Browse Articles

Multipronged Protein Engagement by a Ruthenium(II) Sunitinib Hydrazide Complex Elicits ROS‐Independent Immunogenic Cell Death

ABSTRACT Metal‐based immunogenic cell death (ICD) inducers commonly rely on elevated reactive oxygen species (ROS) to trigger endoplasmic reticulum (ER) stress. The central regulator of inflammatory signaling, NF‐κB, can amplify oxidative stress responses and promote pro‐tumorigenic signaling. Thus, strategies that induce ICD independently of ROS may represent a conceptual shift from ROS‐driven paradigms. Here we show that using a hydrazide derivative of a clinical angiogenesis inhibitor sunitinib to form a Ru(II)–sunitinib hydrazide complex ( 5 ) inhibits NF‐κB signaling (reduced p65 phosphorylation and blocked p50–p65 nuclear translocation), suppresses VEGFR2 phosphorylation, and decreases telomerase activity (cell‐free TRAP assay), thereby redirecting cellular responses toward apoptotic ICD. The sunitinib hydrazide provides the VEGFR2 and telomerase inhibition properties but it also promotes NF‐κB (p50–p65) nuclear translocation and ROS generation. In contrast, the intracellular ROS levels remain largely unchanged with 5 which inhibits the NF‐κB pathway. Simultaneous inhibition of VEGFR2, NF‐κB, and telomerase enforces sustained non‐oxidative ER–mitochondrial stress, triggering DAMP release and apoptotic immunogenic cell death. Folate‐targeted PEG–PCL micellar delivery ( 5@PFC ) improves tumor selectivity fourfold and suppresses tumor growth in immunocompetent 4T1 mice, accompanied by an increased intratumoral CD4:CD8 ratio, indicating enhanced immune activation.

Precise Iodide‐Trap Strategy for Photothermally Stable Spiro‐OMeTAD‐Based Perovskite Solar Cells

ABSTRACT Photothermal stress induces irreversible iodide ion migration in perovskite solar cells (PVSCs) based on 2,2',7,7'‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9'‐spirobifluorene (spiro‐OMeTAD). Diffused iodide ions lead to weak physical interfacial contact and de‐doping of spiro‐OMeTAD, posing substantial challenges to photothermal stability. Here we present a dual iodide‐trap strategy to precisely trap mobile iodide ions, retaining high hole transport capacity in spiro‐OMeTAD and robust interfacial stability under photothermal stress. Specifically, 2,3,5,6‐tetrafluoro‐4‐iodobenzamide (TFIBA) is innovatively devised as an inhibitor to construct precise iodide ion traps on perovskite surfaces via directional halogen bonding. Moreover, (bis(trifluoroacetoxy)iodo)pentafluorobenzene (FPIFA) as an ideal dopant ensures rapid and controllable p‐doping of spiro‐OMeTAD without air assistance, with a byproduct providing an additional trap against iodide invasion. Consequently, the resulting device achieves an efficiency of 26.81% with T 93 lifetime over 1140 h under standard illumination at 85°C, representing one of the highest stabilities for spiro‐OMeTAD‐based PVSCs. These findings exhibit a viable route toward efficient and photothermally stable PVSCs for commercialization.

A Transiently Activated Rotaxane Mechanocatalyst

ABSTRACT The activation of a latent catalyst by mechanical force, upon impact or fatigue for example, offers great promise for the creation of self‐healing or stress‐reporting polymer materials. Until now, such mechanocatalysts have relied on the scission of a covalent bond to generate the desired catalytic species, a process generally irreversible or difficult to control. Here, we report a transient [2]rotaxane mechanocatalyst featuring a thiourea active site, whose catalytic activity can be readily switched on by mechanical force, while spontaneously returning to an inactive state in the absence of force. In solution, the catalytic efficiency remains undiminished after 5 cycles, marking the first example of a recyclable mechanocatalyst. Benefiting from the low activation force threshold required to rupture noncovalent interactions, the catalytic efficiency in the solid state is comparable to that observed in solution. Moreover, it catalyzes the ring‐opening polymerization of lactide in the solid state under simple compression without main chain degradation. Although the overall catalytic efficiency still needs further improvement, this new mechanocatalytic system shows its potential for the development of force‐responsive materials.

