Browse Articles

Spontaneous Intracellular Formation of Covalent Organic Frameworks via Enzyme-Initiated Cascade Reactions to Boost Cancer Radiotherapy

Mixed Nd ^4+/3+ and Cluster Magnetism in Hexagonal Perovskite 12R-Ba ₄ NdMn ₃ O _12−γ

Narrow-Bandgap Zero-Dimensional Chiral Hybrid Perovskites

Multiresponsive Isotropic Structural Color in Cholesteric Liquid Crystals

Unmasking DNA Resonances by Suppression of Hyperpolarized Water

Sulfilimines Are Azide Alternatives for Nitrene-Mediated Aromatic C-to-N Transmutation

Tuning Core Fluidity in Emulsion Nanoparticles for Stable and Transition-Metal-Free Responsive ¹⁹ F MRI Probes

Chemoselective Coordination–Insertion Polymerization of Cyclic Carbamates to Circular Polyurethanes with Diverse Architectures

Remarkable Effect of Electric Field Direction on Electrothermally Catalytic Selective Oxidation of (Meth)acrolein over a Heteropolyacid

Bis-hydroxylation of Homocitrulline Catalyzed by a Multinuclear Nonheme Iron Oxidative Enzyme during RiPP Biosynthesis

Macrocyclic Dual‐ and Tetra‐Borated Multi‐Resonance Thermally Activated Delayed Fluorescence Materials Based on Tetraazacyclophane

ABSTRACT In multiple‐resonance‐induced thermally activated delayed fluorescence (MR‐TADF) materials with a meta B‐π‐B configuration, most studies mainly focused on linear multi‐boron frameworks. In this study, we report two macrocyclic dual‐ and tetra‐borated MR‐TADF materials based on tetraazacyclophane (DPN2B and DPN4B). By rationally selecting boron sources and reaction conditions, one‐pot double and quadruple borylation reactions were achieved. In toluene, DPN2B and DPN4B exhibit deep blue narrowband emission peaking at 451 and 442 nm, with full widths at half maximum of 22 and 25 nm, respectively. Solution‐processed organic light‐emitting diodes (OLEDs) based on DPN2B and DPN4B show pure‐blue electroluminescence with peaks at 458 and 452 nm, with maximum external quantum efficiencies of 6.4% and 4.0%, respectively. The DPN2B‐based device achieves Commission Internationale de l’Éclairage coordinates of (0.14 and 0.07). This work provides a practical macrocyclic molecular design strategy for developing multi‐borated MR‐TADF emitters and OLEDs.

Predicting Catalyst Performance From Pt/CeO ₂ Redispersion Kinetics

ABSTRACT Quantitative description of the structural dynamics of nanoparticles by kinetic data is challenging but would represent a significant knowledge leap, as this would enable the forecast of their properties, e.g., in catalysis. A striking example in catalysis is the redispersion of Pt nanoparticles into single atoms in Pt/CeO 2 ‐based catalysts. In this work, we combined environmental transmission electron microscopy (ETEM) measurements with catalytic data to monitor the individual decay of Pt nanoparticles on defined CeO 2 nanocubes. Supported by density functional theory modeling, this provides unprecedented insight into their dynamic behavior, including kinetics. We observed that the rate of noble metal redispersion is strongly dependent on the local structural environment: the presence of other nearby nanoparticles and heterogeneities on the CeO 2 surface reduced the redispersion rate. Independent of the initial particle size and local environment, the particle volume decreases linearly in time, indicating a constant flux of Pt atoms from the nanoparticles. These findings at the atomic scale were correlated to the observed changes in the integral catalytic performance, allowing a first prediction of the catalyst activity based on the redispersion process and demonstrating how atomic‐scale kinetic insights can be correlated to macroscopic effects.

