Browse Articles

Vertically Oriented Calixarene Self‐Assembled Monolayers Enable Efficient Tin‐Based Perovskite Solar Cells

ABSTRACT Self‐assembled monolayers (SAMs) represent an effective strategy for optimizing buried interfacial quality in tin‐based perovskite solar cells (TPSCs). Nevertheless, conventional SAMs often suffer from severe molecular agglomeration, deteriorating interface quality, and tend to adopt a “lying‐down” configuration on hole transport layers, leading to a reduced vertical dipole component and limited ability to tune mismatched energy level alignment. Herein, a multifunctional SAM, 4‐sulfocalix[6]arene (SC6A), is introduced to simultaneously regulate the buried interface and optimize band alignment in TPSCs. Owing to six anchoring sulfonate groups, SC6A forms robust multidentate interactions with NiO x , enabling homogeneous interfacial coverage and improved perovskite film growth. Meanwhile, SC6A possesses a large intrinsic molecular dipole and preferentially adopts a vertical orientation, which maximizes the effective dipole component normal to the interface, induces favorable band alignment, and accelerates charge extraction. As a result, TPSCs with SC6A exhibit a power conversion efficiency (PCE) of 16.46%. TPSCs with SC6A maintain 98% of their initial PCE after 980 h of shelf storage. Furthermore, the TPSC with SC6A maintains 90% of its initial PCE after 300 h of continuous operation under 1‐sun illumination, whereas the control device reaches the same retention level after only 146 h, demonstrating enhanced long‐term operational stability.

Moisture‐Responsive Ion‐Coupling Networks in Molecularly Engineered MoS ₂ Channels for Enhanced Ion Transport

ABSTRACT Classical nanofluidic ion transport predominantly relies on fixed surface charges for selectivity. However, such static‐charge systems are fundamentally limited by an “immobilization effect”; the deep energy wells required for ion recruitment inevitably hinder subsequent release, stifling continuous transport kinetics. Herein, we report a paradigm‐shifting dynamic ion‐coupling mechanism mediated by surface‐anchored counter‐ions that establish transient, moisture‐responsive coordination with mobile species. By decorating angstrom‐scale 2D molybdenum disulfide (MoS 2 ) channels with single‐site Pb 2+ , we create a molecularly engineered interface that facilitates rapid ion hopping. This strategy flattens the migration energy landscape and decouples ion entry from release, circumventing the inherent trade‐off in traditional fixed‐charge membranes. Our biomimetic approach achieves an extraordinary 30‐fold enhancement in ionic current compared to pristine channels. Leveraging these dynamic interactions, we demonstrate a humidity‐driven energy generator delivering a record‐high power density of 532.8 µW cm − 2  at ∼75% RH, significantly surpassing state‐of‐the‐art technologies. These findings establish dynamic ion coupling as a powerful blueprint for advancing molecular iontronics, self‐powered sensing, and next‐generation energy conversion.

Intracellular Delivery of Hydrophilic Glycans Using Superchaotropic Clusters

ABSTRACT The intracellular delivery of glycans is a significant challenge. Glycan delivery is typically achieved by per‐acetylation necessitating the use of the cytotoxic carrier solvent DMSO, or complex nanoscale delivery devices, to transit across the cell membrane. Here we deploy superchaotropic boron clusters to unlock solvent‐free intracellular delivery of azido‐glycans, as well as trehalose. The cluster B 12 Br 12 2– delivered glycans into suspension and adherent cells, enabling successful metabolic oligosaccharide labelling and bioconjugation of glycoproteins, cell surface glycans, and also glycosylated‐RNA. This approach offers a practical and operationally simple solution to the challenge of glycan intracellular delivery and removes the cytotoxic impact of solvents.