One‐Pot Conversion of Acridines Into Phototherapeutic Near‐Infrared Spirocyanines

ABSTRACT As near‐infrared (NIR) bio‐imaging and phototherapeutic agents, polymethine cyanines have disadvantages in optical properties due to the fast nonradiative transition. Herein, we reported a small‐sized and spirocycle‐fused trimethine acridinocyanine (SpiroCY) via one‐pot oxidative trimerization using oxygen as the oxidant. Theoretical calculations using the Automated Design of Chemical Reaction (ADCR) program elucidate the formation of the O 2 ‐derived hydroperoxyl radical (HO 2 • ) and demonstrate a radical cascade reaction (RCR) mechanism for spirocyanine synthesis. The spiro‐functionalization effect greatly reshapes the photophysical properties of the parent acridinocyanine by improving brightness and suppressing H‐aggregation due to the three‐dimensional architecture and enhanced rigidity, which allows for mitochondria‐targeted NIR‐I and NIR‐II cell imaging at a very low dose (10−100 nM); and switches the parent acridinocyanine into a potential antitumor drug and Type‐I photosensitizer generating superoxide anion radical (O 2 •− ) and hydroxyl radical ( • OH) under 808 nm light irradiation for efficient photodynamic therapy. This work provides a new insight for dye functionalization, adds mechanistic understandings of the spirocyclic effect, and paves a way for developing spiro dyes as unique NIR‐I and NIR‐II imaging and phototherapeutic agents.

Intergrowth Fluorite Slabs Modulate Interstitial Fluorine to Enhance Fluoride‐Ion Conductivity

ABSTRACT Layered fluorite‐type compounds are largely restricted to double‐layer ( n = 2) slabs, and thicker fluorite blocks remain difficult to stabilize and control. Among the few examples, MSnF 4 (M = Pb, Ba) with a quadruple layer exhibits high fluoride‐ion conductivity, yet its structural complexity obscures the atomistic ion transport mechanism. Here we report two intergrowth fluoroiodides, Sn 2 Pb 5 F 12 I 2 ( n = 3 + 4) and Sn 5 Pb 5 F 17 I 3 ( n = 3 + 4 + 3), in which triple and quadruple slabs are periodically intergrown and separated by iodine layers. Their fluoride‐ion conductivities were evaluated alongside those of double‐layer (PbFI), triple‐layer (Pb 2 BaF 5 I), and quadruple‐layer (Pb 4 F 7 I) fluoroiodides. While conductivity increases monotonically with slab thickness in the simple layered series, the intergrowth phases outperform Pb 4 F 7 I with quadruple layers despite incorporating less conductive triple layers. Sn 2 Pb 5 F 12 I 2 and Sn 5 Pb 5 F 17 I 3 exhibit room‐temperature conductivities of ∼0.8 × 10 −3 and ∼0.2 × 10 −3 S cm– 1 , respectively. This enhancement is associated with modulation of octahedral‐site occupancy enabled by intergrowth stacking, which tunes interstitial‐fluorine concentration without aliovalent cation substitution, thereby avoiding detrimental dopant–carrier interactions. These results establish fluorite‐slab thickness and intergrowth stacking as a unified, doping‐free structural strategy to control anion‐carrier density and ion mobility in layered fluorite materials.

Co‐Localization‐Gated Multivalent DNA Logic Gate for Programmable Cell Recognition

ABSTRACT Achieving precise and robust cell‐surface recognition in complex biological environments is challenging due to inherent trade‐offs in affinity, specificity, and off‐target binding. Herein, we present a programmable molecular device that integrates Boolean logic computation with spatial confinement to overcome these limitations. Our system employs valence‐controllable, split DNAzyme modules assembled on a tetrahedral DNA nanostructure (TDN). The peroxidase‐mimicking activity is stringently gated by a cell‐surface AND logic, requiring the co‐localization of two adjacent modules on target protein clusters for activation. This spatial constraint effectively eliminates stochastic or unintended signal leakage originating from solution‐phase reactions or nontarget cells. Upon activation, the DNAzyme catalyzes the biotinylation of neighboring membrane protein clusters, generating stable multivalent adhesion sites. Quantitative dissociation kinetics reveal that the trivalent design of the DNAzyme modules promotes highly cooperative binding, resulting in uniform, long‐lived complexes on target cells. We demonstrate that this approach enables specific recognition and highly efficient isolation of target cells from mixed cell populations and clinical samples, showcasing a strategy for programming high‐fidelity molecular interactions on interested cell surfaces.

