Unlocking the potential of azide-phosphine Staudinger reaction for the synthesis of poly(arylene iminophosphorane)s and materials therefrom.

Iminophosphoranes with the general formula (RP═NR') have great potential in synthetic chemistry as valuable precursors/intermediates in organic synthesis or as building blocks for various organic compounds. However, the synthetic approaches and conditions to prepare iminophosphoranes are still poorly understood, limiting the utility of this chemistry for organic materials. In this article, a simple and efficient synthesis of previously unattainable poly(arylene iminophosphoranes) is reported.

Crystallization and Optical Behaviour of Nanocomposite Sol-Gel TiO:Ag Films.

Sol-gel spin coating method was employed for depositing TiO and Ag-doped TiO films. The effects of Ag doping and the annealing temperatures (300-600 °C) were studied with respect to their structural, morphological, vibrational, and optical properties. Field Emission Scanning Electron microscopy (FESEM) investigation exhibited the grained, compact structures of TiO-based films.

Spatio-Selective Reconfiguration of Mechanical Metamaterials Through the Use of Dynamic Covalent Chemistries.

Mechanical metamaterials achieve unprecedented mechanical properties through their periodically interconnected unit cell structure. However, their geometrical design and resulting mechanical properties are typically fixed during fabrication. Despite efforts to implement covalent adaptable networks (CANs) into metamaterials for permanent shape reconfigurability, emphasis is given to global rather than local shape reconfiguration.

Gaussian model of fluctuating membrane and its scattering properties.

A mathematical model is developed to jointly analyze elastic and inelastic scattering data of fluctuating membranes within a single theoretical framework. The model builds on a nonhomogeneously clipped time-dependent Gaussian random field. This specific approach provides one with general analytical expressions for the intermediate scattering function for any number of sublayers in the membrane and arbitrary contrasts.

Two-Step Wetting of Nanoporous Carbons: Small-Angle Scattering Analysis of Capillary Rise.

Numerous applications of nanoporous materials require their pores to be filled with liquids. In spite of its huge technological importance, the conditions for the wetting of nanometer-sized pores and its phenomenology are still poorly understood. We report on capillary rise experiments with water in carbon xerogels, with synchrotron small-angle scattering used to follow the process in situ at the nanometer scale.

Solid Polymer Electrolytes with Sacrificial End Groups for a Wide Oxidative Potential and Stable Interface in Lithium Metal Batteries.

Poly(ethylene glycol) (PEG), despite being the most studied polymer electrolyte, suffers from serious drawbacks, which require fundamental studies behind its underperformance in lithium batteries. Here, we report the effect of the terminal group on triarm PEG stars bearing either hydroxyl (TPEG-OH) or carbonate-ketone (TPEG-Carb-ket) terminal groups. The latter is synthesized by a ring-opening reaction triggered by the -OH end group of TPEG-OH and results in a carbonate-ketone functionality.

Development of In Situ Methods for Preparing La-Mn-Co-Based Compounds over Carbon Xerogel for Oxygen Reduction Reaction in an Alkaline Medium.

Metal oxides containing La, Mn, and Co cations can catalyze oxygen reduction reactions (ORRs) in electrochemical processes. However, these materials require carbon support and optimal interactions between both compounds to be active. In this work, two approaches to prepare composites of La-Mn-Co-based compounds over carbon xerogel were developed.

Small-Angle Scattering Indicates Equilibrium Instead of Metastable Capillary Condensation in SBA-15 Mesoporous Silica.

Questions about the origin of the adsorption/desorption hysteresis in mesoporous materials are as old as sorption experiments themselves. The historical conception that underlines most existing methods to extract pore size distributions from sorption data assumes that adsorption is a metastable process and that desorption takes place at thermodynamic equilibrium. In this work, we measure nitrogen and argon sorption on a series of 14 SBA-15 ordered mesoporous silicas and use small-angle X-ray scattering to independently determine their pore sizes.

Reversing the relative time courses of the peptide bond reaction with oligopeptides of different lengths and charged amino acid distributions in the ribosome exit tunnel.

The kinetics of the protein elongation cycle by the ribosome depends on intertwined factors. One of these factors is the electrostatic interaction of the nascent protein with the ribosome exit tunnel. In this computational biology theoretical study, we focus on the rate of the peptide bond formation and its dependence on the ribosome exit tunnel electrostatic potential profile.

Normal-to-Supercooled Liquid Transition in Molecular Glass-Formers: A Hidden Structural Transformation Fuelled by Conformational Interconversion.

Molecular dynamics and transport coefficients change significantly around the so-called Arrhenius crossover in glass-forming systems. In this article, we revisit the dynamic processes occurring in a glass-forming macrocyclic crown thiaether above its glass transition, revealing two crossover temperatures: at 309 and at 333 K. We identify the second one as the Arrhenius crossover that is closely related to the normal-to-supercooled liquid transition in this compound.

Design, manufacturing and testing of a green non-isocyanate polyurethane prosthetic heart valve.

The sole effective treatment for most patients with heart valve disease is valve replacement by implantation of mechanical or biological prostheses. However, mechanical valves represent high risk of thromboembolism, and biological prostheses are prone to early degeneration. In this work, we aim to determine the potential of novel environmentally-friendly non-isocyanate polyurethanes (NIPUs) for manufacturing synthetic prosthetic heart valves.

