Columnar Fe2O3 arrays via plasma-enhanced growth: Interplay of fluorine substitution and photoelectrochemical properties

A single-step plasma enhanced-chemical vapor deposition (PE-CVD) route for the synthesis of F-doped iron(III) oxide nanomaterials is presented. Growth experiments, performed from a fluorinated Fe(II) β-diketonate precursor on Indium Tin Oxide (ITO) between 200 and 400 °C, yielded columnar β-Fe₂O₃ arrays with a preferential (100) growth direction. The fluorine content in the deposits could be adjusted by the sole variation of the deposition temperature controlling, in turn, the optical absorption and energy bandgap. Photocurrent measurements and Mott–Schottky analyses, carried out in Na₂SO₄ solution under one sun illumination, evidenced a conductivity switch from n- to p-type upon increasing fluorine amount in the obtained nanomaterials. The sample photocurrent density, donor content and flatband potential support the hypothesis that a progressive substitution of oxygen by fluorine in the iron(III) oxide lattice can alter electronic structure and extend charge carrier lifetimes, making anion-doped β-Fe₂O₃ an efficient water oxidation catalyst.     

Synthesis and biological evaluation of isosteric analogues of FK866, an inhibitor of NAD salvage

One of the great challenges of medicinal chemistry is to create novel, effective, chemotherapeutic agents that show specificity for cancer cells combined with low systemic toxicity. A novel idea is to target the enzymes of the NAD biosynthesis and recycling pathways given that cancer cells display a higher NAD turnover rate than healthy cells. To this end, the compound FK866 (APO866; (E)-N-[4-(1-benzoylpiperidin-4-yl) butyl]-3-(pyridin-3-yl) acrylamide), which blocks nicotinamide phosphoribosyltransferase (NMPRTase) has entered clinical trials as a potential chemotherapeutic agent. Here we report the synthesis of analogues of FK866 synthesized by click chemistry.     

Graphene decoration with metal nanoparticles: towards easy integration for sensing applications

A simple and versatile method for the decoration of CVD grown graphene with metal nanoparticles is presented. The mechanism of nanoparticle formation is galvanic displacement resulting in physically adsorbed clusters. The single layer graphene obtained by this method can be easily transferred. Integration onto a gas sensing transducer is presented as proof of concept.     

Hybrid Polyoxometalates: Merging Organic and Inorganic Domains for Enhanced Catalysis and Energy Applications

Organic–inorganic hybrids based on polyoxometalate scaffolds(POMs) are a unique class of molecular metal-oxides featuring a composite surface, whereby the merging of complementary domains stimulates new functions and enhances performances. The interaction between the organic and inorganic components can be designed via covalent and/or non-covalent strategies, yielding novel molecular systems with key applications in catalysis and materials science. Selected examples of such a rewarding approach will be illustrated, including the synthesis of tailored POM-based catalysts, and their application in homogeneous systems and on electrocatalytic surfaces for water splitting and renewable energy production.     

Distributional Effects of Transport Taxes： An Incidence Analysis

Wider use of economic instruments in the field of environmental and energy policy provides several benefits. These instruments not only create market-based incentives for environmentally friendly behaviors but also represent effective opportunities to collect revenues. In this context, energy and transport-related taxes play a major role, even if their extensive use has raised several concerns over equity issues. The main objective of the paper is to investigate the redistributive burden of existing transport taxes on Italian households. An incidence analysis is carried out on a sample of more than 23,000 Italian families for the year 2009. Some alternative policy options are also analyzed to provide some suggestions on how to countervail the potential negative regressive effects that might arise. We find that vehicle ownership taxes, if properly set, can represent a promising opportunity to blend together budget and equity needs. To obtain a better indication of the progressivity or regressivity of certain policy designs, we rely on some summary indexes, such as the Kakwani measure of progressivity and the Reynolds-Smolensky measure of redistributive capacity of a tax.     

Identification of Hck Inhibitors As Hits for the Development of Antileukemia and Anti‐HIV Agents

Hematopoietic cell kinase (Hck) is a member of the Src family of non‐receptor protein tyrosine kinases. High levels of Hck are associated with drug resistance in chronic myeloid leukemia. Furthermore, Hck activity has been connected with HIV‐1. Herein, structure‐based drug design efforts were aimed at identifying novel Hck inhibitors. First, an in‐house library of pyrazolo[3,4‐d]pyrimidine derivatives, which were previously shown to be dual Abl and c‐Src inhibitors, was analyzed by docking studies within the ATP binding site of Hck to select the best candidates to be tested in a cell‐free assay. Next, the same computational protocol was applied to screen a database of commercially available compounds. As a result, most of the selected compounds were found active against Hck, with K_i values ranging from 0.14 to 18.4 μM , confirming the suitability of the computational approach adopted. Furthermore, selected compounds showed an interesting antiproliferative activity profile against the human leukemia cell line KU‐812, and one compound was found to block HIV‐1 replication at sub‐toxic concentrations.     

Shear Strength and Stiffness of Sands Containing Plastic or Nonplastic Fines

This paper presents the results of a systematic laboratory investigation on the static behavior of silica sand containing various amounts of either plastic or nonplastic fines. Specimens were reconstituted using a new technique suitable for element testing of homogeneous specimens of sands containing fines deposited in water (e.g., alluvial deposits, hydraulic fills, tailings dams, and offshore deposits). The fabric of sands containing fines was examined using the environmental scanning electron microscope (ESEM). Static, monotonic, isotropically consolidated, drained triaxial compression tests were performed to evaluate the stress-strain-volumetric response of these soils. Piezoceramic bender element instrumentation was developed and integrated into a conventional triaxial apparatus; shear-wave velocity measurements were made to evaluate the small-strain stiffness of the sands tested at various states. The intrinsic parameters that characterize critical state, dilatancy, and small-strain stiffness of clean, silty, and clayey sands were determined. All aspects of the mechanical behavior investigated in this study (e.g., stress-strain-volumetric response, shear strength, and small-strain stiffness) are affected by both the amount and plasticity of the fines present in the sand. Microstructural evaluation using the ESEM highlighted the importance of soil fabric on the overall soil response.     

Microwave‐Assisted Fast Cyclohexane Oxygenation Catalyzed by Iron‐Substituted Polyoxotungstates

Under microwave irradiation, iron‐substituted polyoxotungstates (Fe‐POMs) catalyze cyclohexane oxygenation to A/K oil with 90–95% selectivity, unmatched turnover frequencies (40–400 h⁻¹), and multi‐turnover regime (>1000 TON). Such a rapid reaction protocol allowed the screening of so‐called inorganic Fe‐synzymes with 1–4 nuclearity, including a family of Krebs‐type isostructural complexes. Product distribution, kinetic analysis, mechanistic probes and fitting calculations, are consistent with a radical chain oxidation propagated by Fe‐catalysed decomposition of organic peroxides which ultimately depends on the redox‐properties and structural arrangement of the iron moiety within the POM cage.