Promising optimization of the CeO2/CeCl3 cycle by reductive dissolution of cerium(IV) oxide

Although thermochemical cycles could constitute a promising approach to large-scale hydrogen production, physicochemical studies have shown that they will be difficult to implement because of poor reactivity. Most cycles involve solid–gas systems in which the reactivity is limited by interface passivation processes. To mitigate this difficulty a new approach is described based on a preliminary study performed with the UT-3 cycle. Replacing bromine by chlorine and iron by cerium not only simplifies the cycle from four reactions to three, but also allows the use of much less hazardous reactants while ensuring greater theoretical energy efficiency than the UT-3 cycle. In the proposed new reaction architecture the cycle can be partially carried out in the aqueous phase by reductive dissolution of cerium(IV) oxides to cerium(III) chlorides in an azeotropic hydrochloric acid solution. This has many advantages and could be used to optimize the operating temperatures, enhance reaction progress by eliminating reaction products at the interface, enhance the reaction kinetics by eliminating the solid diffusion layers, systematically regenerate the reactants within the process itself, and also facilitate gas separation by differential solubility. The assessment also shows that photon activation by dissociation of chlorine radicals during the first step, the reverse Deacon reaction, could allow the first two reactions to occur at lower temperatures near 100 °C.     

Nitrogen transformations and retention in planted and artificially aerated constructed wetlands

Nitrogen (N) processing in constructed wetlands (CWs) is often variable, and the contribution to N loss and retention by various pathways (nitrification/denitrification, plant uptake and sediment storage) remains unclear. We studied the seasonal variation of the effects of artificial aeration and three different macrophyte species (Phragmites australis, Typha angustifolia and Phalaris arundinacea) on N processing (removal rates, transformations and export) using experimental CW mesocosms. Removal of total nitrogen (TN) was higher in summer and in planted and aerated units, with the highest mean removal in units planted with T. angustifolia. Export of ammonium (NH₄⁺), a proxy for nitrification limitation, was higher in winter, and in unplanted and non-aerated units. Planted and aerated units had the highest export of oxidized nitrogen (NO_y), a proxy for reduced denitrification. Redox potential, evapotranspiration (ETP) rates and hydraulic retention times (HRT) were all predictors of TN, NH₄⁺ and NO_y export, and significantly affected by plants. Denitrification was the main N sink in most treatments accounting for 47-62% of TN removal, while sediment storage was dominant in unplanted non-aerated units and units planted with P. arundinacea. Plant uptake accounted for less than 20% of the removal. Uncertainties about the long-term fate of the N stored in sediments suggest that the fraction attributed to denitrification losses could be underestimated in this study.     

Dynamics of learning near singularities in layered networks

We explicitly analyze the trajectories of learning near singularities in hierarchical networks, such as multilayer perceptrons and radial basis function networks, which include permutation symmetry of hidden nodes, and show their general properties. Such symmetry induces singularities in their parameter space, where the Fisher information matrix degenerates and odd learning behaviors, especially the existence of plateaus in gradient descent learning, arise due to the geometric structure of singularity. We plot dynamic vector fields to demonstrate the universal trajectories of learning near singularities. The singularity induces two types of plateaus, the on-singularity plateau and the near-singularity plateau, depending on the stability of the singularity and the initial parameters of learning. The results presented in this letter are universally applicable to a wide class of hierarchical models. Detailed stability analysis of the dynamics of learning in radial basis function networks and multilayer perceptrons will be presented in separate work.     

Development and operation of alternative oxygen electrode materials for hydrogen production by high temperature steam electrolysis

High temperature steam electrolysis (HTSE) is one of the most promising ways for hydrogen mass production. To make this technology suitable from an economical point of view, each component of the system has to be optimized, from the balance of plant to the single solid oxide electrolysis cell. At this level, the optimization of the oxygen electrode is of particular interest since it contributes to a large extent to the cell polarization resistance. The present paper is focused on alternative oxygen electrode materials with improved performances compared to the usual ones mainly based on perovskite structure. Two nickelates, with compositions La₂NiO_4+δ and Nd₂NiO_4+δ are investigated and evaluated in HTSE operation at the button cell level. The performances of the Ln₂NiO_4+δ - containing cells (Ln = La, Nd) is improved compared to a cell containing the classical Sr-doped LaMnO₃ (LSM) perovskite oxygen electrode showing that nickelates are promising candidates for HTSE oxygen electrodes, especially for operation below 800 °C. Indeed, current densities determined at 1.3 V are 1.1 times larger for the La₂NiO_4+δ - containing cell and 1.6 times larger for the Nd₂NiO_4+δ one compared to the LSM - containing cell at 850 °C, whereas at 750 °C they are 1.8 and 4.4 times larger, respectively. Thanks to the use of a reference electrode, by coupling impedance spectroscopy and polarization measurements, the overpotential of each working electrode is deconvoluted from the complete cell voltage under HTSE operating conditions.     

