The RHIM of the Immune Adaptor Protein TRIF Forms Hybrid Amyloids with Other Necroptosis-Associated Proteins

TIR-domain-containing adapter-inducing interferon-β (TRIF) is an innate immune protein that serves as an adaptor for multiple cellular signalling outcomes in the context of infection. TRIF is activated via ligation of Toll-like receptors 3 and 4. One outcome of TRIF-directed signalling is the activation of the programmed cell death pathway necroptosis, which is governed by interactions between proteins that contain a RIP Homotypic Interaction Motif (RHIM). TRIF contains a RHIM sequence and can interact with receptor interacting protein kinases 1 (RIPK1) and 3 (RIPK3) to initiate necroptosis. Here, we demonstrate that the RHIM of TRIF is amyloidogenic and supports the formation of homomeric TRIF-containing fibrils. We show that the core tetrad sequence within the RHIM governs the supramolecular organisation of TRIF amyloid assemblies, although the stable amyloid core of TRIF amyloid fibrils comprises a much larger region than the conserved RHIM only. We provide evidence that RHIMs of TRIF, RIPK1 and RIPK3 interact directly to form heteromeric structures and that these TRIF-containing hetero-assemblies display altered and emergent properties that likely underlie necroptosis signalling in response to Toll-like receptor activation.     

Basic Substances,a Sustainable Tool to Complement and Eventually Replace Synthetic Pesticides in the Management of Pre and Postharvest Diseases: Reviewed Instructions for Users

Synthetic pesticides are widely used to protect crops from pathogens and pests, especially for fruits and vegetables, and this may lead to the presence of residues on fresh produce. Improving the sustainability of agriculture and, at the same time, reducing the adverse effects of synthetic pesticides on human health requires effective alternatives that improve the productivity while maintaining the food quality and safety. Moreover, retailers increasingly request fresh produce with the amounts of pesticides largely below the official maximum residue levels. Basic substances are relatively novel compounds that can be used in plant protection without neurotoxic or immune-toxic effects and are still poorly known by phytosanitary consultants (plant doctors), researchers, growers, consumers, and decision makers. The focus of this review is to provide updated information about 24 basic substances currently approved in the EU and to summarize in a single document their properties and instructions for users. Most of these substances have a fungicidal activity (calcium hydroxide, chitosan, chitosan hydrochloride, Equisetum arvense L., hydrogen peroxide, lecithins, cow milk, mustard seed powder, Salix spp., sunflower oil, sodium chloride, sodium hydrogen carbonate, Urtica spp., vinegar, and whey). Considering the increasing requests from consumers of fruits and vegetables for high quality with no or a reduced amount of pesticide residues, basic substances can complement and, at times, replace the application of synthetic pesticides with benefits for users and for consumers. Large-scale trials are important to design the best dosage and strategies for the application of basic substances against pathogens and pests in different growing environments and contexts.     

Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight

Two very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe₃)₂}₂)₂⋅C₇H₈] and the heteroleptic [{LO^NO4}BaOB{CH(SiMe₃)₂}₂] stabilised by the multidentate aminoetherphenolate {LO^NO4}⁻, are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe₃)₂}₂)₂⋅C₇H₈] shows, in particular, resilient η⁶-coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe₃)₂}₂⋅thf₂] and [Ba{N(SiMe₃)₂}₂]₂, this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R₂BOH and hydrosilanes HSiR′₃, yielding borasiloxanes R₂BOSiR′₃ in a controlled fashion. The assessment of substrate scope indicates that, for now, the reaction is limited to bulky borinic acids. Kinetic analysis shows that the rate-limiting step of the catalytic manifold traverses a dinuclear transition state. A detailed mechanistic scenario is proposed on the basis of DFT computations, the results of which are fully consistent with experimental data. It consists of a stepwise process with rate-determining nucleophilic attack of a metal-bound O-atom onto the incoming hydrosilane, involving throughout dinuclear catalytically active species.     

N-Boc-Amides in Cross-Coupling Reactions

Since 2015, the use of amides as electrophilic partners in cross-coupling reactions has experienced exponential growth. Diverse amide derivatives have been studied and among them N-Boc-amides have shown good activities towards various cross-coupling reactions and presents, in our view, an important synthetic usefulness. This review describes the recent developments of these chemical transformations involving N-Boc-amides.     

When a Red–NIR-Emissive Cs2[Mo6Br14] Interacts with an Active Diureasil–PEO Matrix: Design of Tunable and White-Light-Emitting Hybrid Material

Hybrid materials that combine diureasil matrices and octahedral molybdenum clusters have been synthesized to design lead-, cadmium- and rare-earth-free emitters for lighting or optoelectronic applications. This association leads to homogeneous and stable hybrids, for which the emission color can be tailored in the entire visible range, including white light; this is thanks to effective energy transfers from the host to the nanocluster.     

Accelerating the development of phase-change random access memory with in-fab plasma profiling time-of-flight mass spectrometry

We demonstrate the potential of using plasma profiling time-of-flight mass spectrometry (PP-TOFMS) to accelerate process developments for phase-change random access memory (PCRAM) applications, which require advanced materials with composition-driven properties. We assess the performances of PP-TOFMS for the chemical depth-profiling of GeSbTe phase change materials, first after deposition steps to investigate the top surface layer and the incorporation of silicon into the amorphous matrix, then after the thermal annealing step to refine in situ capping strategies, and finally in close loop with etching process steps. Comparison of reference-free semiquantitative PP-TOFMS analysis based on ion beam ratio with Rutherford backscattering spectrometry shows remarkable agreement (~10% relative). PP-TOFMS proves to be a fast screening tool, which allows process monitoring and selection of samples that indeed need more complex analysis.     

Balancing Ligand Flexibility versus Rigidity for the Stepwise Self-Assembly of M12L24 via M6L12 Metal–Organic Cages

Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd²⁺. As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M₂( L1 )₄, M₆( L2 )₁₂, and M₁₂( L2 )₂₄ cages. By controlling the self-assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen-bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests.     

On the diophantine equation (x − 1)(y − 1) = (z − 1)

Let k ≥ 3 be an integer. We study the possible existence of pairs of distinct positive integers (a, b) such that any of the three numbers a + 1, b + 1, and ab + 1 is a k-th power. We further investigate several related questions.     

Selective Encapsulation of Disaccharide Xylobiose by an Aromatic Foldamer Helical Capsule

Xylobiose sequestration in a helical aromatic oligoamide capsule was evidenced by circular dichroism, NMR spectroscopy, and crystallography. The preparation of the 5 kDa oligoamide sequence was made possible by the transient use of acid‐labile dimethoxybenzyl tertiary amide substituents that disrupt helical folding and prevent double helix formation. Binding of other disaccharides was not detected. Crystallographic data revealed a complex composed of a d ‐xylobiose α anomer and two water molecules accommodated in the right‐handed helix. The disaccharide was found to adopt an unusual all‐axial compact conformation. A dense network of 18 hydrogen bonds forms between the guest, the cavity wall, and the two water molecules.