Accessing carbon, boron and germanium spiro stereocentres in a unified catalytic enantioselective approach.

Achieving substrate generality in asymmetric catalysis remains a long-standing goal, particularly for the selective construction of chiral heteroatoms. Compared with carbon, sulfur, phosphorus and silicon stereogenic centres, methods for the construction of their boron and germanium congeners remain very scarce. Chiral (hetero) spirocycles are of relevance in several research domains.

Broadband transient full-Stokes luminescence spectroscopy.

Materials emitting circularly polarized light (CPL) are highly sought after for applications ranging from efficient displays to quantum information technologies. However, established methods for time-resolved CPL (TRCPL) characterization have notable limitations, generally requiring a compromise between sensitivity, accessible timescales and spectral information. This has limited the acquisition of in-depth photophysical insight necessary for materials development.

Screening macrocyclic peptide libraries by yeast display allows control of selection process and affinity ranking.

Macrocyclic peptides represent an attractive drug modality due to their favourable properties and amenability to in vitro evolution techniques such as phage or mRNA display. Although very powerful, these technologies are not without limitations. In this work, we address some of their drawbacks by developing a yeast display-based strategy to generate, screen and characterise structurally diverse disulfide-cyclised peptides.

Rethinking chemical research in the age of large language models.

Large language models (LLMs) offer opportunities for advancing chemical research, including planning, optimization, data analysis, automation and knowledge management. Deploying LLMs in active environments, where they interact with tools and data, can greatly enhance their capabilities. However, challenges remain in evaluating their performance and addressing ethical issues such as reproducibility, data privacy and bias.

Deep Eutectic Solvents Formed by Complex Hydrides: A New Class of Hydrogen-Rich Liquid.

Deep eutectic solvents (DESs) are novel mixtures that exhibit a significant depression in melting points compared to their individual components. This work finds that combining tetrabutylammonium borohydride (TBABH) with ammonia borane (AB) yields new, stable, hydrogen-rich liquids under ambient conditions, with a glass transition as low as -50 °C. Liquid mixtures containing up to 6.

Single-Layer and Stack Dielectric Elastomer Actuators Using Polysiloxanes Modified with Ethylsulfonyl Groups.

Dielectric elastomer actuators (DEAs) are soft transducers well-suited to precise motion applications in robotics and prosthetics. However, low dielectric permittivity or very soft elastomers result in a high operating voltage or low force output. These issues can be mitigated using high dielectric permittivity elastomers in a stack actuator.

CO Adsorption Dynamics during CO Electrolysis in Aprotic Organic Electrolytes.

Carbon dioxide electrolysis (COE) in fully aprotic organic electrolytes primarily yields oxalate (CO), carbon monoxide (CO), and carbonate (CO). To understand this system, we investigated the adsorption dynamics in the CO adsorption region (COAR) using attenuated total reflectance surface-enhanced infrared absorption spectroscopy on polycrystalline Cu in a DMSO/DMF-based electrolyte. A distinct vibrational feature at 2007 cm, emerged after the COE onset potential (-1.

Low-dose photodynamic therapy promotes vascular E-selectin expression in chest malignancies, improving immune infiltration and tumor control.

Background: Chest malignancies such as non-small cell lung cancer (NSCLC) or pleural mesothelioma (PM) have an ominous prognosis. Photodynamic therapy (PDT) of NSCLC and PM improves patient survival, but the precise underlying mechanism remains unknown. Here, we hypothesized that low-dose PDT (L-PDT) alters the expression of tumor endothelial cell adhesion molecules favoring immune cell recruitment and tumor control.

Enantioselective synthesis of 1,2-disubstituted thiocyclobutanes Michael addition.

We report the diastereoselective and enantioselective synthesis of thio-substituted cyclobutanes a sulfa-Michael addition using cyclobutenes. In the presence of DBU, various thio-cyclobutane esters and amides were obtained in up to quantitative yield and >95 : 5 dr. Using a chiral chinchona-based squaramide bifunctional acid-base catalyst and an -acyl-oxazolidinone-substituted cyclobutene, thio-cyclobutanes were obtained with high yield and enantioselectivity (er up to 99.

