Spirobifluorene Dimers: Understanding How The Molecular Assemblies Drive The Electronic Properties

Spirobifluorene (SBF) is one of the most important scaffolds used in the design of organic semi-conductors (OSCs) for electronics. In recent years, among all the structures developed for these applications, SBF dimers have been highlighted due to their great potential in thermally activated delayed fluorescence and in phosphorescent organic light-emitting diodes. Attaching two SBF units generate 10 dimers, each possessing its own structural specificity, which in turn drives its electronic properties. These ten SBF dimers are gathered herein. Understanding how the molecular assembly determines the electronic properties has been one of the pillars of organic electronics. This is the goal of this article. As positional isomerism is a key tool to design OSCs, defining the design guidelines for the SBF scaffold appears of interest for the future of this building block. Herein, the importance of the two main parameters involved in the electrochemical and photophysical properties, namely the nature of the phenyl linkages and the steric congestion between the two SBF units is discussed. The combination of these two parameters drives the electronic properties but their respective weight is different as a function of the regioisomer involved or of the property considered (frontier orbitals energy level, absorption, fluorescence, phosphorescence).     

Wastewater treatment by radial freezing with stirring effects

Radial freezing experiments on wastewater models were conducted in the presence of imposed stirring in order to remove impurities. The studied samples (dilute Na-montmorillonite suspensions charged with nitrates and with zinc or lead) were placed inside a cylindrical annulus, cooled at a controlled temperature around -7 degrees C at its inner wall which rotated around a vertical axis. The freezing front propagated toward the still outer wall which was maintained at a constant temperature around +1 degrees C. Thanks to stirring, considerable purification rates up to 99.97% were attained. It was also demonstrated that combining radial freezing and stirring ended in residual concentrations which agreed with drinking water standards.     

Influence of geometrical and operational parameters on the axial dispersion in an aerated channel reactor

Residence time distribution experiments have been performed on an activated sludge 3000 m³ channel reactor aerated by gas diffusion (for different liquid flowrates under constant aeration rate and constant water depth) and on a bench-scale channel reactor aerated from the bottom (for different liquid and gas flowrates and water depths) in order to characterize their hydrodynamics. Both units can be modeled as plug flow reactors with axial dispersion. A general correlation has been obtained to predict the axial dispersion coefficient as a function of the gas and liquid velocities and the geometrical parameters of the full-scale and bench-scale reactors. Finally, to facilitate the simulation of biological reactions in transient state, an equivalent model based on tanks-in-series with variable back-mixing flowrate is proposed.     

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.     

Stereoselective Monoamine Oxidase‐Catalyzed Oxidative Aza‐Friedel–Crafts Reactions of meso‐Pyrrolidines in Aqueous Buffer

We disclose the highly diastereoselective combination of monoamine oxidase‐catalyzed oxidation of meso‐pyrrolidines and aza‐Friedel–Crafts reactions in aqueous buffer to give valuable enantioenriched 2‐substituted pyrrolidines in a formal double C H activation process. A range of secondary as well as tertiary amines were shown to be suitable substrates for the biocatalytic oxidation and subsequent addition of a variety of C‐nucleophiles.

     

Copper‐Catalyzed Asymmetric Conjugate Addition of Dimethylzinc to Acyl‐N‐methylimidazole Michael Acceptors: Scope,Limitations and Iterative Reactions

An efficient copper‐catalyzed enantioselective conjugate addition of dimethylzinc to unsaturated 2‐acyl‐N‐methylimidazoles has been achieved using a chiral bidentate hydroxyalkyl‐NHC ligand. The reactions proceed with excellent regioselectivity (1,4 vs. 1,6 and 1,8) in extended conjugated systems to afford the 1,4‐adducts in high enantioselectivities. This regioselectivity could be ascertained by DFT studies highlighting the crucial role of the imidazole ring. Thanks to the development of efficient protocols to regenerate the unsaturated 2‐acyl‐N‐methylimidazole moiety, an iterative process has been developed ultimately leading to 3,5,7 all‐syn or anti‐anti polydeoxypropionate stereodiads.

     

The interaction between molten gallium and the hydrocarbon medium induced by ultrasonic energy—can gallium carbide be formed?

Ultrasonic irradiation of molten gallium in organic liquids (decane, dodecane, etc.) results in dispersion of the gallium into nanometric spheres. These were examined by several analytical methods XRD, DSC, Raman and IR spectroscopy) as well as electron microscopy (SEM, TEM) and found to be composed of Ga and C. The DSC analysis indicates that the Ga has possibly reacted with carbon, while the Raman spectrum of the product demonstrates a strong additional peak that could not be identified. This work explores the possibility that the product is gallium carbide or another gallium‐carbon complex. To investigate the nature of the product, we performed detailed extended X‐ray absorption fine structure (EXAFS) and X‐ray absorption near‐edge structure (XANES) analyses. On the basis of DSC, IR, and Raman it appear to be formation of GaC, whereas the analysis by EXAFS and XANES demonstrated that the gallium is found to be in a higher reduced state (almost metallic), supported by carbon. The question that remains open in addition to the one related to the formation of galium carbide is whether a complex structure, including oxygen contamination is involved in the layers surrounding the Ga as indicated by the EXAFS results.