Cationic Microenvironment Enhancing Covalent Organic Frameworks for Electrocatalytic CO ₂ to CH ₄ Conversion

ABSTRACT Electrocatalytic reduction of CO 2 to CH 4 is hindered by sluggish proton‐coupled electron transfer kinetics and competing reaction pathways. Herein, we introduce a cationic microenvironment strategy that integrates reactant enrichment, proton regulation, and intermediate stabilization within a single framework. A tetra‐alkylammonium cation‐functionalized copper porphyrin covalent organic framework (Cu‐Tph‐COF‐N + ) achieves a CH 4 Faradaic efficiency of 66.8% at −1.2 V versus RHE, together with markedly enhanced turnover frequency and partial current density relative to its hydroxyl‐functionalized analogue. Mechanistically, the cationic framework generates a localized electrostatic field that concentrates CO 2 near active sites through charge‐dipole interactions while cooperatively interacting with hydrated K + ions to modulate proton transfer, thereby suppressing hydrogen evolution without compromising proton availability. The resulting electronic modulation at Cu porphyrin stabilizes key *COOH and *CHO intermediates and facilitates C–H bond formation, as supported by theoretical calculations and in situ spectroscopy. This work highlights cationic microenvironment engineering as a concise and general strategy to steer multi‐step CO 2 electroreduction toward deep reduction products.

Dual Lewis Acid Sites Enabling Passivation‐Resistant Sulfur Oxidation Coupled Hydrogen Evolution Reaction

ABSTRACT The coupling of the sulfide oxidation reaction (SOR) with the hydrogen evolution reaction (HER) is a promising approach for energy‐saving hydrogen production and sulfide‐containing wastewater treatment. However, transition metal‐based catalysts suffer from sluggish kinetics and sulfur passivation at high current densities. Herein, an oxygen‐coordinated iridium single‐atom anchored on a nickel surface (Ir 1 O‐Ni/C) is designed to generate adjacent dual Lewis‐acid sites, thereby constructing a species‐selective catalytic surface. Mechanistic analysis reveals that the dual Lewis acid sites polarize interfacial water, reconstructing hydrogen bonding networks to promote water supply and enhancing their dissociation for HER, while strong Lewis acid−base interactions expedite the adsorption and conversion of sulfide ions during SOR. Meanwhile, the electron‐deficient Ni alleviates the excessive adsorption of neutral S 8 * and H*, thereby suppressing sulfur accumulation and accelerating hydrogen release. The optimized Ir 1 O‐Ni/C catalyst achieves a current density of 1 A cm −2 at an overpotential of 280 mV for HER, and requires only 0.67 V to deliver 500 mA cm −2 for SOR, with stable flow cell operation for over 50 h. The versatility of the approach is demonstrated by Ru/Pt x O‐Ni/C, which all show improved activity compared with the conventional Ni/C catalysts, providing atomic‐level insights into the development of bifunctional catalytic systems.

Carbon‐Confined Fe ₃ C/Fe ₃ N Janus Interfaces for Selective Nitric Oxide‐to‐Ammonia Electroreduction

ABSTRACT Electrocatalytic nitric oxide reduction to ammonia couples pollutant valorization with sustainable nitrogen conversion, but high activity and selectivity require concurrent control of NO transport, NO activation, and hydrogenation at the gas‐liquid‐solid interface. Here, we report a self‐supported, noble‐metal‐free Fe 3 C/Fe 3 N@C catalyst, composed of earth‐abundant Fe, C, and N, featuring defect‐rich Fe 3 C/Fe 3 N Janus nanostructures confined within graphitic carbon. The catalyst achieves an NH 3 yield rate of 468.3 µmol h −1 cm −2 with a Faradaic efficiency of 94.2% at −0.6 V versus RHE, placing it among the most efficient reported NORR electrocatalysts. Mechanistic studies reveal that the graphitic carbon shell facilitates NO diffusion by alleviating the steric and dynamic constraints imposed by the hydrogen‐bonded water network. At the Janus interface, Fe 3 C sites preferentially adsorb and activate NO, whereas nitrogen‐vacancy‐rich Fe 3 N sites promote H 2 O dissociation to supply reactive *H for subsequent hydrogenation. This spatial coupling of mass‐transfer promotion, NO activation, and interfacial *H generation enables efficient and selective NO‐to‐NH 3 electroreduction. These findings establish carbon‐confined, earth‐abundant carbide/nitride Janus interfaces as a promising design principle for high‐performance NORR catalysts.