Catalytic C–F Bond Activation at Room Temperature: Enolate Cross‐Couplings Enabled by [Pd(1‐MeNAP)TFA] ₂ and LiHMDS

ABSTRACT Due to their exceptional stability, only few transition metal catalysts are capable of activating C─F bonds for C–C‐coupling reactions, usually under harsh conditions or with highly reactive nucleophiles. We herein report that a methyl naphthyl (MeNAP) palladium trifluoroacetate/ t BuBrettPhos catalyst with lithium bis(trimethylsilyl)amide (LiHMDS) as the base enables α‐arylations of in situ generated enolates with non‐activated aryl fluorides. The reaction proceeds under mild conditions at room temperature and extends to ketone, ester, nitrile, and even amide enolates. DFT calculations reveal that the coordination of lithium salts to the fluorine atom decisively facilitates the insertion of Pd into the C─F bond, explaining why this so far elusive reaction is now possible at such exceptionally mild conditions.

Water Is Not Universally Promotional: Size‐Dependent Inversion of Water Effects in Methanol Steam Reforming

ABSTRACT Water is widely assumed to be universally promotional in methanol steam reforming. Here, we show that this assumption fails when metal nuclearity and support hydroxyl chemistry are considered. Using a well‐defined set of Pt single‐atom and nanoparticle catalysts supported on hydroxyl‐rich CeO 2 and hydroxyl‐poor Al 2 O 3 , we uncover a striking, size‐dependent inversion of water effects. On CeO 2 ‐supported Pt nanoparticles, water activation generates surface hydroxyls that withdraw electron density from Pt, weaken CO adsorption and alleviate CO poisoning, thereby enhancing activity. In contrast, the same hydroxyl species inhibit methanol conversion on single‐atom Pt by competing for adsorption sites and stabilizing kinetically trapped formate intermediates. These opposing effects vanish on Al 2 O 3 , where water activation is limited. This size‐dependent inversion extends to other single‐atom catalysts and reducible supports (e.g., Pd 1 /CeO 2 , Rh 1 /CeO 2 ), confirming its generality and establishing a predictive framework for understanding and controlling water effects in reforming catalysis.

Factors associated with lymphedema after breast cancer surgery: a cross-sectional comparative study from Yazd, Iran

Additive‐Free, Efficient, and Stable All‐Polymer Solar Cells Enabled by Congeneric Molecule Construction for Integrated Solar‐Storage Applications

ABSTRACT Organic solar cells are attractive for wearable electronics, in particular, all‐polymer solar cells (all‐PSCs) offer superior intrinsic stability and higher output voltage, enabling direct matching with the energy storage and conversion systems. However, all‐PSCs typically suffer from disordered morphology and poor donor–acceptor compatibility, requiring processing additives that compromise long‐term stability. Here, we introduce a structural homology strategy, using donor and acceptor polymers that share the same bithiophene imide building block, to eliminate the need for additives. This design strengthens intermolecular interactions, enhances molecular ordering, and suppresses energy loss, yielding an open‐circuit voltage of 0.94 V, a 12% improvement over the benchmark PM6:Y6 system. The chemical homology also reduces the Flory–Huggins interaction parameter and improves donor–acceptor compatibility, allowing the active layer to spontaneously form an ideal nanoscale fibrillar interpenetrating network. The resulting additive‐free all‐PSCs achieve a record power conversion efficiency of 19.12%, together with exceptional thermal stability ( T 80   =  1128 h), photostability ( T 80   = 756 h), and mechanical robustness. By integrating a 70 cm 2 large‐area all‐polymer module with series‐connected zinc–air batteries, we demonstrate a self‐sustaining, solar‐rechargeable system that delivers continuous power under both illumination and darkness, offering a practical pathway for next‐generation flexible and wearable electronics.