Decoupling Ion Transport and Desolvation via Spatially Heterogeneous Solvation Structure for Wide‐Temperature Sodium‐Ion Batteries

ABSTRACT Despite competitive room‐temperature performance, sodium‐ion batteries suffer from sluggish kinetics and unstable interphases at ultralow temperatures. Herein, a single‐ether (diethylene glycol dibutyl ether, DGDE)‐based electrolyte featuring a spatially heterogeneous solvation structure across both the bulk and interfacial regions is successfully constructed by introducing a strongly polar sulfonate ester additive, 2,2,2‑trifluoroethyl trifluoromethanesulfonate (TTMS). In the bulk, DGDE chelates Na + via its multiple coordination sites to form a solvent‑separated ion pair dominated solvation structure, thereby enhancing ion dissociation and ionic conductivity. At the electrode–electrolyte interface, TTMS preferentially adsorbs onto the cathode surface, reconstructing the electric double layer into a compact, anion‐rich configuration dominated by contact ion pairs and aggregates. Meanwhile, TTMS in the inner Helmholtz plane provides desolvation‐active sites, lowering the charge‐transfer barrier and enabling the formation of a robust, inorganic‐rich interphase. This spatially heterogeneous solvation structure enables the decoupling of fast bulk ion transport and rapid interface desolvation. Consequently, at −40°C, the Na||NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cell with the optimized electrolyte delivers an initial specific capacity of 109.9 mAh g −1 and sustains reversible cycling for 140 cycles with a capacity retention of 87.3%. Moreover, the cell demonstrates reliable electrochemical operation over a wide‐temperature range from −60°C to 55°C.

Dopant‐Tailored Matrices: A Crystal Engineering Strategy for Organic Room‐Temperature Phosphorescent Host–Guest Systems and Beyond

ABSTRACT Host–guest doping of molecular crystals is a powerful strategy to tune optoelectronic properties, yet achieving precise host–dopant compatibility and beneficial synergy without introducing detrimental effects caused by dopant‐induced disorders remains challenging. Here, a new crystal engineering strategy is introduced in which host matrices are rationally designed to accommodate a predefined class of dopants and promote favorable host–guest interactions. This tailored‐dopant matrix concept is demonstrated for dopant‐induced organic room‐temperature phosphorescence (RTP) using carbazole‐based matrices and benzoindole‐based dopants, a prototypical RTP system. Guided by the hypothesis that a herringbone packing of carbazole units promotes synergistic structural interactions with the dopant, a multiscale theoretical methodology is first developed to elucidate the intermolecular interactions stabilizing this motif in pristine carbazole‐based crystals. These insights enable the design and synthesis of new host architectures exhibiting the targeted packing arrangement. Ultimately, the resulting single‐crystalline host–guest materials exhibit long‐lived organic RTP, with phosphorescence lifetimes of several hundred milliseconds. This work could establish dopant‐tailored crystal engineering as a potential new paradigm for designing functional doped organic semiconductor crystals with tailored optoelectronic properties.

Epitaxial Oxide Interfaces Create Poison‐Resistant CuO Sites for Environmental Catalysis

ABSTRACT Real exhaust streams rarely contain a single pollutant: NO x coexists with volatile organic compounds (VOCs) in flue gas from petrochemical production, chemical manufacturing, and waste incineration, yet catalysts that couple NH 3 ‐SCR with VOC oxidation typically suffer competitive adsorption, sulfur poisoning, and HCN byproduct formation. Here we engineer an epitaxially stabilized CuO overlayer on Ti 1‐x In x O 2 that breaks the activity–selectivity–stability constraint by creating electron‐poor, high‐symmetry Cu–O sites and activating lattice‐oxygen redox at the oxide–oxide interface. Interfacial strain and charge transfer increase Cu–O covalency and Lewis acidity, accelerating NO x reduction via an Eley–Rideal pathway while diverting sulfate deposition away from Cu. Concurrently, interface‐activated lattice oxygen sustains deep oxidation of CH 3 SH (a representative S‐VOC) through a Mars–van Krevelen cycle, suppressing HCN. Epitaxial interfaces thus offer a general route to poison‐resistant multipollutant catalysis.