Supramolecular engineering in hybrid perovskite optoelectronics.

This review explores the emerging field of supramolecular engineering in hybrid organic-inorganic perovskite optoelectronics. The incorporation of supramolecular agents has shown transformative effects on the crystallization, morphology, stability, and performance of perovskite-based materials and devices. We systematically review the types of supramolecular interactions, mechanisms of supramolecular engineering crystallization, synthesis of perovskite quantum dots, and interface engineering advancements for device stability.

Enantioconvergent Cobalt-Catalyzed Hydroalkylation for the Construction of Fluoro, Chloro, and Trifluoromethyl Stereogenic Centers.

Organic compounds containing a chiral, halogenated aliphatic carbon center are useful in medicinal chemistry, but their enantioselective synthesis remains difficult. Here, we develop a general approach to access these compounds through cobalt-catalyzed hydroalkylation of allenes and alkenes with dihaloamides. The reactions of allenes and terminal alkenes lead to alkylation only at the terminal position.

Lithium-Mediated Ammonia Electrosynthesis over Orderly Arranged Dipoles Regulated Solid-Electrolyte Interphase.

The electrocatalytic lithium-mediated nitrogen reduction reaction (Li-NRR) is considered as a promising alternative to the energy-intensive Haber-Bosch route. However, the solid electrolyte interphase that is derived from the electrolyte easily hinders the diffusion and nucleation of Li, which ultimately suppresses N activation and the subsequent protonation process. Herein, we successfully construct surface oxygen vacancies (O) on commercial BaTiO (BTO) nanoparticles and further drive the phase transition from cubic/tetragonal to rhombohedral, which enhances the ferroelectricity of O-enriched BaTiO (BTOV) and produces orderly arranged dipoles.

Dopamine Dopes the Performance of Perovskite Solar Cells.

The electron transport layer (ETL) is a crucial component of perovskite solar cells (PSCs) as it greatly influences their photovoltaic performance. Among various currently used ETL materials, SnO₂ stands out due to its unique advantages, including low-temperature fabrication and rapid electron extraction capability and excellent energy match of its conduction band edge with that of the commonly used perovskite formulations. However, the currently employed SnO₂ layers contain surface defects, such as hydroxyl groups and oxygen vacancies that impair the desired growth of highly crystalline and defect less perovskite films during solution processing of n-i-p type PSCs reducing their power conversion efficiency (PCE) and stability.

The HP1 box of KAP1 organizes HP1α for silencing of endogenous retroviral elements in embryonic stem cells.

Repression of endogenous retroviral elements (ERVs) is facilitated by KAP1 (KRAB-associated protein 1)-containing complexes, however the underlying mechanism remains unclear. Here, we show that binding of KAP1 to the major component of the heterochromatin spreading and maintenance network, HP1α, plays a critical role in silencing of repetitive elements. Structural, biochemical and mutagenesis studies demonstrate that the association of the HP1 box of KAP1 (KAP1) with the chromoshadow domain of HP1α (HP1α) leads to a symmetrical arrangement of HP1α and multimerization that may promote the closed state of chromatin.

Active Passivation Charge Transport in n-i-p Perovskite Solar Cells Approaching 26% Efficiency.

In n-i-p planar perovskite solar cells (PSCs), the electron transport layer (ETL) and the hole transporting layer play a crucial role in realizing high power conversion efficiency (PCE). Herein, a TiO-SDBA-SnO stacked ETL is reported, where 4,4'-sulfonyldibenzoic acid (SDBA) serves as an active passivation agent to suppress charge recombination and enhance interface quality. SDBA effectively passivates oxygen vacancies in sputtered TiO, while simultaneously promoting SnO nucleation and improving film quality.

Synthesis of Bicyclo[1.1.1]Pentane Z-Substituted Enamides, Enol Ethers, and Vinyl Sulfides Using Iodine (III) Reagents.

Bicyclo[1.1.1]pentanes (BCPs) are well-studied bioisosteres for para-substituted benzene rings, and numerous methods for synthesizing 1,3-difunctionalized BCPs have been developed.

Solar-driven Plastic Reforming With CO Conversion to Value-Added Chemicals Using Bifunctional Copper Hydroxide Catalyst.

