Coinage Metal-Catalyzed Asymmetric Reactions of ortho-Alkynylaryl and Heteroaryl Aldehydes and Ketones

Coinage metals have become the metal of choice due to their excellent catalytic activity in organic transformation processes. Combining various chiral ligands and coinage metals became a productive area of research and access to heterocyclic derivatives according to an efficient and sustainable manner. This review was devoted to the various recently developed coinage metal-catalyzed domino processes of ortho-alkynylaryl and heteroaryl aldehydes and ketones leading to functionalized heterocycles. Various gold chiral complexes were presented, and methods of preparations of chromenes along with indoles were covered. Ag-chiral complexes are also prone to interesting activities such as cyclization followed by reduction and functionalization with enolizable ketones or (diazomethyl)phosphonate. Asymmetric Cu-catalyzed domino cyclization and asymmetric transfer hydrogenation reactions efficiently led to functionalized chromenes. Some remarkable examples involving copper associated with ruthenium in the context of a cyclization and asymmetric hydrogenation process were also presented.     

Orienting the Demixion of a Diblock‐copolymer Using 193 nm Interferometric Lithography for the Controlled Deposition of Nanoparticles

DUV interferometric lithography and diblock copolymer self‐organization have successfully been combined to provide a simple and highly collective nanopatterning technique enabling the organization of nanoparticles over several orders of magnitude, from nanometre to millimetre. The nanostructural changes at the surface of the polymer film after thermal annealing have been monitored by AFM and the process parameters optimized for obtaining a long‐range organization of the lamellar domains. In particular, the impact of the annealing conditions and geometric parameters of the substrate patterns have been investigated. The nanopatterns resulting from the lamellar demixion of (PS‐b‐MMA) were used for a controlled deposition of nanoparticles. The affinity of the hydrophobic particles for the PS block was demonstrated, opening new doors towards the preparation of high‐density arrays of nanoparticles with potential applications in data storage.

     

Analysis and reconstruction of a pulsed jet in crossflow by multi-plane snapshot POD

In this work, snapshot proper orthogonal decomposition (POD) is used to study a pulsed jet in crossflow where the velocity fields are extracted from stereoscopic particle image velocimetry (SPIV) results. The studied pulsed jet is characterized by a frequency f = 1 Hz, a Reynolds number Re _j  = 500 (based on the mean jet velocity ${\overline{U}_{j}}$  = 1.67 cm/s and a mean velocity ratio of R = 1). Pulsed jet and continuous jet are compared via mean velocity field trajectory and Q criterion. POD results of instantaneous, phase-averaged and fluctuating velocity fields are presented and compared in this paper. Snapshot POD applied on one plane allows us to distinguish an organization of the first spatial eigenmodes. A distinction between “natural modes” and “pulsed modes” is achieved with the results obtained by the pulsed and unforced jet. Secondly, the correlation tensor is established with four parallel planes (multi-plane snapshot POD) for the evaluation of volume spatial modes. These resulting modes are interpolated and the volume velocity field is reconstructed with a minimal number of modes for all the times of the pulsation period. These reconstructions are compared to orthogonal measurements to the transverse jet in order to validate the obtained three-dimensional velocity fields. Finally, this POD approach for the 3D flow field reconstruction from experimental data issued from planes parallel to the flow seems capable to extract relevant information from a complex three-dimensional flow and can be an alternative to tomo-PIV for large volume of measurement.     

Detection of pathogenic Staphylococcus aureus bacteria by gold based immunosensors

We describe the elaboration of ultra-sensitive immunosensors, to detect the bacterial pathogen Staphylococcus aureus. We utilized commercially available polyclonal anti-S. aureus antibody as receptor. Immunosensors were elaborated by building a self-assembled monolayer (SAM) of thiolamine onto planar gold-coated sensor chips. Then, Protein A was covalently linked to the thiolated SAM using glutaraldehyde as cross-linking agent. After a blocking step by Bovine Serum Albumin (BSA), the antibody was immobilized by affinity to Protein A. This step-by-step construction was monitored by Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and Quartz Crystal Microbalance with Dissipation (QCM-D). In a first stage, the parameters of immunosensor elaboration were optimized using a model rabbit IgG. The accessibility of receptors and the homogeneity of their distribution were checked by PM-RAIRS, QCM-D, and by immuno-gold scanning electron microscopy. Then, the specific rabbit anti-S. aureus antibody was immobilized and the resulting sensing layer was applied to the detection of the pathogen target. Independent detection of bacteria immobilized on the sensors by fluorescent imaging allowed validation of the specificity of recognition toward the pathogen as well as a quantitative response of the sensor. Using PM-RAIRS as transducing technique allowed us to enhance sensitivity and reach a very competitive detection level (10⁵ CFU mL^?1).     