Neutrophil extracellular traps and active myeloperoxidase concentrate in lamellar tissue of equids with naturally occurring laminitis.

Laminitis is a pathology of the equine digit ultimately leading to a failure of the dermo-epidermal interface. Neutrophil activation is recognized as a major factor in SIRS-associated laminitis and has recently been described in induced endocrinopathic laminitis evidenced by the presence of myeloperoxidase (MPO). Neutrophil extracellular traps (NET) are released with neutrophil activation.

Revisiting Dynamic Processes and Relaxation Mechanisms in a Heterocyclic Glass-Former: Direct Observation of a Transient State.

Despite decades of studies, a clear understanding of near- phenomena remains challenging for glass-forming systems. This review delves into the intricate molecular dynamics of the small, heterocyclic thioether, 6-methyl-2,3-dihydro-1,4-benzodithiine (MeBzS), with a particular focus on its near- cold crystallization and relaxation mechanisms. Investigating isothermal crystallization kinetics at various temperatures reveals a significant interplay between its molecular dynamics and recrystallization from a supercooled liquid.

Design of 3D-Photoprintable, Bio-, and Hemocompatible Nonisocyanate Polyurethane Elastomers for Biomedical Implants.

Polyurethanes (PUs) have adjustable mechanical properties, making them suitable for a wide range of applications, including in the biomedical field. Historically, these PUs have been synthesized from isocyanates, which are toxic compounds to handle. This has encouraged the search for safer and more environmentally friendly synthetic routes, leading today to the production of nonisocyanate polyurethanes (NIPUs).

Preparation of Dinitrogen Trioxide for Organic Synthesis: A Phase Equilibrium Approach.

Dinitrogen trioxide (NO) is a potent nitrosating agent featured with high reactivity and appealing atom economy. Because of its instability and the entanglement of chemical and phase equilibria, NO has rarely been utilized in organic synthesis as a stock reagent with well-defined composition. In this review, the preparations of pure NO and its concentrated solution (>0.

Intensified Continuous Flow Process for the Scalable Production of Bio-Based Glycerol Carbonate.

A subtle combination of fundamental and applied organic chemistry toward process intensification is demonstrated for the large-scale production of bio-based glycerol carbonate under flow conditions. The direct carbonation of bio-based glycidol with CO is successfully carried out under intensified flow conditions, with Barton's base as a potent homogeneous organocatalyst. Process metrics for the CO coupling step (for the upstream production, output: 3.

Cascade Exotherms for Rapidly Producing Hybrid Nonisocyanate Polyurethane Foams from Room Temperature Formulations.

For decades, self-blown polyurethane foams─found in an impressive range of materials─are produced by the toxic isocyanate chemistry and are difficult to recycle. Producing them in existing production plants by a rapid isocyanate-free self-blowing process from room temperature (RT) formulations is a long-lasting challenge. The recent water-induced self-blowing of nonisocyanate polyurethane (NIPU) formulations composed of a CO-based tricyclic carbonate, diamine, water, and a catalyst successfully addressed the isocyanate issue, however failed to provide foams at RT.

Molecular Dynamics and Near- Phenomena of Cyclic Thioethers.

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4'-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound ), 2,3,14,15-bis(4',4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound ), and 2,3,8,9-bis(4',4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound ). The compounds exhibit relatively high glass transition temperatures (), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers.

Covalent Adaptable Networks through Dynamic ,-Acetal Chemistry: Toward Recyclable CO-Based Thermosets.

Finding new chemistry platforms for easily recyclable polymers has become a key challenge to face environmental concerns and the growing plastics demand. Here, we report a dynamic chemistry between CO-sourced alkylidene oxazolidones and thiols, delivering circular non-isocyanate polyurethane networks embedding ,-acetal bonds. The production of oxazolidone monomers from CO is facile and scalable starting from cheap reagents.

Revisiting the Paradigm of Reaction Optimization in Flow with a Priori Computational Reaction Intelligence.

The use of micro/meso-fluidic reactors has resulted in both new scenarios for chemistry and new requirements for chemists. Through flow chemistry, large-scale reactions can be performed in drastically reduced reactor sizes and reaction times. This obvious advantage comes with the concomitant challenge of re-designing long-established batch processes to fit these new conditions.

Common scab disease: structural basis of elicitor recognition in pathogenic species.

Common scab is a disease caused by a few species that affects important root and tuber crops including potato, beet, radish, and parsnip, resulting in major economic losses worldwide. In this work, we unveiled the molecular basis of host recognition by these pathogens by solving the structure of the sugar-binding protein CebE of in complex with cellotriose, the main elicitor of the pathogenic lifestyle of these bacteria. We further revealed that the signaling pathway from CebE-mediated transport of cellotriose is conserved in all pathogenic species except which causes soft rot disease in sweet potatoes.

Inhalation powder development without carrier: How to engineer ultra-flying microparticles?

Particle engineering technologies have led to the commercialization of new inhaled powders like PulmoSol or PulmoSphere. Such platforms are produced by spray drying, a well-known process popular for its versatility, thanks to wide-ranging working parameters. Whereas these powders contain a high drug-loading, we have studied a low-dose case, in optimizing the production of powders with two anti-asthmatic drugs, budesonide and formoterol.