is used. The simulations serve primarily to assess the suitability of the DEM–CFD approach and particularly the validity of the above drag model, although the results available may also prove very useful to investigate the prevailing mechanisms. To analyze a sufficiently broad variety of cases, involving different solid species, size ratios and operating conditions, three systems selected amongst the published literature are considered. The comparison of simulation and experimental observation is carried out in terms of overall bed and mixed layer interface heights, voidage and component distributions along bed height and time evolution of the species centers of mass. Simulations with liquid velocities below, above and at the critical inversion conditions are carried out. Additionally, simulations using a drag force model traditionally used for monodisperse beds are reported for comparison. The results not only demonstrate the importance of correctly accounting for the local size distribution in the bed, but also prove the validity of the overall computational approach. The predictions of the simulations are in good to excellent agreement with experiments, depending on the system considered, both in terms of critical velocity and, most notably, expansion of the individual components in the bed. The analysis of the hydrodynamics in the bed allows to investigate the local particle flow field, highlighting the presence of a steady irregular motion of the solids in apparently chaotic vortices continuously forming and disappearing, which is thought to be the mechanism responsible for mixing. The fluid–particle interaction forces exhibit a constant profile along bed height, even in the presence of a strongly non-uniform concentration profile.     

Recycling of waste glasses into partially crystallized glass foams

Waste soda-lime glass, alone or mixed with wastes from the manufacturing of glass fibers, was successfully converted into partially crystallized glass foams by a particularly simple and economic processing, consisting of a direct heating of glass powders at temperatures from 900 to 1050 °C. The foaming operated by the oxidation of SiC, inserted as powder additive, was found to depend on a complex combination of processing temperature, soaking time, tendency of the investigated glasses toward devitrification, and amount of MnO₂, acting as oxidation promoter. Selected combinations led to foams with a good microstructural homogeneity and mechanical strength, suitable for application as aggregates in lightweight concrete.     

Isolation and Characterization of Squamous Cell Carcinoma-Derived Stem-like Cells: Role in Tumor Formation

In human epidermis, keratinocyte stem cells (KSC) are characterized by high levels of β₁-integrin, resulting in the rapid adhesion to type IV collagen. Since epithelial tumors originate from KSC, we evaluated the features of rapidly adhering (RAD) keratinocytes derived from primary human squamous cell carcinoma of the skin (cSCC). RAD cells expressed higher levels of survivin, a KSC marker, as compared to non-rapidly adhering (NRAD) cells. Moreover, RAD cells proliferated to a greater extent and were more efficient in forming colonies than NRAD cells. RAD cells also migrated significantly better than NRAD cells. When seeded in a silicone chamber and grafted onto the back skin of NOD SCID mice, RAD cells formed tumors 2–4 fold bigger than those derived from NRAD cells. In tumors derived from RAD cells, the mitotic index was significantly higher than in those derived from NRAD cells, while Ki-67 and survivin expression were more pronounced in RAD tumors. This study suggests that SCC RAD stem cells play a critical role in the formation and development of epithelial tumors.     

The Dynamics of Lysozyme from Bacteriophage Lambda in Solution Probed by NMR and MD Simulations

¹⁵N NMR relaxation studies, analyses of NMR data to include chemical shifts, residual dipolar couplings (RDC), NOEs and H^N–H^α coupling constants, and molecular dynamics (MD) simulations have been used to characterise the behaviour of lysozyme from bacteriophage lambda (λ lysozyme) in solution. The lower and upper lip regions in λ lysozyme (residues 51–60 and 128–141, respectively) show reduced ¹H–¹⁵N order parameters indicating mobility on a picosecond timescale. In addition, residues in the lower and upper lips also show exchange contributions to T₂ indicative of slower timescale motions. The chemical shift, RDC, coupling constant and NOE data for λ lysozyme indicate that two fluctuating β‐strands (β3 and β4) are populated in the lower lip region while the N terminus of helix α6 (residues 136–139) forms dynamic helical turns in the upper lip region. This behaviour is confirmed by MD simulations that show hydrogen bonds, indicative of the β‐sheet and helical secondary structure in the lip regions, with populations of 40–60 %. Thus in solution λ lysozyme adopts a conformational ensemble that will contain both the open and closed forms observed in the crystal structures of the protein.     

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

CO₂ is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO₂ into useful products are receiving increased attention. The utilization of CO₂ as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO₂ as building block is discussed. CO₂ can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described . The factors that have limited so far the conversion of large volumes of CO₂ are analyzed and options for large‐scale CO₂ catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry     

Effect of alumina nanoparticles on the thermal properties of carbon fibre‐reinforced composites

In this work, we investigated the thermal behaviour of a carbon‐fibre composite impregnated with nano‐alumina‐based nanocomposites. First of all, we demonstrated that it is possible to obtain good dispersion and distribution of nanoparticles by mechanical mixing. In all the studied filler percentages, the presence of the ceramic filler did not affect the processability of the blends and the mechanical properties of the composites. First, the thermal stability of the nanocomposites was investigated by thermogravimetric analysis (TGA). Then, the fire reaction of the fibre‐reinforced composites was studied at different heat fluxes, by TGA, cone calorimeter and exposure to a direct flame. In presence of an oxidizing hyperthermal environment, the experimental data suggested the role of ceramic particles as anti‐oxidizer agent for the char and the carbon fibres. Moreover, the use of alumina nanoparticles allowed a slight reduction of heat release rate. Particularly at a heat flux of 35 kW/m², the burnt material containing the higher quantity of nano‐alumina maintained a residual structural integrity because of the higher presence of char that bound together the fibres. To estimate the integrity of the composites after exposure to a direct flame (heat flux 500 kW/m²), mechanical tests were carried out on the burnt specimens. Copyright © 2013 John Wiley & Sons, Ltd.     

Preceramic Polymer‐Derived SiAlON as Sintering Aid for Silicon Nitride

Two kinds of sintering additives based on the polysiloxanes or polysilazanes filled with nano‐sized powders as SiAlON precursors were tested for the densification of Si₃N₄‐based ceramics. The results showed that both systems can be successfully used as additives for the preparation of Si₃N₄ ceramics with favorable mechanical characteristics. The ceramics were sintered with 18 wt% of preceramic polymer‐based mixture, and good fracture resistance and high hardness values were obtained after sintering in optimized conditions (temperature, dwell time, nitrogen pressure). Higher densification temperatures and longer holding times were required for sintering of samples with polysilazane‐based precursors. The best toughness values were approximately 5 MPa·m^0.5, while the highest hardness was about 19 GPa. The differences in mechanical properties of the prepared composites can be related to the phase composition, microstructure and different chemical bonds present in the ceramic residue generated upon pyrolysis and final densification.