Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions

The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (Cu^I/Cu^I*/Cu⁰) was suggested.     

Formulation of Cannabidiol in Colloidal Lipid Carriers

In this study, the general processability of cannabidiol (CBD) in colloidal lipid carriers was investigated. Due to its many pharmacological effects, the pharmaceutical use of this poorly water-soluble drug is currently under intensive research and colloidal lipid emulsions are a well-established formulation option for such lipophilic substances. To obtain a better understanding of the formulability of CBD in lipid emulsions, different aspects of CBD loading and its interaction with the emulsion droplets were investigated. Very high drug loads (>40% related to lipid content) could be achieved in emulsions of medium chain triglycerides, rapeseed oil, soybean oil and trimyristin. The maximum CBD load depended on the type of lipid matrix. CBD loading increased the particle size and the density of the lipid matrix. The loading capacity of a trimyristin emulsion for CBD was superior to that of a suspension of solid lipid nanoparticles based on trimyristin (69% vs. 30% related to the lipid matrix). In addition to its localization within the lipid core of the emulsion droplets, cannabidiol was associated with the droplet interface to a remarkable extent. According to a stress test, CBD destabilized the emulsions, with phospholipid-stabilized emulsions being more stable than poloxamer-stabilized ones. Furthermore, it was possible to produce emulsions with pure CBD as the dispersed phase, since CBD demonstrated such a pronounced supercooling tendency that it did not recrystallize, even if cooled to −60 °C.     

O2‐mediated dehydrogenative amination of phenols

A method was developed for the direct dehydrogenative construction of C? N bonds between unprotected phenols and a series of cyclic anilines without resorting to any kind of metal activation of either substrate and without the use of halides. The resulting process relies on the exclusively organic activation of molecular oxygen and the subsequent oxidation of the aniline substrate. This allows the coupling of ubiquitous phenols, thus furnishing aminophenols through an atom‐economical and most sustainable dehydrogenative amination method. This new reactivity, which relies on the intrinsic organic reactivity of cumene in what can be seen as a modified Hock activation process of oxygen, is expected to have a large impact on the formation of C? N bonds in organic synthesis.     

The cantilever strip plate under torision, bending or flexure at infinity

A homogeneous, isotropic plate occupies the region 0x ₁, |x ₂|a, |x ₃|h, where the ratio h/a is sufficiently small so that the classical theory of thin plate bending applies. The short end of the plate at x ₁=0 is clamped while the long sides are free. This cantilever plate is now loaded at x ₁=+ by an applied twisting moment, by a bending moment or by flexure. Despite the fundamental nature of these problems, and the long history of thin plate theory, no solutions are to be found in the existing literature that will determine (for instance) the important unknown resultants V ₁, M ₁₁ at the clamped end x ₁=0. The main reason for this is that this combination of boundary conditions leads to severe oscillating singularities of the field in the corners (0, ±a). The fact that such singularities must exist is widely known, but we present here for the first time a method of solution that takes these singularities fully into account.Our numerical results show that the values of M ₁₁, V ₁ on x ₁=0 bear little resemblance to those of the corresponding Saint-Venant solutions, which do not fully satisfy the boundary conditions at the clamped end. Indeed, significantly large values of these resultants were found at points far enough from the corners so as to be relevant in actual engineering applications. Also of interest are certain weighted integrals of M ₁₁, V ₁ which we calculate. These constants determine the effect of the clamping at large distances (greater than 4a, say) from the cla,ped end. At such distances, the effect of the clamping is merely to impose an additional rigid body deflection on the plate.Finally, we consider the plate of finite length. Provided that the aspect ratio is 2 or more, we give accurate approximate solutions for the torsion, bending or flexure of a finite plate clamped at both ends.     

Contrôle par rotation ou par aspiration de l'écoulement autour d'un cylindre calculé par Simulation des Grandes Échelles

Control of the flow around a circular cylinder is studied using Large Eddy Simulation. The influence of control by rotation and suction on the flow characteristics is considered for several Reynolds numbers. Comparisons with experiments were conducted at $\mathit{Re}={10}^5$ for the flow with and without control. A drag reduction up to 30% is obtained for an usual suction intensity. To cite this article: G. Fournier et al., C. R. Mecanique 333 (2005).     

Co-continuity interval in immiscible polymer blends by dynamic mechanical spectroscopy in the molten and solid state

The work focuses on the detection of the co-continuity window in immiscible polymer blends. The purpose of the paper is to describe how rheological techniques can help to evaluate the composition range of the co-continuous morphology through the study of a particular system: PEO/PVDF-HFP. First, the blends were characterized by selective dissolution experiments and SEM observations. Then the ability of dynamic mechanical spectroscopy to detect the co-continuity was investigated in the melt and in the solid state. The evolution of the storage modulus of molten blends with their composition at a constant low frequency gives information about the co-continuity interval, especially as far as the onset of the continuity of the PEO phase is concerned. Then the immiscibility of the polymers and the continuity of PVDF-HFP as a function of blend composition have been highlighted by means of dynamic mechanical spectrometry below the melting point of PVDF-HFP. Comparison with results from classical methods shows fair agreement.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Iron complexes as photoinitiators for radical and cationic polymerization through photoredox catalysis processes

Six iron complexes (FeCs) with various ligands have been designed and synthesized. In combination with additives (e.g., iodonium salt, N‐vinylcarbazole, amine, or chloro triazine), the FeC‐based systems are able to efficiently generate radicals, cations, and radical cations on a near UV or visible light‐emitting diode (LED) exposure. These systems are characterized by an unprecedented reactivity, that is, for very low content 0.02% FeC‐based systems is still highly efficient in photopolymerization contrary to the most famous reference systems (Bisacylphosphine oxide) illustrating the performance of the proposed catalytic approach. This work paves the way for polymerization in soft conditions (e.g., on LED irradiation). These FeC‐based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations and can operate through oxidation or/and reduction cycles. The photochemical mechanisms for the formation of the initiating species are studied using steady state photolysis, cyclic voltammetry, electron spin resonance spin trapping, and laser flash photolysis techniques. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 42–49