Modulation of Cellular Fate of Vinyl Triarylamines through Structural Fine Tuning: To Stay or Not To Stay in the Mitochondria?

Mitochondria are involved in many cellular pathways and dysfunctional mitochondria are linked to various diseases. Hence efforts have been made to design mitochondria-targeted fluorophores for monitoring the mitochondrial status. However, the factors that govern the mitochondria-targeted potential of dyes are not well-understood. In this context, we synthesized analogues of the TP-2Bzim probe belonging to the vinyltriphenylamine (TPA) class and already described for its capacity to bind nuclear DNA in fixed cells and mitochondria in live cells. These analogues ( TP-1Bzim, TPⁿ-2Bzim, TP¹⁺-2Bzim, TN-2Bzim ) differ in the cationic charge, the number of vinylbenzimidazolium branches and the nature of the triaryl core. Using microscopy, we demonstrated that the cationic derivatives accumulate in mitochondria but do not reach mtDNA. Under depolarisation of the mitochondrial membrane, TP-2Bzim and TP¹⁺-2Bzim translocate to the nucleus in direct correlation with their strong DNA affinity. This reversible phenomenon emphasizes that these probes can be used to monitor ΔΨ_m variations.     

Quantitative Assessment of Affinity Selection Performance by Using DNA-Encoded Chemical Libraries

DNA-encoded chemical libraries are often used for the discovery of ligands against protein targets of interest. These large collections of DNA-barcoded chemical compounds are typically screened by using affinity capture methodologies followed by PCR amplification and DNA sequencing procedures. However, the performance of individual steps in the selection procedures has been scarcely investigated, so far. Herein, the quantitative analysis of selection experiments, by using three ligands with different affinity to carbonic anhydrase IX as model compounds, is described. In the first set of experiments, quantitative PCR (qPCR) procedures are used to evaluate the recovery and selectivity for affinity capture procedures performed on different solid-phase supports, which are commonly used for library screening. In the second step, both qPCR and analysis of DNA sequencing results are used to assess the recovery and selectivity of individual carbonic anhydrase IX ligands in a library, containing 360 000 compounds. Collectively, this study reveals that selection procedures can be efficient for ligands with sub-micromolar dissociation constants to the target protein of interest, but also that selection performance dramatically drops if 10⁴ copies per library member are used as the input.     

Intracellular Fate of Hydrophobic Nanocrystal Self‐Assemblies in Tumor Cells

Control of interactions between nanomaterials and cells remains a biomedical challenge. A strategy is proposed to modulate the intralysosomal distribution of nanoparticles through the design of 3D suprastructures built by hydrophilic nanocrystals (NCs) coated with alkyl chains. The intracellular fate of two water‐dispersible architectures of self‐assembled hydrophobic magnetic NCs: hollow deformable shells (colloidosomes) or solid fcc particles (supraballs) is compared. These two self‐assemblies display increased cellular uptake by tumor cells compared to dispersions of the water‐soluble NC building blocks. Moreover, the self‐assembly structures increase the NCs density in lysosomes and close to the lysosome membrane. Importantly, the structural organization of NCs in colloidosomes and supraballs are maintained in lysosomes up to 8 days after internalization, whereas initially dispersed hydrophilic NCs are randomly aggregated. Supraballs and colloidosomes are differently sensed by cells due to their different architectures and mechanical properties. Flexible and soft colloidosomes deform and spread along the biological membranes. In contrast, the more rigid supraballs remain spherical. By subjecting the internalized suprastructures to a magnetic field, they both align and form long chains. Overall, it is highlighted that the mechanical and topological properties of the self‐assemblies direct their intracellular fate allowing the control intralysosomal density, ordering, and localization of NCs.