Flash Sintering of Nanocrystalline Zinc Oxide and its Influence on Microstructure and Defect Formation

We report the sintering behavior of nanocrystalline zinc oxide under external AC electric field between 0 and 160 V/cm. In situ acquisition of density by means of laser dilatometry, evaluation of specimen temperature, real‐time measurement of electric field and current help analyze this peculiar behavior. Field strength and blocking electrodes significantly affect densification and microstructure, which was evaluated in the vicinity of the flash event and for the fully sintered material. High current densities flow through the sample at high electric fields, entailing a sudden increment of the temperature estimated to several hundreds of K and an exaggerated grain growth. In contrast, low current density flows through the sample at lower electric fields, which guarantees normal grain growth and highest final density. Macroscopic photoluminescence measurements give insights into the development of the defect structure. Electric fields are expected to enhance defect mobility, explaining the high densification rates observed during the sintering process.     

Role of Methyl Salicylate on Oviposition Deterrence in Arabidopsis thaliana

Plants attacked by herbivores have evolved different strategies that fend off their enemies. Insect eggs deposited on leaves have been shown to inhibit further oviposition through visual or chemical cues. In some plant species, the volatile methyl salicylate (MeSA) repels gravid insects but whether it plays the same role in the model species Arabidopsis thaliana is currently unknown. Here we showed that Pieris brassicae butterflies laid fewer eggs on Arabidopsis plants that were next to a MeSA dispenser or on plants with constitutively high MeSA emission than on control plants. Surprisingly, the MeSA biosynthesis mutant bsmt1-1 treated with egg extract was still repellent to butterflies when compared to untreated bsmt1-1. Moreover, the expression of BSMT1 was not enhanced by egg extract treatment but was induced by herbivory. Altogether, these results provide evidence that the deterring activity of eggs on gravid butterflies is independent of MeSA emission in Arabidopsis, and that MeSA might rather serve as a deterrent in plants challenged by feeding larvae.     

Copper‐Catalyzed Trifluoromethylation of Aliphatic N‐Arylhydrazones: A Concise Synthetic Entry to 2‐Trifluoromethylindoles from Simple Aldehydes

The copper‐catalyzed C(sp²) H trifluoromethylation of N,N‐disubstituted hydrazones using the Togni reagent is demonstrated to proceed efficiently for aliphatic aldehyde‐derived substrates. The success of the reactions relied on the choice of the N,N‐diphenylamino group as the terminal hydrazone amino group where N,N‐dialkylamino groups were preferred for (hetero)aromatic aldehyde‐derived substrates. In addition, the trifluoromethylated N‐arylhydrazones are shown to be ideal substrates for Fischer indole synthesis allowing a straightforward, three‐step access to 2‐trifluoromethylindole derivatives from simple aldehydes.

     

Direct comparison of Eulerian–Eulerian and Eulerian–Lagrangian simulations for particle-laden vertical channel flow

Particle-laden flows in a vertical channel were simulated using an Eulerian–Eulerian, Anisotropic Gaussian (EE-AG) model. Two sets of cases varying the overall mass loading were done using particle sizes corresponding to either a large or small Stokes number. Primary and turbulent statistics were extracted from these results and compared with counterparts collected from Eulerian–Lagrangian (EL) simulations. The statistics collected from the small Stokes number particle cases correspond well between the two models, with the EE-AG model replicating the transition observed using the EL model from shear-induced turbulence to relaminarization to cluster-induced turbulence as the mass loading increased. The EE-AG model was able to capture the behavior of the EL simulations only at the largest particle concentrations using the large Stokes particles. This is due to the limitations involved with employing a particle-phase Eulerian model (as opposed to a Lagrangian representation) for a spatially intermittent system that has a low particle number concentration.     

The grain-boundary resistance of CeO2 ceramics: A combined microscopy-spectroscopy-simulation study of a dilute solution

Weakly acceptor-doped ceria ceramics were characterized structurally and compositionally with advanced transmission electron microscopy (TEM) techniques and electrically with electrochemical impedance spectroscopy (EIS). The grain boundaries studied with TEM were found to be free of second phases. The impedance spectra, acquired in the range 703 ≤ T/K ≤ 893 in air, showed several arcs that were analyzed in terms of bulk, grain-boundary, and electrode responses. We ascribed the grain-boundary resistance to the presence of space-charge layers. Continuum-level simulations were used to calculate charge-carrier distributions (of acceptor cations, oxygen vacancies, and electrons) in these space-charge layers. The acceptor cations were assumed to be mobile at high (sintering) temperatures but immobile at the temperatures of the EIS measurements. Space-charge formation was assumed to be driven by the segregation of oxygen vacancies to the grain-boundary core. Comparisons of data from the simulations and from the EIS measurements yielded space-charge potentials and the segregation energy of vacancies to the grain-boundary core. The space-charge potentials from the simulations are compared with values obtained by applying the standard, analytical (Mott–Schottky and Gouy–Chapman) expressions. The importance of modelling space-charge layers from the thermodynamic level is demonstrated.     

