Browse Articles

In Situ Embedded Catalytic Sites Accelerate Redox Kinetics for High‐Performance Sodium–Sulfur Batteries

ABSTRACT Sodium–sulfur (Na–S) batteries are hindered by sluggish sulfur conversion kinetics and polysulfides dissolution. Although catalysts are widely introduced to improve kinetics, the crucial question persists in how catalytic sites can be effectively accessible to polysulfides especially when pursuing a highly confined sulfur redox pathway. Here we bring catalyst accessibility into focus and demonstrate that a synthetic strategy based on in situ embedded catalytic sites maximizes catalytic accessibility and efficiency. Through a bottom‐up, precursor‐integrated host synthesis route, we in situ embedded Nb 2 O 5 catalyst into carbon nanotubes in parallel with formation of extensive nanoporosity. Subsequent sulfur impregnation yields a cathode structure (I‐Nb 2 O 5 @C–S) featuring abundant catalyst–pore–sulfur triple‐phase interfaces. As a result, I‐Nb 2 O 5 @C−S delivers among the most promising sulfur utilization in literature, achieving 1540 mAh g −1 at 0.1 C, and 1044 mAh g −1 at 3 C with a low‐capacity decay of 0.027% per cycle over 1500 cycles. In contrast, a counterpart with spatially isolated Nb 2 O 5 and sulfur exhibits deficient catalytic accessibility and negligible improvement in sulfur redox kinetics. Kinetic diagnostics, combined with niobium K‐edge and operando sulfur K‐edge x‐ray absorption spectroscopy, reveal that direct accessibility of catalytic sites to sulfur is essential for synergizing polysulfide confinement and kinetic improvement.

Donor‐Glycolated Quinoidal Polymers Enable Fast N‐Type Organic Electrochemical Transistors

ABSTRACT Fast, stable n‐type organic mixed ionic‐electronic conductors remain scarce. We report a donor glycolated, quinoidal design that facilitates efficient n‐doping and spatially separates hydrophilic side chains from n‐doping sites to preserve electronic pathways. The resulting polymer PQ‐gT, synthesized from a glycolated bithiophene donor and a quinoidal bifuran‐dione acceptor, exhibits high mixed conduction with a figure of merit of µC * = 10.9 F cm −1 V −1 s −1 . In planar accumulation‐mode organic electrochemical transistors (OECTs), it exhibits nearly symmetric sub‐millisecond transients with switching on‐ and off‐times of τ on / τ off = 0.5/0.2 ms. These values represent the fastest operation for this type of device architecture. Partial donor replacement with dialkoxybithiazole tunes packing and suppresses swelling, raising µC * to 21.5 F cm −1 V −1 s −1 at 25% substitution, albeit with slower switching. In vertical OECTs, PQ‐gT supports balanced ambipolar operation with ∼1 ms switching and enables a single‐material complementary inverter (gain ≈ 40 V V −1 at V IN < 100 mV) that is stable over 10 000 cycles and functional up to 200 Hz. This donor‐glycolated quinoidal strategy furnishes intrinsically fast, aqueous‐stable n‐type organic mixed ionic‐electronic conductors for bioelectronic circuits.

Photopatternable and Stretchable Random Polymer Semiconductor via Oxetane Side‐Chain Engineering

ABSTRACT Flexible electronic devices demand semiconducting materials that combine high charge transport performance, mechanical resilience, and compatibility with advanced patterning techniques. Conventional photolithography is incompatible with polymer semiconductors, and existing photo‐crosslinking strategies often compromise mobility due to backbone side reactions. Here we report an oxetane side‑chain engineering strategy that enables a diketopyrrolopyrrole (DPP)‑based random terpolymer, PDPPSe‑oxe17 , to form robust crosslinked networks under mild UV irradiation with iodonium salt photoinitiators. Controlled incorporation of oxetane groups (17 mol%) preserves the electronic structure of the conjugated backbone while enabling rapid ring‑opening polymerization for high‑resolution photopatterning. The polymer exhibits a high hole mobility of 2.19 ± 0.28 cm 2 V − 1 s − 1 , which slightly increases to 2.27 ± 0.19 cm 2 V − 1 s − 1 after crosslinking—representing one of the highest mobilities reported for photopatterned OFETs. The resulting 3D polyoxetane network imparts good mechanical robustness, allowing films to withstand 108% strain and retain ∼85% and ∼76% mobility at 30% and 50% strain. Even at 100% strain, the mobility remains ∼1.4 ± 0.12 cm 2 V − 1 s − 1 , whereas non‑crosslinked counterparts retain only ∼3% of their initial mobility. This work establishes a generalizable molecular design principle for intrinsically photopatternable and stretchable polymer semiconductors.

