Characterization and catalytic activity of soft-templated NiO-CeO2 mixed oxides for CO and CO2 co-methanation

Nanosized NiO,CeO₂ and NiO-CeO₂ mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical composition,structure,morphology and texture.On the catalysts submitted to the same reduction pretreatment adopted for the activity tests the surface basic properties and specific metal surface area were also determined.NiO and CeO₂ nanocrystals of about 4 nm in size were obtained,regardless of the Ni/Ce molar ratio.The Raman and X-ray photoelectron spectroscopy results proved the formation of defective sites at the NiO-CeO₂ interface,where Ni species are in strong interaction with the support.The microcalorimetric and Fourier transform infrared analyses of the reduced samples highlighted that,unlike metallic nickel,CeO₂ is able to effectively adsorb CO₂,forming carbonates and hydrogen carbonates.After reduction in H2 at 400°C for 1 h,the catalytic performance was studied in the CO and CO₂ co-methanation reaction.Catalytic tests were performed at atmospheric pressure and 300°C,using CO/CO₂/H₂ molar compositions of 1/1/7 or 1/1/5,and space velocities equal to 72000 or 450000 cm³?h^-1?gcat^-1.Whereas CO was almost completely hydrogenated in any investigated experimental conditions,CO₂ conversion was strongly affected by both the CO/CO₂/H₂ ratio and the space velocity.The faster and definitely preferred CO hydrogenation was explained in the light of the different mechanisms of CO and CO₂ methanation.On a selected sample,the influence of the reaction temperature and of a higher number of space velocity values,as well as the stability,were also studied.Provided that the Ni content is optimized,the NiCe system investigated was very promising,being highly active for the CO_x co-methanation reaction in a wide range of operating conditions and stable(up to 50 h)also when submitted to thermal stress.     

Atomistic Simulations of Functionalized Nano-Materials for Biosensors Applications

Nanoscale biosensors, a highly promising technique in clinical analysis, can provide sensitive yet label-free detection of biomolecules. The spatial and chemical specificity of the surface coverage, the proper immobilization of the bioreceptor as well as the underlying interfacial phenomena are crucial elements for optimizing the performance of a biosensor. Due to experimental limitations at the microscopic level, integrated cross-disciplinary approaches that combine in silico design with experimental measurements have the potential to present a powerful new paradigm that tackles the issue of developing novel biosensors. In some cases, computational studies can be seen as alternative approaches to assess the microscopic working mechanisms of biosensors. Nonetheless, the complex architecture of a biosensor, associated with the collective contribution from “substrate–receptor–analyte” conjugate in a solvent, often requires extensive atomistic simulations and systems of prohibitive size which need to be addressed. In silico studies of functionalized surfaces also require ad hoc force field parameterization, as existing force fields for biomolecules are usually unable to correctly describe the biomolecule/surface interface. Thus, the computational studies in this field are limited to date. In this review, we aim to introduce fundamental principles that govern the absorption of biomolecules onto functionalized nanomaterials and to report state-of-the-art computational strategies to rationally design nanoscale biosensors. A detailed account of available in silico strategies used to drive and/or optimize the synthesis of functionalized nanomaterials for biosensing will be presented. The insights will not only stimulate the field to rationally design functionalized nanomaterials with improved biosensing performance but also foster research on the required functionalization to improve biomolecule–surface complex formation as a whole.     

Axitinib in Ponatinib-Resistant B-Cell Acute Lymphoblastic Leukemia Harboring a T315L Mutation

Adult acute lymphoblastic leukemia (ALL) with BCR-ABL1 rearrangement (Philadelphia chromosome, Ph) is a hematological aggressive disease with a fatal outcome in more than 50% of cases. Tyrosine kinase inhibitors (TKIs) targeting the activity of BCR-ABL1 protein have improved the prognosis; however, relapses are frequent because of acquired somatic mutations in the BCR-ABL1 kinase domain causing resistance to first, second and third generation TKIs. Axitinib has shown in vitro and ex vivo activity in blocking ABL1; however, clinical trials exploring its efficacy in ALL are missing. Here, we presented a 77-year-old male with a diagnosis of Ph positive ALL resistant to ponatinib and carrying a rare threonine to leucine (T315L) mutation on BCR-ABL1 gene. The patient was treated with axitinib at 5 mg/twice daily as salvage therapy showing an immediate although transient benefit with an overall survival of 9.3 months. Further dose-finding and randomized clinical trials are required to assess the real efficacy of axitinib for adult Ph positive ALL resistant to third generation TKIs.     

Light emitting devices based on Si nanoclusters： the integration with a photonic-crystal and electroluminescence properties

We present the properties and potentialities of light emitting devices based on amorphous Si nanoclusters. Amorphousnanostructures may constitute an interesting alternative to Si nanocrystals for the monolithic integration of optical andelectrical functions in Si technology. In fact, they exhibit an intense room temperature electroluminescence (EL). The ELproperties of these devices have been studied as a function of current and of temperature. Moreover, to improve theextraction efficiency of the light, we have integrated the emitting system with a 2D photonic crystal structure opportunelyfabricated by using conventional optical lithography to reduce the total internal reflection of the emitted light. The extractionefficiency in such devices increases by a factor of 4 at a resonance wavelength.     

Effects of carbonaceous nanoparticles from low-emission and older diesel engines on human skin cells

Diesel exhaust particles (DEP) are major constituents of ambient air pollution and are associated with respiratory and cardiovascular diseases as well skin cell alterations in vitro. The epidermal cells are among the first cell populations exposed to chemical pollutants, including DEP, and are an important source of pro-inflammatory mediators. We evaluated the effects of carbonaceous soot particles from current low-emission (Euro IV) diesel engines on the oxidative and inflammatory response of normal human skin cells and compared the results with those induced by carbonaceous soot particles from an older diesel engine (BS) operating under black smoke conditions. We observed that both soot nanoparticles were spontaneously internalised by keratinocytes and distributed mostly around the cell nucleus. Moreover, at the same mass concentration, Euro IV soot particles exhibited a much higher oxidative, pro-fibrotic and toxic potential on these cell types than soot particles from the older diesel engine. These results are in agreement with and confirm our previous findings on human macrophage cells and strengthen the assumption that, at the same mass concentration, soot particles produced under low emission conditions are more cytotoxic than particles from the older diesel engine. This effect could be assigned to the defective surface structure of Euro IV diesel soot, rendering it highly active. Our findings highlight that the reduction of soot emission in terms of mass does not automatically lead to a reduction of the dangerous effects and show that soot particles from different diesel engines possess different biological behaviour towards human cells.