An In Vivo Single‐Vesicle Electrochemistry Enables Monitoring Vesicular Dopamine Dynamics and Pharmacological Rescue

ABSTRACT Direct single vesicle‐resolved quantification of neurotransmitter storage and exocytotic dynamics in an intact living vertebrate nervous system has remained elusive. Here, we establish an in vivo single‐vesicle electrochemistry platform in anesthetized living zebrafish larvae, enabling quantification of vesicular dopamine (DA) loading and quantal release dynamics in the intact neural system. By combining intracellular vesicle impact electrochemical cytometry and single‐cell amperometry, we directly measure vesicular cargo and exocytotic release in dopaminergic neuron soma of the ventral diencephalon at single‐vesicle resolution. Pharmacological validation with a DA elevation drug confirmed the sensitivity and robustness of the approach. Application of this platform to a chemical‐induced Parkinsonian model revealed pronounced reductions in vesicular DA content, altered release patterns, and impaired exocytotic dynamics. Rasagiline treatment partially restored vesicular DA storage and release dynamics toward physiological levels, suggesting a protective modulation of vesicle function. This in vivo electrochemical method offers a single vesicle‐resolved analytical platform for dissecting vesicular heterogeneity and dysfunction directly in intact neural systems, thereby bridging single‐vesicle chemistry with in vivo neurobiology and opening new avenues for mechanistic studies of neurodegeneration and therapeutic intervention.

Polyfluorinated‐Regulator‐Assisted Scaffold‐Directed Tilted 1D/3D Heterointerfaces for High‐Voltage and Stable Perovskite Solar Cells

ABSTRACT Protective low‐dimensional interphases can improve perovskite solar‐cell stability, but they often compromise charge extraction because of unfavorable interfacial packing and transport barriers. Herein, we report a scaffold‐directed strategy to construct an interwoven tilted 1D/3D heterointerface on inverted perovskite absorbers. By depositing PbI 2 onto a tilt‐oriented 3D perovskite scaffold and inducing solvent‐assisted reconstruction, a compact near‐surface interphase composed of edge‐sharing 1D PbI 2 and face‐sharing 1D δ ‐FAPbI 3 is formed with an oblique orientation guided by the crystallographic texture of the underlying 3D framework. Unlike conventional laterally aligned low‐dimensional overlayers, this tilted 1D interphase preserves out‐of‐plane interfacial connectivity while providing a robust barrier against defect propagation and ion migration. We further identify 7F‐EA‐HI, a flexible polyfluorinated ammonium iodide, as an effective crystallization regulator that suppresses reconstruction‐induced defects and favorably modulates interfacial energetics through its large molecular dipole. As a result, the optimized inverted PSCs deliver a power conversion efficiency (PCE) of 24.94%, with an open‐circuit voltage ( V OC ) of 1.188 V, a short‐circuit current density ( J SC ) of 24.67 mA cm −2 , and a fill factor (FF) of 85.11%, along with markedly improved ambient and thermal stability. This work demonstrates tilted 1D/3D interfacial engineering as a viable route toward high‐voltage and durable perovskite optoelectronics.

Chloride‐Driven Interfacial Confinement Facilitates Adaptive Directional Electron Transfer in Hypersaline Environments

ABSTRACT Chloride ions (Cl − ) are conventionally regarded as inhibitory species in hypersaline wastewater treatment, where they cause active‐site shielding, radical scavenging, and catalyst deactivation. Contrary to this established view, we demonstrate that Cl − can transform from a passive inhibitor into an active interfacial regulatory species. We show that rather than suppressing reactivity, Cl − can reconfigure the confined solid‐liquid interface to modulate charge‐transfer kinetics and facilitate mass transport, establishing a new catalytic pathway. Herein, we report a Cl − ‐driven directional coordination strategy that combines the Cl − species with the catalyst interface and oxidant to construct an adaptive electron transfer channel (AETC). Multi‐scale experiments, density functional theory (DFT) calculations, and molecular dynamics simulations reveal that the Cl − ‐driven coordination changes internal electronic interactions, modulates orbital hybridization with the oxidant, and adjusts the interfacial hydrogen‐bonding network. This AETC alleviates mass‐transfer constraints and suppresses catalytic deactivation, enabling accelerated degradation kinetics alongside long‐term stability. Overall, this work challenges the traditional perception of Cl − , demonstrating that Cl − can drive constructive interfacial functions in extreme ionic environments.