Acceptor‐Doped Cerium Oxides Enabling Metallic Nanocatalyst Exsolution for Hydrogen Production From Ammonia

ABSTRACT The development of advanced catalysts with enhanced activity and durability is essential for driving sustainable hydrogen production through ammonia cracking. In this sense, exsolution has gained prominence for generating stable and active nanoparticles socketed into the oxide support with high resistance to sintering. However, challenges remain in expanding these methods to CeO 2 ‐based systems due to the limited solubility of transition metals in fluorite oxides. Here, it is demonstrated that incorporating Gd into the CeO 2 lattice enhances the successful dissolution of Ru and Rh, promoting the exsolution of highly dispersed metallic nanoparticles (∼3 nm), including RuRh alloys. The resulting Ru‐exsolved@Ce 0.8 Gd 0.2 O 2‐δ catalyst exhibits remarkable catalytic activity and long‐term stability in ammonia decomposition for 260 h, outperforming Ru‐impregnated catalysts. In addition, benchmarking against literature values demonstrates that the Ru‐exsolved@Ce 0.8 Gd 0.2 O 2‐δ are among the most active catalysts at 400 °C. This work highlights the potential of lattice modification of CeO 2 ‐based catalytic supports via acceptor doping, resulting in significant metal‐exsolution dispersion and remarkably active catalysts for hydrogen generation via ammonia decomposition, with potential applications that can be expanded to other (electro)catalytic systems.

A High‐Voltage Membrane‐Free Li–Organic Hybrid Flow Battery Using Eutectic Lithium Chemistry

ABSTRACT Membrane‐free redox flow batteries offer simplified design and reduced cost, but their electrochemical performance remains limited. Here, a high‐voltage nonaqueous membrane‐free Li–organic hybrid flow battery was constructed using a biphasic electrolyte. The bottom‐phase anolyte is a deep eutectic solvent formed by lithium hexafluorophosphate and 2,2,2‐trifluoroacetamide, which provides a wide electrochemical stability window of 4.81 V, low viscosity of 13.8 cP, high ionic conductivity of 8.59 mS·cm −1 , and stable compatibility with lithium metal. The top‐phase catholyte is dichloromethane containing a long‐alkyl‐chain phenothiazine derivative, which exhibits excellent redox reversibility and strict confinement in the upper phase. The biphasic system achieved an open‐circuit voltage of approximately 3.6 V and stable operation at 0.5 M concentration, retaining 85.6% of theoretical capacity with a Coulombic efficiency of 97.6% after 100 cycles. In flow configuration, the 0.5 M battery maintained over 92% capacity after 10 days of continuous cycling with minimal self‐discharge. A preliminary cost estimation yielded $134.8 kWh −1 , which is lower than vanadium redox flow batteries, and both electrolyte phases displayed strong flame resistance. This study provides a viable design strategy to enable membrane‐free nonaqueous Li–organic hybrid flow battery by leveraging eutectic lithium chemistry and immiscible solvent interfaces.

Structural and Functional Siderophore Remodeling by Enzymatic Delipidation

ABSTRACT Bacteria employ specialized metabolites called siderophores to acquire scarce iron, but these molecules may serve additional ecological roles. Here, we reveal that Pandoraea species, including environmental isolates and opportunistic pathogens typically acquired from the environment, produce bifunctional lipopeptides that undergo enzymatic remodeling to switch from promoting bacterial motility to optimizing iron capture. Through genome mining and metabolic profiling, we discovered pandorachelins, diazeniumdiolate‐containing siderophores. Comprehensive NMR analysis, derivatization, and isotope labeling established that pandorachelin A is a head‐to‐tail‐fused homodetic cyclopeptide, revising a recently proposed structure. We identified the elusive biosynthetic precursor, pandorachelin B, as a lipocyclopeptide with a lactone moiety and N‐terminal fatty acid. A specialized acylase (PdnM) cleaves the lipid tail of pandorachelin B, triggering an O→N acyl shift that contracts the ring and transforms the biological function: the lipopeptide enables bacterial swarming through surfactant activity, while the delipidated product exhibits enhanced iron‐chelating capacity but no motility promotion. Genetic knockouts, enzyme reconstitution, and phenotypic assays confirm this maturation sequence. The functional switch correlates with ecological niche across Pandoraea species, revealing a sophisticated strategy for niche colonization and nutrient acquisition. These findings identify PdnM as a potential antivirulence target and expand the functional repertoire of bacterial siderophores.