Short Sb···Sb Contacts in Polymorphic Tris( <i>p‐</i> Tolyl)Antimony: A Hallmark of Organoantimony(III) Solid‐State Chemistry?

ABSTRACT Discovery of a polymorph of tris( p‐ tolyl)antimony(III) reveals solid‐state supramolecular dimers connected through short, attractive Sb∙∙∙Sb contacts that, based on theoretical calculations and a systematic screen of the Cambridge Structural Database (CSD), could be an overlooked hallmark of the solid‐state and supramolecular chemistry of trivalent organoantimony(III) compounds. While the previously reported crystal structure of tris( p‐ tolyl)antimony(III) is known to exhibit phenyl embrace motifs, resembling the arsenic or phosphorus analogs, the new polymorph exhibits supramolecular dimers characterized by direct Sb∙∙∙Sb contacts shorter than the sum of the van der Waals radii, and stabilized by a significant dimer dissociation energy of ca. −26 kJ mol −1 established by periodic density‐functional calculations. Theoretical analysis indicates that the contacts are attractive and dispersion‐dominated, with an overview of the CSD showing that such direct Sb···Sb contacts are not unique to this polymorphic form of tris( p‐ tolyl)antimony(III) but appear to be a more general feature of trivalent organoantimony in the solid state. Specifically, the CSD shows that dimers based on short Sb···Sb contacts are found across a number of organoantimony structures, including some of the simplest representatives of the series, such as triphenyl‐ and trimethylantimony, for which the dimer interaction energy is herein calculated to be ca. −13 kJ mol −1 .

Spatial Regulated Noncontact Ru Heterostructure for Cost‐Effective Platinum‐Free Fuel Cells

ABSTRACT Cost‐effective Ru holds tremendous promise to tackle the sluggish hydrogen oxidation reaction (HOR) kinetics. Rational spatial distribution design of heterostructure components is crucial for electrochemical reactions involving multiple intermediates, particularly in fuel cells. In this study, we demonstrate a noncontact heterostructure catalyst featuring spatially separated but functionally synergistic ruthenium (Ru) nanoparticles (NPs) and molybdenum carbide (MoC) clusters (CLs) interconnected by a conductive carbon support (Ru‐MoC/C) for the alkaline HOR. The experimental results and density functional theory (DFT) calculations demonstrate that this configuration achieves a refined division of labor and seamless collaboration in functionality through its ingenious spatial arrangement. Consequently, the Ru‐MoC/C‐based anion exchange membrane fuel cell (AEMFC) with an ultralow Ru loading of 0.05 mg Ru cm −2 and a Co 2 MnO 4 /C cathode achieves a remarkable total specific peak power of 17.4 W mg PGM −1 in H 2 ‐air, surpassing the state‐of‐the‐art catalysts. Moreover, this Pt‐free AEMFC achieves a total platinum‐group‐metal (PGM) utilization of 13.4 W mg −1 at 0.65 V, which surpassing the U.S. Department of Energy (DOE) 2025 target. Additionally, the Ru‐MoC/C‐based fuel cell can maintain stable cell operation at 0.5 A cm −2 for over 110 h. This work highlights the promise of noncontact heterostructure design in developing efficient and durable electrocatalysts and beyond.

Metal Coordination Dynamics Governs Selective Halogenation in α‐KG/Fe‐Dependent Halogenase SyrB2

ABSTRACT α‐Ketoglutarate (α‐KG)‐dependent nonheme iron enzymes catalyze a diverse array of oxidative transformations essential for natural product biosynthesis. However, the mechanism by which α‐KG/Fe‐dependent halogenases achieve selective halogenation while circumventing the thermodynamically favored hydroxylation pathway remains a subject of intense debate. In this study, we elucidate the halogenation mechanism in SyrB2 through extensive computational and crystallographic investigations. Our work reveals that metal coordination dynamics plays a pivotal role in controlling selective C─H bond activation and chlorination in SyrB2. The transformation of the Fe(IV)‐oxo species from an equatorial to an axial conformation enables hydrogen atom transfer from the substrate C─H bond. Subsequent re‐isomerization of the Fe(III)‐OH intermediate to the equatorial conformation is critical for promoting selective chlorination while minimizing competitive hydroxylation. The proposed mechanism is supported by multiple experimental observations, including Mössbauer spectroscopy, nuclear resonance vibrational spectroscopy (NRVS), 2 H‐HYSCORE spectroscopy, and kinetic analysis of reactions with various substrates.