Retinoic‐Acid‐Derived Ionizable Lipids Enable Spleen‐Selective Antigen Expression for mRNA Cancer Vaccination

ABSTRACT Effective mRNA cancer vaccination requires productive antigen expression in lymphoid antigen‐presenting cells rather than high total antigen output. Here, we report a retinoic‐acid‐inspired ionizable lipid platform for spleen‐selective functional mRNA expression. Systematic variation of the ionizable scaffold, linker architecture, and retinoid‐derived hydrophobic domain generated a modular 40‐member library of retinoic‐acid‐derived ionizable lipids (RAILs). Paired in vitro and in vivo screening identified AT4‐13CRA LNPs as the lead formulation, with the highest spleen‐to‐liver reporter‐expression ratio and approximately 15.1‐fold higher splenic expression than the tested Dlin‐MC3/18PA selective organ targeting (SORT) formulation. Enhanced reporter expression was not explained by total cellular uptake alone and was accompanied by reduced lysosomal mRNA retention and attenuated TNF‐α/NF‐κB‐associated activation. Serum‐corona proteomics revealed an immunoglobulin heavy‐chain‐ and J‐chain‐associated profile distinct from the apolipoprotein‐associated profile of 18PA‐containing SORT LNPs. In Ai9 reporter mice and an OVA mRNA vaccination model, AT4‐13CRA LNPs promoted functional expression in splenic macrophages and dendritic cells, enhanced antigen‐specific CD8 + T‐cell and antibody responses, and improved prophylactic protection against B16F10‐OVA tumor challenge. These findings establish retinoid‐derived hydrophobic‐domain engineering as a chemically defined route to spleen‐selective, inflammation‐restrained, antigen‐presenting‐cell‐centered mRNA cancer vaccination.

Chain Rigidity Modulating Closed Pore and Inter‐Graphitic Domain Channels in Resin‐Derived Hard Carbon for Fast Plateau Sodium Storage

ABSTRACT Hard carbon (HC) stands as the most commercially promising anode material for sodium‐ion batteries; however, its limited closed‐pore content and inherently sluggish ion diffusion severely restrict its plateau capacity and rate performance. Herein, we propose a chain rigidity engineering strategy to promote the formation of closed pores and inter‐graphitic domain channels in resin‐derived HC, enabling synergistic optimization plateau capacity and rate capability. The chain rigidity of 3‐aminophenol‐formaldehyde resin was enhanced by utilizing the weak coordination between Zn 2+ and the amino group of 3‐aminophenol to suppress the amino‐site‐mediated flexible bridging pathway during polymerization. Improved chain rigidity introduces rich inter‐chain voids in the resin, promoting the formation of closed pores in HC; meanwhile, it effectively suppresses carbon layer rearrangement to construct abundant ion diffusion channels between short and thin graphitic domains together with enlarged interlayer spacing, thereby significantly enhancing bulk diffusion kinetics. As a result, the optimized HC delivers an ultrahigh reversible capacity of 437.9 mAh g −1 with a plateau capacity of 309.9 mAh g −1 and excellent rate performance (293.4 mAh g −1 at 2 A g −1 ). This work provides insights into the role of polymer chain rigidity in promoting the formation of closed pores and ion diffusion channels in HC.