During coupling with carbon dioxide reduction reactions (CO₂RR), plastic reforming as an effective alternative anodic reaction to replace oxygen evolution reaction (OER), offers dual benefits of reducing energy consumption and producing valuable chemicals. However, balancing the energy requirements of polyethylene terephthalate (PET) oxidation with CO₂RR is challenging, as both half-reactions must operate under compatible conditions for high efficiency. Here, it is developed a bifunctional copper hydroxide catalyst capable of simultaneously converting both PET and CO₂ into valuable chemicals, which simplifies the system complexity.

Phage Display Selection against a Mixture of Protein Targets.

Affinity selections by phage display or other display techniques are typically performed against single targets immobilized as a purified protein. In order to develop cross-specific binders that engage with multiple proteins, such as members of a related family, we herein propose to perform selections against mixtures of proteins as bait. Combined with follow-up selection rounds against the individual proteins, deep sequencing, and single clone enrichment analysis, we expected to distinguish binders that are cross-specific from those that are not.

The Chemical Nature of the Oxide Directs the Stability and Reactivity of Copper|Oxide Interfaces in the Electrochemical CO Reduction Reaction.

Understanding the impact of composition and interfaces between metals and oxides is a goal of interest for many chemical reactions. Herein, we propose a framework to map correlations between the electrochemical behavior of the oxide and the stability and reactivity of metal|oxide interfaces, exemplified by Cu|oxide for the electrochemical CO reduction reaction (CORR). Copper materials interfaced with metal oxides have emerged as promising CORR catalysts for selectivity toward multicarbon products, including alcohols; stability under operation has been reported for some of them.

Homochiral versus Racemic 2D Covalent Organic Frameworks.

The synthesis of homochiral two-dimensional covalent organic frameworks (2D COFs) from chiral π-conjugated building blocks is challenging, as chiral units often lead to misaligned stacking interactions. In this work, we introduce helical chirality into 2D COFs using configurationally stable enantiopure and racemic [5]helicenes as linkers in the backbone of 2D as powders and films. Through condensation with 1,3,5-triformylbenzene (TFB) or 1,3,5-triformylphloroglucinol (TFP), our approach enables the efficient formation of a set of homochiral and racemic 2D .

Encapsulated Co-Ni alloy boosts high-temperature CO electroreduction.

Electrochemical CO reduction into chemicals and fuels holds great promise for renewable energy storage and carbon recycling. Although high-temperature CO electroreduction in solid oxide electrolysis cells is industrially relevant, current catalysts have modest energy efficiency and a limited lifetime at high current densities, generally below 70% and 200 h, respectively, at 1 A cm and temperatures of 800 °C or higher. Here we develop an encapsulated Co-Ni alloy catalyst using SmO-doped CeO that exhibits an energy efficiency of 90% and a lifetime of more than 2,000 h at 1 A cm for high-temperature CO-to-CO conversion at 800 °C.

Carbamate-bond breaking on bulk oxides realizes highly efficient polyurethane depolymerization.

Polyurethane is a versatile plastic finding applications across diverse sectors ranging from construction to household products. Recently, there is growing interest in the chemical recycling of polyurethane via catalytic hydrogenation to recover anilines and polyols. However, examples of heterogeneous catalysts are lacking despite their practicality for scale-up to a commercially relevant level.

SPOCK Tool for Constructing Empirical Volcano Diagrams from Catalytic Data.

Volcano plots, stemming from the Sabatier principle, visualize descriptor-performance relationships, allowing rational catalyst design. Manually drawn volcanoes originating from experimental studies are potentially prone to human bias as no guidelines or metrics exist to quantify the goodness of fit. To address this limitation, we introduce a framework called SPOCK (systematic piecewise regression for volcanic kinetics) and validate it using experimental data from heterogeneous, homogeneous, and enzymatic catalysis to fit volcano-like relationships.

Metal Doping of Strongly Confined Halide Perovskite Nanocrystals under Ambient Conditions.

Halide perovskite nanocrystals are promising materials for optoelectronic applications. Metal doping provides an avenue to boost their performance further, e.g.