Solvation‐Preserving Gelation of Localized High‐Concentration Electrolytes for Lithium Metal Batteries

ABSTRACT Localized high‐concentration electrolytes (LHCEs) exhibit excellent interfacial compatibility with lithium metal anodes and high‐nickel cathodes, whereas the introduction of polymer networks during gelation may alter their intrinsic solvation structures. Here, we report a solvation‐preserving gel electrolyte formed via in situ polymerization of a fluorinated polymer network within a 1,2‐Dimethoxyethane (DME)‐based LHCE. Unlike conventional gel polymer electrolytes, the fluorinated polymer exhibits limited Li + coordination, thereby largely preserving the localized high‐concentration solvation environment during gelation. This design couples the preserved LHCE solvation chemistry with a fluorinated polymer framework, enabling synergistic regulation of electrode–electrolyte interfaces and enhanced electrochemical performance. Meanwhile, the fluorinated polymer network further improves safety by reducing electrolyte flammability. Lithium symmetric cells achieve stable cycling over 2000 h, while LiNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM9)|Li full cells deliver 82.2% capacity retention after 300 cycles and operate stably up to 4.5 V. At the pouch‐cell level, a gravimetric energy density of 394.3 Wh kg −1 is achieved under lean‐electrolyte conditions, while no thermal runaway is observed up to 300°C. This work demonstrates that preserving solvation structure via rational polymer network design enables simultaneous improvements in interfacial stability, safety, and practical performance in quasi‐solid‐state lithium metal batteries.

Uncaging Iridium(III) Complexes for Combined Photodynamic and Photoactivated Chemotherapy

ABSTRACT Inorganic photochemotherapy enables precise spatial and temporal control over anticancer drug activation, offering a promising strategy to reduce systemic toxicity. Two iridium(III) complexes of general formula [Ir(L)(ppy)(terpy)]PF 6 with L = N ‐acetyl‐ L ‐cysteinato methyl ester (cys) or N ‐acetyl‐ L ‐selenocysteinato methyl ester (sec), were developed as light‐activatable prodrugs with sulfur‐ and selenium‐based “caging” groups. Both complexes are stable in the dark but undergo light induced bond cleavage upon visible light activation, following distinct photochemical pathways dictated by the coordinated chalcogen. For the cys complex, an initial oxygen‐dependent formation of a sulfinato intermediate is followed by Ir─S bond cleavage. In contrast, the selenium complex first releases dehydroalanine due to Se─C bond cleavage, forming an unprecedented selenite intermediate [Ir(SeO 3 )(ppy)(terpy)], which was characterized by single crystal x‐ray diffraction. The photoactivation leads to high singlet oxygen production quantum yields (40%–48%), consistent with a type II photodynamic therapy (PDT) mechanism. Both complexes exhibit minimal dark toxicity (EC 50  &gt; 150 µM) but potent photocytotoxicity in A549 cells under blue and green light photoactivation (460 and 520 nm). This new class of photocaged iridium(III) pro‐sensitizer shows promise for combined PACT/PDT applications and demonstrates how chalcogen coordination modulates the photoreactivity and therapeutic efficacy of metal complexes.

Adsorption‐Engineered Hydrocarbon Ionomers for Durable Proton‐Exchange Membrane Fuel Cells

ABSTRACT Reducing reliance on perfluoroalkyl substances (PFAS) in proton‐exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long‐term durability, a persistent challenge in catalyst‐layer design. Here, we identify oxidation‐driven ionomer‐catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer‐bonded cathodes and introduce an adsorption‐engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon‐supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm − 2 at 0.65 V under fully humidified H 2 /air conditions (80°C and 150 kPa abs ), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)‐bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion‐bonded cathodes (14%). These findings establish adsorption‐engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high‐performance PFAS‐free PEM fuel cell electrodes.