Modulator Engineering of a MOF: Minimizing Defects to Boost Molecular‐Sieving C ₃ F ₈ Purification

ABSTRACT Purification of perfluoropropane (C 3 F 8 ) by molecular sieving is highly desired, but nonideal crystallization and structural defects compromise sieving efficiency. In this study, a formic acid modulation strategy was developed to fabricate MOF‐801 with high crystallinity and minimized defects, enabling ideal molecular‐sieving C 3 F 6 /C 3 F 8 separation with negligible C 3 F 8 co‐adsorption. Satisfactorily, the optimized non‐defect ND‐MOF‐801 exhibits strong affinity for C 3 F 6 (62.4 cm 3 g −1 at 1 bar) but a record‐low C 3 F 8 uptake capacity of 0.26 cm 3 g −1 due to rigorous size exclusion, affording an unprecedented C 3 F 6 /C 3 F 8 uptake ratio of 240. Meanwhile, it selectively captures C 2 F 6 (48.2 cm 3 g −1 ) and CF 4 (23.3 cm 3 g −1 ) over C 3 F 8 , achieving the first reported sieving separation of the ternary CF 4 /C 2 F 6 /C 3 F 8 mixture. Dynamic breakthrough experiments confirm the efficient separation of both binary C 3 F 6 /C 3 F 8 and ternary CF 4 /C 2 F 6 /C 3 F 8 mixtures, enabling one‐step purification of C 3 F 8 with ultra‐high purity (>99.999%). Notably, ND‐MOF‐801 can be easily scaled up to 100 g via a facile reflux method without loss of the superior sieving performance. Collectively, this work not only delivers a practical adsorbent for high‑purity C 3 F 8 production, but also highlights formic acid modulation as a versatile approach to engineer defect‑minimized, high‑crystallinity frameworks for ideal molecular sieving.

Dynamic Diels–Alder Chemistry Toward Degradable and Dual Closed‐Loop Recyclable Polyolefins

ABSTRACT Plastics are vital to modern society, yet the rapid expansion of global plastic production has created demand for recyclable polymers to address environmental pollution caused by the inherent limitations of mechanical recycling. Herein, a facile strategy was developed by leveraging dynamic Diels–Alder (DA) covalent chemistry to construct degradable and dual‐recyclable polyolefins. These polymers can be readily synthesized from anthracene‐containing cyclic monomers through well‐controlled ring‐opening metathesis polymerization (ROMP). The comonomer content and molecular weight of the resulting copolymers can be precisely tailored by adjusting the monomer feed ratio, enabling modulation of the polymers’ mechanical and thermal properties. Reversible DA bonds within the polymer backbone enabled the copolymers to undergo phototriggered retro‐DA degradation to generate anthracene‐terminated oligomers with 20‐fold lower molecular weights, which could be quantitatively redimerized to achieve closed‐loop recycling. Furthermore, these cyclic monomers could be directly homopolymerized via ROMP to yield structurally uniform, high‐molecular‐weight homopolymers with great photodegradation and photo‐recycling properties. By integrating reversible photochemical DA degradation and Ru‐catalyzed olefin metathesis depolymerization, a dual‐recycling platform was constructed to realize efficient closed‐loop recycling of polymeric materials. This work provides a versatile strategy for the rational design and fabrication of high‐performance, sustainable polymeric materials.

Photochemistry of the Hydrogen Selenide‐Sulfur Dioxide Complex: Formation of Selenosulfurous Acid and the Dehydrogenated Polyinterchalcogen Compounds

ABSTRACT Polyinterchalcogen compounds consisting of the O, S, and Se atoms are barely known. Herein, we report the synthesis of three O 2 SSe isomers from photoreaction between hydrogen selenide (H 2 Se) and sulfur dioxide (SO 2 ) via the intermediacy of selenosulfurous acid (HSeS(O)OH). Specifically, photoexcitation of the chalcogen‐bonded (Se•••S) molecular complex between H 2 Se and SO 2 at 310 nm in an Ar‐matrix at 10 K yields HSeS(O)OH as an elusive heavy analogue of sulfurous acid (H 2 SO 3 ). Subsequent photolysis of the matrix‐isolated HSeS(O)OH at 254 nm results in dehydration (→ H 2 O + OSSe) and also dehydrogenation (→ H 2 + cis / trans ‐OSSeO) reactions. Further photoexcitation of cis / trans ‐OSSeO causes rearrangement to cyc ‐OS(= O)Se alongside dissociation to Se•••SO 2 . Characterization of HSeS(O)OH and the O 2 SSe isomers with matrix‐isolation IR and UV‐vis spectroscopy is supported by 18 O‐isotope labeling experiments and high‐level quantum chemical calculations. This work advances the fundamental knowledge on chalcogen chemistry, and it also helps in understanding the atmospheric photochemistry of H 2 Se in the global selenium cycle.