Structural and Functional Characterization of 4-Hydroxyphenylacetate 3-Hydroxylase from Escherichia coli

The hydroxylation of phenols into polyphenols, which are valuable chemicals and pharmaceutical products, is a challenging reaction. The search for green synthetic processes has led to considering microorganisms and pure hydroxylases as catalysts for phenol hydroxylation. Herein, we report the structural and functional characterization of the flavin adenine dinucleotide (FAD)-dependent 4-hydroxyphenylacetate 3-monooxygenase from Escherichia coli, named HpaB. It is shown that this enzyme enjoys a relatively broad substrate specificity, which allows the conversion of a number of non-natural phenolic compounds, such as tyrosol, hydroxymandelic acid, coumaric acid, hydroxybenzoic acid and its methyl ester, and phenol, into the corresponding catechols. The reaction can be performed by using a simple chemical assay based on formate as the electron donor and the organometallic complex [Rh(bpy)Cp*(H₂O)]²⁺ (Cp*: 1,2,3,4,5-pentamethylcyclopentadiene, bpy: 2,2′-bipyridyl) as the catalyst for FAD reduction. The availability of a crystal structure of HpaB in complex with FAD at 1.8 Å resolution opens up the possibility of the rational tuning of the substrate specificity and activity of this interesting class of phenol hydroxylases.     

Synthesis and Anticancer Properties of Oxazepines Related to Azaisoerianin and IsoCoQuines

In this article, we report the synthesis and biological properties of a series of novel oxazepines related to isoCA-4 having significant antitumor properties. Among them, three oxazepin-9-ol derivatives display a nanomolar or a sub-nanomolar cytotoxicity level against five human cancer cell lines (HCT116, U87, A549, MCF7, and K562). It was demonstrated that the lead compound in this series inhibits tubulin assembly with an IC₅₀ value of 1 μM and totally arrests the cellular cycle in the G2/M phase at the low concentration of 5 nM in HCT116 and K562 cells. Molecular modeling studies perfectly corroborates these promising results.     

Al2O3-ZrO2 Finely Structured Multilayer Architectures from Suspension Plasma Spraying

Suspension plasma spraying (SPS) is an alternative to conventional atmospheric plasma spraying (APS) aiming at manufacturing thinner layers (i.e., 10-100 μm) due to the specific size of the feedstock particles, from a few tens of nanometers to a few micrometers. The staking of lamellae and particles, which present a diameter ranging from 0.1 to 2.0 μm and an average thickness from 20 to 300 nm, permits to manufacture finely structured layers. Moreover, it appears as a versatile process able to manufacture different coating architectures according to the operating parameters (suspension properties, injection configuration, plasma properties, spray distance, torch scan velocity, scanning step, etc.). However, the different parameters controlling the properties of the coating, and their interdependences, are not yet fully identified. Thus, the aim of this paper is, on the one hand, to better understand the influence of operating parameters on the coating manufacturing mechanisms (in particular, the plasma gas mixture effect) and, on the other hand, to produce Al₂O₃-ZrO₂ finely structured layers with large varieties of architectures. For this purpose, a simple theoretical model was used to describe the plasma torch operating conditions at the nozzle exit, based on experimental data (mass enthalpy, arc current intensity, thermophysical properties of plasma forming gases, etc.) and the influences of the spray parameters were determined by mean of the study of sizes and shapes of spray beads. The results enabled then to reach a better understanding of involved phenomena and their interactions on the final coating architectures permitting to manufacture several types of microstructures.     

Cytotoxicity of CeO2 nanoparticles for Escherichia coli. Physico-chemical insight of the cytotoxicity mechanism

The production of nanoparticles (NPs) is increasing rapidly for applications in electronics, chemistry, and biology. This interest is due to the very small size of NPs which provides them with many interesting properties such as rapid diffusion, high specific surface areas, reactivity in liquid or gas phase, and a size close to biomacromolecules. In turn, these extreme abilities might be a problem when considering a potentially uncontrolled exposure to the environment. For instance, nanoparticles might be highly mobile and rapidly transported in the environment or inside the body through a water or air pathway. Accordingly, the very fast development of these new synthetic nanomaterials raises questions about their impact on the environment and human health. We have studied the impact of a model water dispersion of nanoparticles (7 nm CeO2 oxide) on a Gram-negative bacteria (Escherichia coli). The nanoparticles are positively charged at neutral pH and thus display a strong electrostatic attraction toward bacterial outer membranes. The counting of colony forming units (CFU) after direct contact with CeO2 NPs allows for the defining of the conditions for which the contact is lethal to Escherichia coli. Furthermore, a set of experiments including sorption isotherms, TEM microscopy, and X-ray absorption spectroscopy (XAS) at cerium L3 edge is linked to propose a scenario for the observed toxic contact.     

Thermal and economic evaluation of heat recovery measures for indoor ice rinks

A comparative study of three ventilation systems supplying air to a typical Canadian indoor ice rink illustrates the power, energy and operating cost savings which can be achieved by using the relatively warm air from the air cooled condensers of the refrigeration system. The direct use of this warm air for ventilation results in a reduction of energy consumption during the winter amounting to 24.2% of the yearly consumption of the heating system. On the other hand, the use of a heat exchanger to heat the ventilation air results in energy consumption reductions throughout the year. Depending on the size of the heat exchanger these gains can be as high as 60.8% of the heating energy consumption by the existing system. Based on actual prices of electricity and the heat exchanger it is established that the cost savings over the life of the equipment are at least three times higher than the cost of the heat exchanger.