Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces.

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts' functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment.

Bridging the gap: RNAylation conjugates RNAs to proteins.

In nature, the majority of known RNA-protein interactions are transient. Our recent study has depicted a novel mechanism known as RNAylation, which covalently links proteins and RNAs. This novel modification bridges the realms of RNA and protein modifications.

Utilization of a Branched Late-Stage Clickable Biotinylated Chassis on the Example of a Pittsburgh B Analogue.

Biotinylation is probably the most frequent and practically useful modification of molecules to facilitate selective and highly affine binding to (strept)avidin for immobilization, enrichment, and purification for further (bio)chemical or (bio)physical investigations. We present a protecting-group-free synthesis of a branched biotin bis-azide that enables dual-payload late-stage functionalization with arbitrary alkynes via click chemistry. Utility of the chassis is briefly showcased on the example of a valuable Pittsburgh B analogue, which binds pathological protein aggregates, commonly found in neurodegenerative diseases.

Space charge governs the kinetics of metal exsolution.

Nanostructured composite electrode materials play a major role in the fields of catalysis and electrochemistry. The self-assembly of metallic nanoparticles on oxide supports via metal exsolution relies on the transport of reducible dopants towards the perovskite surface to provide accessible catalytic centres at the solid-gas interface. At surfaces and interfaces, however, strong electrostatic gradients and space charges typically control the properties of oxides.

A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation.

High-entropy materials are an emerging pathway in the development of high-activity (electro)catalysts because of the inherent tunability and coexistence of multiple potential active sites, which may lead to earth-abundant catalyst materials for energy-efficient electrochemical energy storage. In this report, we identify how the multication composition in high-entropy perovskite oxides (HEO) contributes to high catalytic activity for the oxygen evolution reaction (OER), i.e.

Atomistic Insights into Activation and Degradation of LaSrCoO Electrocatalysts under Oxygen Evolution Conditions.

The stability of perovskite oxide catalysts for the oxygen evolution reaction (OER) plays a critical role in their applicability in water splitting concepts. Decomposition of perovskite oxides under applied potential is typically linked to cation leaching and amorphization of the material. However, structural changes and phase transformations at the catalyst surface were also shown to govern the activity of several perovskite electrocatalysts under applied potential.

Discovery of Inhibitors of DNA Methyltransferase 2, an Epitranscriptomic Modulator and Potential Target for Cancer Treatment.

Selective manipulation of the epitranscriptome could be beneficial for the treatment of cancer and also broaden the understanding of epigenetic inheritance. Inhibitors of the tRNA methyltransferase DNMT2, the enzyme catalyzing the -adenosylmethionine-dependent methylation of cytidine 38 to 5-methylcytidine, were designed, synthesized, and analyzed for their enzyme-binding and -inhibiting properties. For rapid screening of potential DNMT2 binders, a microscale thermophoresis assay was established.

Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis.

The oxygen evolution reaction (OER) is one of the key kinetically limiting half reactions in electrochemical energy conversion. Model epitaxial catalysts have emerged as a platform to identify structure-function-relationships at the atomic level, a prerequisite to establish advanced catalyst design rules. Previous work identified an inverse relationship between activity and the stability of noble metal and oxide OER catalysts in both acidic and alkaline environments: The most active catalysts for the anodic OER are chemically unstable under reaction conditions leading to fast catalyst dissolution or amorphization, while the most stable catalysts lack sufficient activity.

Evolution of surface and sub-surface morphology and chemical state of exsolved Ni nanoparticles.

Nanoparticle formation by dopant exsolution (migration) from bulk host lattices is a promising approach to generate highly stable nanoparticles with tunable size, shape, and distribution. We investigated Ni dopant migration from strontium titanate (STO) lattices, forming metallic Ni nanoparticles at STO surfaces. scanning probe measurements confirmed the presence of nanoparticles at the H treated surface.

Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysis.

The Co-O covalency in perovskite oxide cobaltites such as LaSrCoO is believed to impact the electrocatalytic activity during electrochemical water splitting at the anode where the oxygen evolution reaction (OER) takes place. Additionally, space charge layers through band bending at the interface to the electrolyte may affect the electron transfer into the electrode, complicating the analysis and identification of true OER activity descriptors. Here, we separate the influence of covalency and band bending in hybrid epitaxial bilayer structures of highly OER-active LaSrCoO and undoped and less-active LaCoO.

Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions.

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La Sr MnO epitaxial thin films, both at the surface and throughout the bulk.

Exsolution of Embedded Nanoparticles in Defect Engineered Perovskite Layers.

Exsolution phenomena are highly debated as efficient synthesis routes for nanostructured composite electrode materials for the application in solid oxide cells (SOCs) and the development of next-generation electrochemical devices for energy conversion. Utilizing the instability of perovskite oxides, doped with electrocatalytically active elements, highly dispersed nanoparticles can be prepared at the perovskite surface under the influence of a reducing heat treatment. For the systematic study of the mechanistic processes governing metal exsolution, epitaxial SrTiNbNiO thin films of well-defined stoichiometry are synthesized and employed as model systems to investigate the interplay of defect structures and exsolution behavior.

Pyocin S5 Import into Pseudomonas aeruginosa Reveals a Generic Mode of Bacteriocin Transport.

Pyocin S5 (PyoS5) is a potent protein bacteriocin that eradicates the human pathogen in animal infection models, but its import mechanism is poorly understood. Here, using crystallography, biophysical and biochemical analyses, and live-cell imaging, we define the entry process of PyoS5 and reveal links to the transport mechanisms of other bacteriocins. In addition to its C-terminal pore-forming domain, elongated PyoS5 comprises two novel tandemly repeated kinked 3-helix bundle domains that structure-based alignments identify as key import domains in other pyocins.