Finite element modelling of cold drawing for high-precision tubes

Cold tube drawing is a metal forming process that allows manufacturers to produce high-precision tubes. The dimensions of the tube are reduced by pulling it through a conical converging die with or without inner tool. In this study, finite element modelling has been used to give a better understanding of the process.This paper presents a model that predicts the final dimensions of the tube with very high accuracy. It is validated thanks to experimental tests. Moreover, five studies are performed with this model, such as investigating the influence of the die angle on the drawing force or the influence of relative thickness on tube deformation.     

Laser ablation of energetic polymer solutions: effect of viscosity and fluence on the splashing behavior

Laser plasma thrusters are a new kind of propulsion system for small satellites, and work with the thrust created by the laser ablation of a target. Liquid polymer solutions are very promising fuels for such systems, provided that no splashing of the target occurs, because ejection of droplets strongly decreases the performances of the system. We have investigated the nanosecond infrared laser ablation of glycidyl azide polymer solutions containing carbon nanoparticles as absorber. Shadowgraphy imaging revealed two cases, namely splashing regime and solid-like behavior. The transition between both regimes depends on the viscosity of the solution and on the laser fluence, and is explained by the recoil force acting on the target. Appropriate conditions to avoid splashing were identified, showing that this liquid polymer solution is a suitable fuel for laser plasma thrusters.     

Captured and cross-linked palladium nanoparticles

Polystyrene-poly(ethylene glycol) resin-captured cross-linked palladium nanopaticles were prepared via a straightforward route, and their heterogeneous behavior was truly confirmed by various tests. They were applied to aqueous Suzuki cross-coupling reactions with various aryl bromides and recycled up to six times without loss of activity.     

Morphology of MgO smoke crystallites upon etching in wet environment

The etching of MgO smoke in wet conditions – an archetype for aqueous dissolution of oxide crystals – is explored on the basis of transmission electron microscope (TEM) analyses. In pure water with neutral pH, in acid solutions and in moist air, the MgO cubic crystallites show first (1 1 0) truncations of the 〈1 1 0〉 edges and then (1 1 1) cuts at the corners. Criteria are given to characterize (1 1 0) and (1 1 1) cuts on the TEM images. It is shown that (1 1 0) truncations appear independently of the formation of the (1 1 1) cuts and are associated with a stationary state. The picture is fully consistent with the previous suggestion of a “constrained Wulff profile” [9] which explains the formation of (1 1 0) cuts by excluding (1 1 1) facets.     

Tracy–Widom at High Temperature

We investigate the marginal distribution of the bottom eigenvalues of the stochastic Airy operator when the inverse temperature \(\beta \) tends to \(0\) . We prove that the minimal eigenvalue, whose fluctuations are governed by the Tracy–Widom \(\beta \) law, converges weakly, when properly centered and scaled, to the Gumbel distribution. More generally we obtain the convergence in law of the marginal distribution of any eigenvalue with given index \(k\) . Those convergences are obtained after a careful analysis of the explosion times process of the Riccati diffusion associated to the stochastic Airy operator. We show that the empirical measure of the explosion times converges weakly to a Poisson point process using estimates proved in Dumaz and Virág (Ann Inst H Poincaré Probab Statist 49(4):915–933, 2013). We further compute the empirical eigenvalue density of the stochastic Airy ensemble on the macroscopic scale when \(\beta \rightarrow 0\) . As an application, we investigate the maximal eigenvalues statistics of \(\beta _N\) -ensembles when the repulsion parameter \(\beta _N\rightarrow 0\) when \(N\rightarrow +\infty \) . We study the double scaling limit \(N\rightarrow +\infty , \beta _N \rightarrow 0\) and argue with heuristic and numerical arguments that the statistics of the marginal distributions can be deduced following the ideas of Edelman and Sutton (J Stat Phys 127(6):1121–1165, 2007) and Ramírez et al. (J Am Math Soc 24:919–944, 2011) from our later study of the stochastic Airy operator.