The role of ceria-based nanostructured materials in energy applications

Ceria (CeO2) is enjoying increasing popularity in catalytic applications, and in some cases has established itself as an irreplaceable component. The reasons for such success stem from the intrinsic structural and redox properties of ceria. Reducing the ceria particles to the nanoscale has a profound impact on the catalytic behavior. The proliferation of improved synthetic methods that allow control over the final morphology and size of the nano-structures is opening new possibilities in terms of catalytic potential, particularly for energy-related applications

The electrifying effects of carbon-CeO2 interfaces in (electro)catalysis

Abstract The exceptional and unique properties of cerium dioxide have encouraged scientists to exploit this material beyond its traditional role as a promoter in automotive engines. Electrochemical processes relevant to fuel cells, electrolyzers, and sensors can be facilitated or even directly catalyzed by the CeO2, whose redox properties are ideal for electrochemistry. However, given the insulating nature of pure ceria, the inclusion of conductive materials at the boundary with the metal oxide is necessary to boost the catalytic activity. Carbon in its various forms and morphologies is a dominant component in ceria-based electrocatalysts, significantly facilitating electron transfers and providing high surface area and improved stability. Moreover, given the improved electronic conductivity of reduced CeO2 in the wake of the decreased grain boundary impedance, the combination with a conductive component, such as carbon, can facilitate a reduction of the ceria

Predicting crystal structures: the Parrinello-Rahman method revisited

By suitably adapting a recent approach [A. Laio and M. Parrinello, PNAS, 99, 12562 (2002)] we develop a powerful molecular dynamics method for the study of pressure-induced structural transformations. We use the edges of the simulation cell as collective variables. In the space of these variables we define a metadynamics that drives the system away from the local minimum towards a new crystal structure. In contrast to the Parrinello-Rahman method our approach shows no hysteresis and crystal structure transformations can occur at the equilibrium pressure. We illustrate the power of the method by studying the pressure-induced diamond to simple hexagonal phase transition in a model of silicon.Comment: 5 pages, 2 Postscript figures, submitte

The Role of Structured Carbon in Downsized Transition Metal-Based Electrocatalysts toward a Green Nitrogen Fixation

Electrocatalytic Nitrogen Reduction Reaction (NRR) to ammonia is one of the most recent trends of research in heterogeneous catalysis for sustainability. The stark challenges posed by the NRR arise from many factors, beyond the strongly unfavored thermodynamics. The design of efficient heterogeneous electrocatalysts must rely on a suitable interplay of different components, so that the majority of research is focusing on development of nanohybrids or nanocomposites that synergistically harness the NRR sequence. Nanostructured carbon is one of the most versatile and powerful conductive supports that can be combined with metal species in an opportune manner, so as to guide the correct proceeding of the reaction and boost the catalytic activity

Carbon nanotubes and catalysis: the many facets of a successful marriage

Carbon nanotubes have emerged as unique carbon allotropes that bear very interesting prospects in catalysis. Their use is mostly related to that of supports for inorganic metal catalysts, including molecular catalysts, metal nanoparticles, metal oxides or even more complex hierarchical hybrids. However, several reports have shown that they can intriguingly act as metal-free catalysts, with performance often superior to that of other carbon materials, in particular when ad hoc organic functional groups are attached prior to catalytic screening. The range of catalytic reactions is quite wide, and it includes standard organic synthesis, electrocatalysis, photocatalysis as well as other important industrial processes. In the last few years, the energy sector has acquired a dominant role as one of the most sought-after fields of application, given its ever-increasing importance in society

Electrocatalytic CO2 reduction: role of the cross-talk at nano-carbon interfaces

The electrocatalytic CO2 reduction reaction (CO2RR) is an interfacial process, involving a minimum of three phases at the contact point of gaseous CO2 with the electrodic surface and the liquid electrolyte. As a consequence, surface chemistry at composite interfaces plays a central role for CO2RR selectivity and catalysis. Each interface defines a functional boundary, where active sites are exposed to a unique environment, with respect to distal sites in the bulk of organic and inorganic domains. While the individual role of each component-type is hardly predictable "a-solo", the interface ensemble works via a strategic interplay of individual effects, including: (i) enhanced electrical conductivity, (ii) high surface area and exposure of the interfacial catalytic sites, (iii) favorable diffusion and feeding of reactants, (iv) complementary interactions for the "on/off" stabilization of cascade intermediates, (v) a secondary sphere assistance to lower the activation energy of bottleneck steps, (vi) a reinforced robustness and long-term operation stability. Selected CO2RR case studies are compared and contrasted to highlight how the organic domains of carbon nanostructures merge with metal and metal-oxide active sites to separate tasks but also to turn them into a cooperative asset of mutual interactions, thus going beyond the classic "Divide et Impera" rule

Arothron: an R package for virtual anthropology to build endocast and to perform digital reconstruction