Carlos M. Cruz

Frequency‐Adaptive Elastomers Through Cooperative Dynamics of Liquid‐Crystalline Domains and a Rubber Matrix

ABSTRACT Elastomers are highly suitable for components requiring conformal deformation under load, but their low modulus sensitivity to frequency limits the material's ability to resist dynamic damage. Here we report a phase‐separated elastomer that remains compliant at low loading frequency and stiffens strongly at high frequency, while preserving elastic recovery. The elastomer comprises a carboxylated nitrile rubber (XNBR) matrix and dispersed liquid‐crystalline (LC) domains. Under slow loading, the dispersed phase can relax local stress through mesogen reorientation. In contrast, the same domains become increasingly load‐bearing under faster loading as this motion is constrained. As a result, the modulus of the phase‐separated elastomer increases by 6.2‐fold from 0.01 to 100 Hz, compared with about 2.2‐fold for the neat XNBR. In addition to rate stiffening, the materials retain resilience, low hysteresis, and long‐term dimensional stability, leading to significantly improved resistance to abrasive wear (77.4% reduction in mass loss), repeated impact (83.7% reduction in damaged ratio), and notch propagation (over 30 000 cycles) upon high‐frequency loading, compared with the neat XNBR. These results show that cooperative dynamics between a recoverable rubber matrix and LC domains can provide a useful route to elastomers that combine compliance with adaptive mechanical protection.

Macrocycle‐Based Charge‐Transfer Cocrystals: From Host–Guest Recognition to Multifunctional Solid‐State Materials

ABSTRACT Macrocycle‐based charge‐transfer (CT) cocrystals have recently emerged as a distinctive class of adaptive supramolecular solids that bridge molecular recognition and solid‐state functional materials. Unlike conventional CT assemblies, these systems combine host–guest chemistry with intermolecular donor–acceptor interactions, enabling simultaneous regulation of molecular packing, electronic coupling, and excited‐state processes. The coexistence of cavity‐confined complexation and exo‐wall CT assembly, together with the dynamic nature of host–guest interactions, provides unique opportunities for constructing stimuli‐responsive materials whose structures and functions can be continuously modulated by external inputs. In this Review, we discuss the fundamental principles underlying the design and construction of macrocycle‐based CT cocrystals and highlight how adaptive host–guest recognition governs CT interactions and emergent solid‐state properties. Recent advances in vapochromic sensing, molecular separation, photothermal conversion, luminescence modulation, and multifunctional integrated systems are systematically summarized, with particular emphasis on competitive and cooperative structural regulation mechanisms. Finally, we outline current challenges and future directions toward programmable, multicomponent, and application‐oriented CT materials. By establishing connections between supramolecular structure, CT behavior, and functional output, this Review aims to provide a conceptual framework for the development of next‐generation adaptive molecular solids.

Wafer‐Scale Ultrafine Wrinkle Architectures of TMDCs for Multifunctionality

ABSTRACT Intensely applied strain from wrinkled architecture mitigates intrinsic limitations of 2D materials while enhancing their capabilities through spatially modulated electronic and catalytic properties. Here, this study introduces a deterministic wafer‐scale fabrication strategy that enables densely distributed ultrafine wrinkled architectures in atomically thin molybdenum disulfide (MoS 2 ) crystals, achieving tensile strains up to 3.29% over 50% of the scan area. The wrinkle structures are obtained by modulating the parameters of a wet transfer method, including transfer liquid media, thermal energy, and polystyrene (PS) solution concentrations. Collectively, these results demonstrate a practical route to wafer‐scale fabrication of ultrafine wrinkle structures. The wrinkled MoS 2 (w‐MoS 2 ) exhibits optimal multifunctional device performance in electronics and as a hydrogen evolution catalyst. In a hydrogen evolution reaction (HER), the lowest Tafel slope (52.3 mV dec −1 ) is observed, comparable to that of metallic TMDC catalysts. Furthermore, our w‐MoS 2 memory device displays an on/off ratio of 5 × 10 7 with a large memory window corresponding to 65% of the total gate voltage ( V GS ) sweep range. This simple and innovative morphology engineering offers a viable and reproducible pathway toward high‐performance electronic and catalytic functionalities in highly strained 2D materials.