Longitudinal digital speech assessment in progressive supranuclear palsy

Supramolecular Polymer‐Surfactant Co‐Assemblies for Multivalent HSV‐1 Inhibition

ABSTRACT Supramolecular assemblies are of fundamental importance for cellular life and bio‐interactive materials. The structure and function of these assemblies are decisively influenced by the design of their molecular components. In this work, we present a modular synthetic strategy for six novel bio‐functional surfactants with a sulfonate headgroup (termed SupraVir surfactants). These amphiphilic molecules were designed for strong interactions with viral envelope proteins, virus inhibition, and to co‐assemble water‐soluble benzene‐1,3,5‐tricarboxamide derivatives (BTAs) to generate surfactant‐grafted supramolecular polymers. Systematic spectroscopic and microscopic studies showed that the morphology of the co‐assemblies strongly depends on the surfactant‐BTA ratio. At surfactant ratios higher than 1, the native BTA nanofibers were disrupted, resulting in micellar architectures. In the test with herpes simplex virus (HSV‐1), fibrous supramolecular polymers show significantly lower half‐maximal inhibitory concentrations (IC 50 ) compared to the corresponding micellar aggregates of the pure surfactants. Interestingly, the co‐assemblies exhibited lower cytotoxicity than the functional surfactants alone, probably due to their structured incorporation into the polymeric scaffold. The dynamics of the co‐assemblies, probed by hydrogen‐deuterium exchange mass spectrometry (HDX‐MS), showed correlations to the effectiveness. These results demonstrate a new co‐assembly strategy of functional positioning antiviral surfactants in supramolecular scaffolds for the development of multivalent antiviral materials.

Gender and aridity drive essential oil chemodiversity in Tunisian Pistacia lentiscus for tailored bioresource valorisation

Abstract The essential oil composition of Tunisian female and male Pistacia lentiscus leaves from semi-arid to arid bioclimates was investigated across three phenological stages using gas chromatography-mass spectrometry-flame ionization detection (GC-MS/FID). Monoterpene hydrocarbons (44.67–60.59%) and sesquiterpene hydrocarbons (8.18–29.72%) were dominant, with limonene, sabinene, α- and β-pinene, terpinen-4-ol, germacrene D, γ-terpinene and β-caryophyllene as major components. Principal component analysis (PCA) revealed significant chemical differentiation based on plant gender and climatic factors. Male samples showed higher α-pinene and β-pinene content while female samples were enriched in limonene and germacrene D. Semi-arid male samples contained more sabinene, terpinene-4-ol and γ-terpinene than the arid samples. Female specimens from semi-arid zone accumulated higher limonene than arid counterparts. Phenological stage had minor effects. Our study provides three novel findings: (1) We examined sex, climate, and phenology together for the first time. (2) Aridity drives a clear chemotype shift in males—semi-arid males produce sabinene/terpinen-4-ol, arid males produce α/β-pinene. (3) In females, aridity causes a 3- to 10-fold limonene reduction while sesquiterpenes persist, revealing a metabolic trade-off. These findings advance understanding of how this Mediterranean shrub adjusts its chemistry to climate and provide a basis for sex- and climate-based harvesting of tailored essential oils.

Palladium‐Catalyzed Annulations of an Anti‐Bredt Olefin

ABSTRACT A famous class of alkene‐containing compounds that have intrigued chemists for more than a century are anti‐Bredt olefins (ABOs). ABOs are a subclass of bridgehead alkenes that reside in small ring systems, thus rendering them unstable and historically challenging to leverage in chemical synthesis. The present study describes metal catalyzed reactions of a [2.2.1]‐bridged bicyclic ABO, wherein two in situ‐generated species, both present in low concentration and generated transiently, undergo a productive reaction. The transformation uses palladium catalysis to unite the aforementioned ABO with indole‐based trapping partners, thus delivering unusual heterocyclic products. The scope of the reaction is reported, as well as computations concerning the putative Pd‐bound ABO species. The latter suggests that the short‐lived ABO is stabilized by Pd via the energetically favorable formation of an intermediate palladacycle. This methodology is expected to prompt the further development of unconventional reactions, including metal‐catalyzed processes of ABOs and other transient olefins.