Arothron is an R package [1] containing brand new tools for geometric morphometric analysis. The package comes with examples pertaining to the field of virtual anthropology, yet it is addressed to the entire audience of geometric morphometricians. The functions embedded in the package allow aligning disarticulated parts belonging to a single specimen (i.e. broken skull fragments), to build internal cavities such as endocasts, and to reproduce and analyse the shapes of three-dimensional objects. Arothron functions import and export landmark coordinates and 3D paths into ’landmarkAscii’ and ’am’ format files. The Digital Tool for Alignment (DTA) is a landmark-based methodology which allows aligning two or more portions of a 3D mesh (i.e. a disarticulated model, DM) by using a reference sample or model (RM) for comparison. To run DTA, a set of anatomical landmarks is defined on two separated portions of the DM. Each point of the landmark sets is moved to the nearest vertex of the triangles. This way, each landmark is identified by a number corresponding to a row of the vertex matrix of the mesh and its position is tracked on the 3D models moved in the Cartesian coordinate system.The second step is the alignment via Generalized Procrustes Analysis (GPA) of each part of the DM on each RM of the comparative sample, where the same landmark configuration as with the DM has been previously defined. The items of the reference sample are previously scaled to the mean of the single scale factors calculated for each half of the DM, separately, and symmetrized via reflection and relabelling, thereby producing a perfectly symmetrical, bilateral, and scaled landmark configurations (to avoid alignment error as introduced by asymmetry). The last step consists in the quantification of the morphological (Euclidean) distances between each part of the DM and the corresponding landmark configurations on each item in the RM set. Computer-Aided Laser Scanner Emulator (CA-LSE) and Automatic Segmentation Tool for 3D objects (AST-3D) are two new tools designed for the reconstruction of virtual cavities and external shapes [2]. CA-LSE provides the reconstruction of the external portions of a 3D mesh by simulating the action of a laser scanner. AST-3D performs the digital reconstruction of anatomical cavities as endocasts. Both tools use the definition of points of views that can be placed externally to the object (CA-LSE) or inside the object (AST-3D). By applying these tools is possible in few minutes to build virtual cavities as endocast, maxillary sinuses and trabecular bone. In the Arothron R package, we supplied three examples of reconstructing: the dental pulp cavity within a deciduous Neanderthal tooth, the network of blood vessels within a human malleus bone, and an endocast of a human skull.The tools could be used in virtual anthropology application.The digital alignment tool is efficient in find ideal alignments of broken pieces. It could be applied as the first step in virtual reconstruction on human fossil specimens that often consist of a disarticulated fragments such as BOU-VP12/130 (Australopithecus garhi), AL-442 (Australopithecus afarensis), OH5 (Paranthropus boisei), ATD6-15 and ATD6-69 (Homo antecessor), Amud 1 (Homo neanderthalensis), Le Moustier 1 (Homo neanderthalensis). The easily and quickly use of the Arothron R package to build virtual cavities may provide a new means largely applicable in virtual Anthropology. References:[1] Profico A., Veneziano A., Melchionna M., Piras P. & Raia P., 2018. Arothron: Geometric Morphometrics Analyses. R package version 1.0.1, developer version available at https://github/Arothron DOI:10.5281/zenodo.1218712.[2] Profico A., Schlager S., Valoriani V., Buzi C., Melchionna M., Veneziano A., Raia P., MoggifiCecchi J. & Manzi G., 2018. Reproducing the internal and external anatomy of fossil bones: Two new automatic digital tools. American Journal of Physical Anthropology

hMENA11a contributes to HER3-mediated resistance to PI3K inhibitors in HER2-overexpressing breast cancer cells.

Human Mena (hMENA), an actin regulatory protein of the ENA/VASP family, cooperates with ErbB receptor family signaling in breast cancer. It is overexpressed in high-risk preneoplastic lesions and in primary breast tumors where it correlates with HER2 overexpression and an activated status of AKT and MAPK. The concomitant overexpression of hMENA and HER2 in breast cancer patients is indicative of a worse prognosis. hMENA is expressed along with alternatively expressed isoforms, hMENA11a and hMENAΔv6 with opposite functions. A novel role for the epithelial-associated hMENA11a isoform in sustaining HER3 activation and pro-survival pathways in HER2-overexpressing breast cancer cells has been identified by reverse phase protein array and validated in vivo in a series of breast cancer tissues. As HER3 activation is crucial in mechanisms of cell resistance to PI3K inhibitors, we explored whether hMENA11a is involved in these resistance mechanisms. The specific hMENA11a depletion switched off the HER3-related pathway activated by PI3K inhibitors and impaired the nuclear accumulation of HER3 transcription factor FOXO3a induced by PI3K inhibitors, whereas PI3K inhibitors activated hMENA11a phosphorylation and affected its localization. At the functional level, we found that hMENA11a sustains cell proliferation and survival in response to PI3K inhibitor treatment, whereas hMENA11a silencing increases molecules involved in cancer cell apoptosis. As shown in three-dimensional cultures, hMENA11a contributes to resistance to PI3K inhibition because its depletion drastically reduced cell viability upon treatment with PI3K inhibitor BEZ235. Altogether, these results indicate that hMENA11a in HER2-overexpressing breast cancer cells sustains HER3/AKT axis activation and contributes to HER3-mediated resistance mechanisms to PI3K inhibitors. Thus, hMENA11a expression can be proposed as a marker of HER3 activation and resistance to PI3K inhibition therapies, to select patients who may benefit from these combined targeted treatments. hMENA11a activity could represent a new target for antiproliferative therapies in breast cancer