Anisotropy‐Driven Discovery of Rare‐Earth‐Free Magnets in Mo ₂ FeB ₂ ‐Type Borides

ABSTRACT Multifunctional materials are critically important for modern technologies. Magnets, especially those relevant to spintronic applications, are essential for energy‐efficient data processing and advanced magnetic devices, while high‐strength materials provide excellent mechanical and thermal stability. Mo 2 FeB 2 ‐type materials are well established for their superior strength and thermal properties, yet their magnetic behavior has remained largely theoretical, dominated by antiferromagnets and, more recently, predicted altermagnets. Building on our recent report of spin‐glass phases exhibiting large anisotropy, we have discovered Mo 2 FeB 2 ‐type high‐temperature ferromagnets: Mn‐rich MoMn 2 B 2 and WMn 2 B 2 . These compounds exhibit magnetic ordering above room temperature, with Curie temperatures (and Weiss constants) of 400 K ( θ  = 229 K) and 380 K ( θ  = +154 K), respectively. Notably, rare‐earth‐free WMn 2 B 2 displays enhanced coercivity with an intrinsic coercivity of 67.6 kA m −1 at 5 K, supported by DFT calculations revealing a large in‐plane magnetocrystalline anisotropy energy of +0.27 meV/f.u., driven by the strong spin‐orbit coupling of tungsten. These findings show that Mn‐rich Mo 2 FeB 2 ‐type borides are promising rare‐earth‐free permanent magnet candidates that combine high‐temperature ferromagnetism, enhanced magnetic anisotropy, and excellent structural stability.

Redox‐Ligand‐Coupled Chemical Reprogramming of Battery Waste Into Metal–Organic Electrodes for Closed‐Loop Energy Storage

ABSTRACT Sustainable battery waste management requires moving beyond element recovery toward full‐component reutilization. Here, we report a redox‐ligand‐coupled chemical reprogramming strategy that transforms chemically distinct components of battery waste into functional energy storage materials. Using LiCoO 2 and polyethylene terephthalate (PET) as a model system, terephthalate and ethylene glycol generated from PET depolymerization act synergistically as coordinating ligands, proton sources, and reductants, enabling the dissolution of cathode materials and their in situ reconstruction into a redox‐active metal–organic framework (cobalt terephthalate, CoTPA) under hydrothermal conditions without external leaching agents or reductants. This self‐reinforcing reaction network couples polymer depolymerization with cathode deconstruction, eliminating external reagents and complex separation processes. The resulting CoTPA anode delivers a reversible capacity of ≈1170 mAh g −1 at 0.1 A g −1 , and retains 92.1% of its initial capacity after 500 cycles at 1 A g −1 . When integrated with regenerated graphite (RG), CoTPA enables a battery‐level closed‐loop dual‐ion battery (DIB) with an energy density of 304 Wh kg −1 (based on total active material mass). The strategy is extended to layered oxide cathodes and diverse PET sources. Beyond conventional recycling, this work establishes a chemistry‐driven paradigm that reprograms waste components into value‐added functional materials, offering a scalable pathway toward circular energy storage.

Evolutionary, Functional and Mechanistic Characterisation of Microbial Terpene Synthase‐Like Genes From Springtails

ABSTRACT Despite previous doubts about the origin of terpenes in springtails, a deep bioinformatic analysis of the genomes of 26 springtails surprisingly revealed the presence of many genes coding for microbial‐type terpene synthases. Five candidate enzymes from Sinella curviseta representing different branches of a phylogenetic tree were selected for investigation, four of which were active in in vitro incubations with an enzyme‐dependent substrate selectivity ranging from farnesyl (FPP) to geranylfarnesyl pyrophosphate (GFPP), with formation of multiple products in all cases. The obtained enzyme products included the new macrocycle sestersinellene, the enantiomer of a sesterterpene produced by a terpene synthase from Leucosceptrum canum and the unusual diterpene sinellene ether representing a novel skeleton, reinforcing springtails as an interesting source of terpenes. Extensive isotopic labelling experiments revealed several unusual mechanistic aspects such as the formation of a series of enantiomerically pure products besides one scalemic compound (germacrene D), as well as an unexpected stereochemical course for a reprotonation step in sinellene ether biosynthesis by ScTC2. Taken together, this study lays the foundation for future research on terpene biosynthesis in Collembola, an ancient lineage of arthropods.