Reversible Multiple Cation Storage in High‐Entropy MXenes for Durable Seawater Batteries

ABSTRACT Rechargeable seawater batteries (SWBs) offer compelling advantages for sustainable energy storage, owing to the natural abundance and intrinsic safety of seawater electrolytes. However, the presence of multiple cations in seawater poses challenges for the reversibility and stability of conventional storage materials. Herein, a high‐entropy strategy is introduced to unlock the electrochemical activity of MXenes toward multiple cations in seawater. Mechanistic studies reveal that the unique “cocktail effect” of high‐entropy MXene accelerates ion transport kinetics and stabilizes the layered structure, enabling reversible storage of monovalent (Na + , K + ) and divalent (Mg 2+ , Ca 2+ ) ions with zero‐strain characteristic. As a proof‐of‐concept, a novel SWB is constructed based on an MXene anode with multiple‐cation storage capability and a polytriphenylamine cathode with Cl − storage chemistry. This SWB achieves a high specific capacity of 155 mAh g −1 , excellent rate capability at 15 A g −1 , and impressive cycling durability over 11000 cycles at 25°C. Furthermore, this SWB functions even at −30°C, broadening the application field of seawater‐based energy devices. Overall, this study provides fundamental insights into the cocktail effect in high‐entropy materials and offers a new strategy for designing advanced electrodes for high‐performance SWBs.

Near‐Infrared Light Photocatalysis Enables Synergistic Cancer Therapy

ABSTRACT Extending photocatalysis into living systems is hindered by the tissue penetration of ultraviolet (UV)/visible light. We herein report a novel near‐infrared (NIR) photocatalyst, constructed by conjugating a Pt(II) porphyrin with a cyanine dye. Upon 808 nm irradiation, it operates via dual energy/electron‐transfer pathways to simultaneously generate reactive oxygen species ( 1 O 2 , O 2 · − , ·OH) and oxidize the metabolic cofactor NADH. This dual action disrupts redox balance and induces immunogenic cell death. Delivered as biocompatible nanoparticles, the system enables precise tumor delineation by fluorescence (FL)/photoacoustic (PA) imaging, and proceeds by activating tumor‐specific cytotoxic T cells, thus impeding both primary and distant tumor progression to achieve high therapeutic efficiency. This work establishes an NIR photocatalytic strategy for synergistic cancer therapy.

CO ₂ as a Redox Shuttle Enables Photocatalytic Dehydrogenative Decarbonylation of Biomass‐Derived Alcohols to Light Alkanes

ABSTRACT The use of CO 2 as a redox shuttle offers an emerging strategy to regulate electron and hydrogen transfer in catalytic transformations, yet its potential remains largely unexplored. In particular, dehydrogenative decarbonylation of alcohols possesses a long‐standing challenge, as it requires the controlled coupling of oxidative alcohol activation with reductive C─C bond cleavage, two intrinsically competing processes that are difficult to balance within a single catalytic system. Considering these, we demonstrate that CO 2 can resolve this mismatch by functioning as a dynamic redox shuttle in a heterogeneous photocatalytic platform. Under visible‐light irradiation, the photocatalyst promotes sequential dehydrogenation of primary alcohols to aldehydes, followed by C─C bond scission and selective formation of alkanes. Mechanistic studies, including isotope labeling, radical trapping, atmosphere‐dependent reactivity, and advanced quantum mechanical calculations reveal that CO 2 is not incorporated into the products but instead transiently interacts with reduced iron sites to facilitate catalyst turnover, suppress unproductive H 2 evolution, and direct hydrogen equivalents toward C─H bond formation. This redox‐shuttling function enables the integration of oxidative and reductive steps within a single photocatalytic cycle, thus opening new opportunities for steering complex redox transformations in photocatalysis.

Room‐Temperature Atomic Weaving of an Anisotropic Pd Single‐Atom‐Layer Catalyst With Orthogonal Strain for Formic Acid Oxidation

ABSTRACT Overcoming the fundamental trade‐off between high activation barriers and rapid desorption kinetics remains a central challenge in electrocatalyst design. Here we show that room‐temperature atomic weaving of anisotropic, freestanding, single‐atom‐thick Pd layers creates a bending‐poisson effect that establishes an orthogonal compressive‐tensile self‐strain network. Tensile‐strain‐induced lattice expansion accelerates spontaneous HCOOH dissociation, leading to dual‐CO adsorption on each Pd atom, while coordinated compressive–tensile domains facilitate product release by freeing bridge sites. In‐depth investigations reveal that compressive strain highly activates valence band with superior electron donation capability, while tensile strain generates accessible orbitals that suppress electronic coupling, collectively yielding a triply split electronic band structure. Consequently, the catalyst achieves a record CO adsorption capacity of 865 m 2  g −1 (372% above theoretical limits), 49.1‐fold formic acid oxidation activity enhancement over Pd/C, 618 mW cm −2 peak fuel cell power density. Moreover, the inherent structural flexibility confers high stability, retaining 89.4% of its initial activity after 440 h of accelerated degradation.

