A Reliable Enantioselective Route to Mono-Protected N1-Cbz Piperazic Acid Building Block

The chiral N1-Cbz, N2-H derivative of the piperazic acid monomer is a valuable building block in the total synthesis of natural products, comprising this nonproteinogenic amino acid. In that context, we wish to report an improved synthetic protocol for the synthesis of both (3R)- and (3S)-piperazic acids bearing the carboxybenzyl protecting group (Cbz) selectively at the N1 position. Our method builds on previously reported protocols, circumventing their potential shortcomings, and optimizing the ultimate selective deprotection at the N2 position, thus, offering an efficient and reproducible pathway to suitably modified piperazates in high optical purity.     

Micro-immunohistochemistry using a microfluidic probe

A flexible method to extract more high-quality information from tissue sections is critically needed for both drug discovery and clinical pathology. Here, we present micro-immunohistochemistry (μIHC), a method for staining tissue sections at the micrometre scale. Nanolitres of antibody solutions are confined over micrometre-sized areas of tissue sections using a vertical microfluidic probe (vMFP) for their incubation with primary antibodies, the key step in conventional IHC. The vMFP operates several micrometres above the tissue section, can be interactively positioned on it, and even enables the staining of individual cores of tissue microarrays with multiple antigens. μIHC using such a microfluidic probe is preservative of tissue samples and reagents, alleviates antibody cross-reactivity issues, and allows a wide range of staining conditions to be applied on a single tissue section. This method may therefore find broad use in tissue-based diagnostics and in research.     

Critical scaling properties at the superfluid transition of 4He in aerogel

We study the superfluid transition of 4He in aerogel by Monte Carlo simulations and finite size scaling analysis. Aerogel is a highly porous silica glass, which we model by a diffusion limited cluster aggregation model. The superfluid is modeled by a three dimensional XY model, with excluded bonds to sites on the aerogel cluster. We obtain the correlation length exponent nu=0.73+/-0.02, in reasonable agreement with experiments and with previous simulations. For the heat capacity exponent alpha, both experiments and previous simulations suggest deviations from the Josephson hyperscaling relation alpha=2-dnu. In contrast, our Monte Carlo results support hyperscaling with alpha=-0.2+/-0.05. We suggest a reinterpretation of the experiments, which avoids scaling violations and is consistent with our simulation results.     

Structural Insights into the Role of β3 nAChR Subunit in the Activation of Nicotinic Receptors

The β3 subunit of nicotinic acetylcholine receptors (nAChRs) participates in heteropentameric assemblies with some α and other β neuronal subunits forming a plethora of various subtypes, differing in their electrophysiological and pharmacological properties. While β3 has for several years been considered an accessory subunit without direct participation in the formation of functional binding sites, recent electrophysiology data have disputed this notion and indicated the presence of a functional (+) side on the extracellular domain (ECD) of β3. In this study, we present the 2.4 Å resolution crystal structure of the monomeric β3 ECD, which revealed rather distinctive loop C features as compared to those of α nAChR subunits, leading to intramolecular stereochemical hindrance of the binding site cavity. Vigorous molecular dynamics simulations in the context of full length pentameric β3-containing nAChRs, while not excluding the possibility of a β3 (+) binding site, demonstrate that this site cannot efficiently accommodate the agonist nicotine. From the structural perspective, our results endorse the accessory rather than functional role of the β3 nAChR subunit, in accordance with earlier functional studies on β3-containing nAChRs.     

High Catalytic Efficiency of a Nanosized Copper-Based Catalyst for Automotives: A Physicochemical Characterization

