A Mixed Ligand Approach for the Asymmetric Hydrogenation of 2‐Substituted Pyridinium Salts

Herein we describe a new methodology for the asymmetric hydrogenation (AH) of 2‐substituted pyridinium salts. An iridium catalyst based on a mixture of a chiral monodentate phosphoramidite and an achiral phosphine was shown to hydrogenate N‐benzyl‐2‐arylpyiridinium bromides to the corresponding N‐benzyl‐2‐arylpiperidines with full conversion and good enantioselectivity. The mechanism of the reaction under optimized conditions was investigated via kinetic measurements and isotopic labeling experiments. Our study suggests that the hydrogenation starts with a 1,4‐hydride addition and that the enantiodiscriminating step involves the reduction of an iminium intermediate.

     

Experimental investigation of water droplet–air flow interaction in a non-reacting PEM fuel cell channel

It has been well documented that water production in PEM fuel cells occurs in discrete locations, resulting in the formation and growth of discrete droplets on the gas diffusion layer (GDL) surface within the gas flow channels (GFCs). This research uses a simulated fuel cell GFC with three transparent walls in conjunction with a high speed fluorescence photometry system to capture videos of dynamically deforming droplets. Such videos clearly show that the droplets undergo oscillatory deformation patterns. Although many authors have previously investigated the air flow induced droplet detachment, none of them have studied these oscillatory modes. The novelty of this work is to process and analyze the recorded videos to gather information on the droplets induced oscillation. Plots are formulated to indicate the dominant horizontal and vertical deformation frequency components over the range of sizes of droplets from formation to detachment. The system is also used to characterize droplet detachment size at a variety of channel air velocities. A simplified model to explain the droplet oscillation mechanism is provided as well.     

Phase-Change Perovskite Microlaser with Tunable Polarization Vortex

Metasurfaces supporting optical bound states in the continuum (BICs) are emerging as simple and compact optical cavities to realize polarization-vortex lasers. The winding of the polarization around the singularity defines topological charges which are generally set by the cavity design and cannot be altered without changing geometrical parameters. Here, a subwavelength-thin phase-change halide perovskite BIC metasurface functioning as a tunable polarization vortex microlaser is demonstrated. Upon the perovskite structural phase transitions, both its refractive index and gain vary substantially, inducing reversible and bistable switching between distinct polarization vortexes underpinned by opposite topological charges. Dynamic tuning and switching of the resulting vector beams may find use in microscopy imaging, particle trapping and manipulation, and optical data storage.     

Low-enthalpy geothermal energy: An opportunity to meet increasing energy needs and reduce CO2 and atmospheric pollutant emissions in Piemonte,Italy

The scope for diffusion of very low-enthalpy geothermal plants in the Piemonte region of Italy, using groundwater heat pumps (GWHP), was analyzed to check environmental sustainability and the benefits in terms of reducing greenhouse gas emissions from fossil fuels. GWHP implementation seemed particularly suitable to the specific characteristics of the Piemonte plain. An important thick and productive shallow aquifer is present across the entire plain beneath the major energy users and is therefore appropriate for geothermal energy development purposes. The building stock could be adapted to heat pumps in different ways, but objective-oriented policies will be required to reach the best results in terms of environmental benefits.     

Peripheral pain mechanisms

A promising new treatment for glioma involves Auger electron emitters such as 125I or 123I conjugated to deoxyuridine (IUdR). However, the presence in tumour deposits of non-proliferating cells with clonogenic potential poses a major limitation to this cycle-specific therapy. We have used multicellular tumour spheroids derived from the human glioma cell line UVW to study [125I]IUdR-targeted radiotherapy in aggregates containing cells in different proliferative states. Autoradiographic identification of labelled cells indicated that nuclear incorporation of [125I]IUdR decreased markedly with increasing size of spheroid. IUdR incorporation was maximal in the surface layer of cells and decreased with depth within spheroids. Radiopharmaceutical uptake corresponded closely to the regions of cell cycling as indicated by staining for the nuclear antigen Ki67. The uptake of drug was enhanced by increasing the duration of incubation from 52 h to 104 h. These observations suggest that significant sparing of non-cycling malignant cells would result from treatment delivered as a single injection of radiolabelled IUdR. To achieve maximal therapeutic effect. IUdR should be administered by multiple injections, by slow release from biodegradable implants or by slow-pump delivery.     

Transient liquid phase bonding of HfC-based ceramics

Transient liquid phase (TLP) bonding enables joining at lower temperatures than traditional bonding techniques and preserves the potential for high-temperature applications, making it particularly attractive for joining ultra-high-temperature ceramics (UHTCs) such as carbides and borides. The feasibility of a TLP joint between “pure” carbides has been recently demonstrated. The present study examines the interactions that occur between undoped HfC or MoSi₂-doped HfC and a Ni/Nb/Ni multilayer interlayer during TLP bonding. Bonding is performed at 1400 °C for 30 min in a high-vacuum furnace. SEM–EDS characterization shows that the reaction layer formed at the interlayer/ceramic interface contains mixed carbides and depending upon the ceramic, Ni–Nb–Hf, or Ni–Nb–Hf–Si, or Ni–Nb–Si alloys. Nanoindentation tests traversing the reaction layer between the bulk ceramic and Nb foil midplane also show a clear transition zone across which the indentation modulus and hardness vary. Crack-free joints have been obtained with undoped HfC. The addition of 5 vol% MoSi₂ introduces small (<5 μm long) isolated cracks within the reaction layer, whereas with 15 vol% MoSi₂ added, cracking was pervasive within the reaction layer. When the reaction layer exceeds a critical thickness, as in the case of the bond obtained with HfC doped with 15 vol% MoSi₂, residual stresses become sufficiently large to cause extensive cracking and bond failure. The results suggest a need to characterize and balance the positive role of additives on sintering with the potentially deleterious role they may have on joining.