Conjugated Thiophene Linker Design of the Self‐Assembled Monolayer Toward Highly Efficient and Stable Organic Solar Cells

ABSTRACT Achieving high power conversion efficiency (PCE) and operational stability remains a critical challenge of organic solar cells (OSCs). While the 2PACz self‐assembled monolayer (SAM) offers suppressed parasitic absorption and facilitated charge collection over the routinely‐used PEDOT:PSS hole‐transport layer (HTL), their operational stability is often limited by the vulnerable chemical structure under high‐energy photon illumination. In this work, we design and synthesize two SAMs, PhPACz and ThPACz, whose flexible alkyl linker between phosphonic acid and carbazole of 2PACz is substituted by rigid phenyl or thiophene to manipulate the HOMO and LUMO orbitals and further mediate the electron density distribution of SAM, thereby promoting charge delocalization at the interface and enhancing photochemical stability. The ThPACz SAM delivers suppressed oxygen defects on the ITO surface and largely enhanced the bond dissociation energy at the vulnerable C‐N bond (from 72.2 kcal/mol in 2PACz to 97.3 kcal/mol in ThPACz), translating to a champion efficiency of 20.5% in D18:L8‐BO binary OSCs, alongside a significantly extended T 80 lifetime (over 7 times) under either visible or 365 nm UV light, outperforming the 2PACz based benchmark. This study underscores the critical role of conjugated linkers in designing high‐performance, stable SAMs for next‐generation OSCs.

Direct Synthesis of Well‐Defined Epoxide‐Terminated Telechelic Polymers via an Alcohol‐Mediated Self‐Switching Strategy

ABSTRACT The one‐step synthesis of well‐defined telechelic polymers represents a highly attractive approach, providing an efficient alternative to conventional stepwise synthetic protocols. However, achieving such control remains challenging due to the competitive nature of chain propagation and end‐group functionalization, which often leads to uncontrolled chain‐end structures and broad dispersities. Here, we report an alcohol‐mediated self‐switching strategy, in which the dominant chain‐end reaction shifts from propagation to end‐group functionalization upon consumption of one monomer component within a single reaction system. Using epichlorohydrin, a multisite monomer, as a model for the ring‐opening alternating copolymerization with cyclic anhydrides, we obtained well‐defined epoxide‐terminated telechelic polyesters with narrow dispersities ( Đ ∼ 1.1), high end‐group fidelity (&gt;99%), and controllable linear, three‐arm, and four‐arm architectures under alcohol‐mediated conditions. Mechanistic studies reveal that monomer activation and stabilization of the living species through hydrogen‐bonding interactions, combined with the zero‐order kinetics of cyclic anhydride, facilitate rapid propagation while suppressing premature functionalization. Subsequent intramolecular cyclization of β‐chlorohydrin living chain ends, along with proton‐transfer‐induced dehydrochlorination of β‐chlorohydrin dormant chain ends, collectively ensure quantitative epoxide end‐group formation. These results elucidate the catalyst‐like roles of alcohol and establish self‐switching of competing chain‐end reactions as a practical strategy for the direct synthesis of well‐defined telechelic polymers.

Porous COF@cMOF Heterojunction‐Assisted Laser Desorption/Ionization Mass Spectrometry for Enhanced Breast‐Cancer Serum Metabolomic Screening

ABSTRACT Early breast‐cancer (BC) screening requires reliable molecular information from minimally invasive samples, yet sensitive detection of small‐molecule metabolites in complex biofluids remains challenging. Herein, a structurally well‐defined porous heterojunction matrix, COF316@CuHHTP, is developed through an in situ epitaxial‐growth strategy for serum metabolomic screening. Porous and chemically robust COF316 serves as the core scaffold, while conductive CuHHTP forms a coherent shell for interfacial charge mediation. The resulting heterojunction enables efficient small‐molecule capture and directional transport through the channels, while enhanced photothermal conversion and optimized charge transport collectively improve desorption/ionization efficiency and sensitivity for small‐molecule metabolites. Consequently, COF316@CuHHTP enables sensitive and robust laser desorption/ionization mass spectrometry (LDI‐MS) analysis, with the maximum signal‐to‐noise (S/N) enhancement reaching ∼194‐fold, ultralow limits of detection (LODs) down to the pmol level, and strong tolerance to high‐salt and protein‐rich conditions. Applied to serum analysis, this platform enables BC diagnosis with excellent discriminatory performance (AUC = 0.996) and identifies 20 disease‐associated metabolic signatures.

Goutam Ghosh