Efficient and Long‐Lived Blue OLEDs by Space‐Confined Triplet Scavenging Modulation in Terminal Emitters

ABSTRACT Blue organic light‐emitting diodes (OLEDs) incorporating multiple‐resonance (MR) emitters have achieved exceptional color purity and external quantum efficiencies (EQEs), yet their operational stability remains limited by triplet accumulation on terminal emitters (TEs). In this study, we report a space‐confined triplet‐scavenging strategy that spatially couples an anthracene‐based triplet‐scavenging unit to the MR core while electronically decoupling them. This architecture enables efficient triplet dissipation without disturbing the intrinsic singlet emission of the MR‐core. Therefore, the proposed BCzBN‐SF1An preserves narrowband blue emission and high photoluminescence quantum yield, while exhibiting an enlarged singlet‐triplet splitting and suppressed delayed emission, consistent with triplet scavenging effect. In hyperfluorescent (HF) OLEDs, BCzBN‐SF1An exhibits a maximum EQE of 22.2% with a significantly reduced efficiency roll‐off. Notably, the device lifetime is extended to 127 h at LT 80 , a threefold improvement over the parent BCzBN‐based device, without sacrificing color purity or efficiency. Transient electroluminescent measurements further reveal suppressed charge trapping and the elimination of delayed emission from TEs, highlighting the synergistic roles of triplet scavenging and optimized charge carrier dynamics. This work demonstrates comprehensive insights into carrier/exciton dynamics, along with an effective molecular design paradigm for simultaneously achieving high efficiency and long operational lifetime in blue HF‐OLEDs through precise triplet exciton management.

Chemical Ordering Command Dynamic Reconstruction for Enhanced Water Oxidation

ABSTRACT Dynamic surface reconstruction fundamentally dictates the active state of electrocatalysts. However, the lack of mastery over reconstruction kinetics typically imposes a trade‐off between high activity and long‐term stability. Here, we demonstrate that the degree of chemical ordering (long‐range atomic site occupancy) deterministically governs the evolution of alloy surfaces under operating conditions. In this design, the chemical ordering acts as a structural template that commands the reconstruction trajectory. During anodic dealloying, the ordered lattice facilitates a controlled, mild pre‐oxidation. This process generates high‐valence Fe/Co/Ni sites that trigger a well‐balanced, synergistic adsorbate evolution mechanism (AEM)/lattice oxygen mechanism (LOM) dual pathway. Unlike disordered counterparts that suffer from severe deterioration, the thermodynamically stable intermetallic core prevents excessive metal dissolution, reducing elemental leaching by 97.2%, guiding the formation of a homogeneous active reconstruction layer. As a result, the catalyst achieves an overpotential of only 335 mV at 1 A cm −2 and maintains exceptional stability for over 1000 h. Even under industrial conditions (6 M KOH, 353 K), it reaches 3 A cm −2 at only 1.50 V. This work establishes chemical ordering as a predictive parameter to govern dynamic reconstruction, offering a robust framework for designing self‐adaptive catalysts that harmonize extreme activity with industrial‐grade durability.

CT imaging-based radiomics and deep learning models for predicting chemotherapy response in advanced pancreatic cancer

Photochemical Ring Opening of Cyclopropyl Silyl Ethers Enables β–β Coupling, Radical‐Polar Crossover and Annulation

ABSTRACT A photochemical radical ring opening strategy is reported in which cyclopropyl silyl ethers undergo single‐electron oxidation and fragmentation under visible‐light photoredox conditions to furnish β‐carbonyl radicals. These intermediates engage electron‐deficient alkenes in a controlled intermolecular addition process that combines radical ring opening with C–C bond formation. The reaction delivers β–β coupling products across a broad substrate scope, including simple and complex alkenes and substrates that undergo regioselective 1,6‐addition. The resulting adducts can be further advanced through downstream annulation chemistry, whereas under modified conditions, the same intermediates can undergo radical–polar crossover and subsequent aldol cyclization, enabling access to three separate product classes from a common cyclopropyl precursor. The synthetic utility of the method is demonstrated through divergent entry into the carbocyclic frameworks of the kaurene and phyllocladane natural product families and the first total synthesis of (−)‐ ent ‐melicodenone C.