The global trend in restrictions on pollutant emissions requires the use of catalytic converters in the automotive industry. Noble metals belonging to the platinum group metals (PGMs, platinum, palladium, and rhodium) are currently used for autocatalysts. However, recent efforts focus on the development of new catalytic converters that combine high activity and reduced cost, attracting the interest of the automotive industry. Among them, the partial substitution of PGMs by abundant non-PGMs (transition metals such as copper) seems to be a promising alternative. The PROMETHEUS catalyst (PROM100) is a polymetallic nanosized copper-based catalyst for automotives prepared by a wet impregnation method, using as a carrier an inorganic mixed oxide (CeO₂-ZrO₂) exhibiting elevated oxygen storage capacity. On the other hand, catalyst deactivation or ageing is defined as the process in which the structure and state of the catalyst change, leading to the loss of the catalyst’s active sites with a subsequent decrease in the catalyst’s performance, significantly affecting the emissions of the catalyst. The main scope of this research is to investigate in detail the effect of ageing on this low-cost, effective catalyst. To that end, a detailed characterization has been performed with a train of methods, such as SEM, Raman, XRD, XRF, BET and XPS, to both ceria–zirconia mixed inorganic oxide support (CZ-fresh and -aged) and to the copper-based catalyst (PROM100-fresh and -aged), revealing the impact of ageing on catalytic efficiency. It was found that ageing affects the Ce–Zr mixed oxide structure by initiating the formation of distinct ZrO₂ and CeO₂ structures monitored by Raman and XRD. In addition, it crucially affects the morphology of the sample by reducing the surface area by a factor of nearly two orders of magnitude and increasing particle size as indicated by BET and SEM due to sintering. Finally, the Pd concentration was found to be considerably reduced from the material’s surface as suggested by XPS data. The above-mentioned alterations observed after ageing increased the light-off temperatures by more than 175 °C, compared to the fresh sample, without affecting the overall efficiency of the catalyst for CO and CH₄ oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO₄ are identified as the main causes for the deactivation after hydrothermal ageing.     

The problem of sharp notch in couple-stress elasticity

The problem of sharp notch in couple-stress elasticity is considered in this paper. The problem involves a sharp notch in a body of infinite extent. The body has microstructural properties, which are assumed to be characterized by couple-stress effects. Both symmetric and anti-symmetric loadings at remote regions are considered under plane-strain conditions. The faces of the notch are considered traction free. To determine the field around the tip of the notch, a boundary-layer approach is followed by considering an expansion of the displacements in a form of separated variables in a polar coordinate system. Our analysis is in the spirit of the Knein–Williams and Karp–Karal asymptotic techniques but it is much more involved than its corresponding analysis of standard elasticity due to the complicated boundary value problem (higher-order system of governing PDEs and additional boundary conditions as compared to the standard theory). Eventually, an eigenvalue problem is formulated and this, along with the restriction of a bounded potential energy, provides the asymptotic fields. The cases of a crack and a half-space are analyzed as limit cases of the general notch problem. Certain deviations from the standard classical elasticity results are noted.     

Visualization of Taylor-Couette and spiral Poiseuille flows using a snapshot FLASH spatial tagging sequence

A new magnetic resonance imaging technique was applied to the Taylor-Couette and spiral Poiseuille (Taylor-Couette with superposed mean axial flux) flows for the first time. The experimental technique is a combination of spatial tagging methods and a snapshot FLASH imaging sequence, which allows the full-field visualization of 2-D slices of the flow field, with image acquisition times approximately half a second. By acquiring images every few seconds, direct visualization of flow patterns can be obtained in the form of cinematography. Tagged images of the Taylor-Couette flow were acquired in both the axial and transverse planes and confirmed previously reported numerical predictions of Taylor cell size. Tagged images of the spiral Poiseuille flows verified that the cells in this flow propagate at a higher velocity than the mean axial flow. In addition, intermittent cell formation was observed as the axial flow was increased.     

Rayleigh waves emitted by a propagating crack in a strain-rate dependent elastic medium

A simple model was proposed for the interpretation of the non-circular form of the Rayleigh wavefronts emitted by a fast running crack in a plate. The surface deformation around the crack tip, due to the high stress concentration there, propagated as a surface wave after fracture of this zone. On the other hand, the moving singularity of the crack tip created a dynamic stress field of varying intensity with time all over the specimen. This dynamic stress field resulted in a significant change of the mechanical properties of a strain-rate dependent material and therefore it influenced the velocity of propagation of fracture-Rayleigh wavefronts. An analysis of this varying dynamic strain field explained the non-circular form of Rayleigh waves, accompanying the propagating crack. For the experimental evaluation of the K₁-factor the method of dynamic caustics was used in conjunction with the high-speed photography technique.     

Pseudodifferential Operators on Spaces of Distributions Associated with Non-negative Self-Adjoint Operators

We consider Hörmander type symbols on a family of spaces associated with non-negative self-adjoint operators, and we prove boundedness of the corresponding pseudodifferential operators on both classical and non-classical Besov and Triebel–Lizorkin spaces. Consequently, this also covers the case of Sobolev spaces. As an application, we obtain boundedness of spectral multipliers on the mentioned spaces.