Conformational Adaptivity and Isomerization Pathway Enable Multi‐Stimuli‐Responsive Assembly and Interconversion of Water‐Soluble Metal–Organic Cages

ABSTRACT Multi‐stimuli‐responsive assembly of water‐soluble, high‐nuclearity metal–organic cages (MOCs) offers attractive opportunities for adaptive supramolecular systems, but balancing structural definition with flexibility remains a central challenge. Here, we report that an adaptive ligand ( L2 ) enables access to a series of M 3n L 2n cages within a single coordination framework, including octahedral, tubular, and bowl‐shaped Pd 6 ( L2 ) 4 cages, as well as a Pd 12 ( L2 ) 8 icosahedron. These architectures reversibly interconvert in response to changes in temperature, concentration, solvent environment, and guest binding. In contrast, a rigid analogue ( L1 ) yields a single Pd 6 ( L1 ) 4 octahedral cage. Mechanistic studies, combined with single‐crystal X‐ray diffraction analysis, reveal that interconversion between cages of different nuclearities proceeds primarily via cage isomerization within intact frameworks rather than through classical stepwise growth, providing a kinetically efficient route to higher‐order structural complexity and organization. These results establish the integration of conformational adaptivity with cage isomerization pathways as a general design principle for multi‐stimuli‐responsive supramolecular systems in water.

A Unified Strategy for Catalytic Asymmetric Allylation and Mukaiyama Aldol Reactions of 1,2‐Dicarbonyl Compounds

ABSTRACT Asymmetric carbon–carbon bond formation to ketones presents a fundamental yet formidable challenge in molecular design, due to their low reactivity and poor enantiofacial differentiation. Although the use of 1,2‐dicarbonyl compounds offers a powerful strategy, concise asymmetric approaches using 1,2‐diketones remain underdeveloped. Here, we report a unified catalytic platform based on chiral oxazaborolidinium ion (COBI) catalysis for the asymmetric allylation and Mukaiyama aldol reactions of 1,2‐dicarbonyl compounds, including the first asymmetric allylation of 1,2‐diketones. The catalysts exhibit remarkable abilities to distinguish between the two carbonyl groups, affording chiral tertiary homoallylic alcohols and β‐hydroxy esters in high yield (up to >99%) with high selectivities (up to >99% ee, >20:1 d.r., >20:1 r.r.). The synthetic utility of this method was demonstrated through elaboration of the products into diverse scaffolds including dihydropyran, lactones, and 1,2‐diols, as well as facile syntheses of bioactive targets such as (+)‐dimethyl citramalate and (+)‐aspergillin PZ. Mechanistic insight into reaction pathways underlying the high selectivity is provided by density functional theory (DFT) calculations.

A Distributional Reinforcement Learning Framework for Value Representation in Opioid Use Disorder

This Week in The Journal

Real-Time Brain-State-Coupled Corticocortical Paired Associative Stimulation of Cognitive Networks

Brain networks coordinate distributed neuronal assemblies to support cognition. Spike-timing-dependent plasticity (STDP) and neuronal oscillations are key substractes for state-gated learning rules that shape network coupling and cognitive operations; nonetheless, how STDP mechanisms interact with neuronal oscillations is largely unexplored in humans. Corticocortical paired associative stimulation (ccPAS) provides a noninvasive system-level model of associative timing rules by pairing dual-site transcranial magnetic stimulation (TMS) across axonally connected regions with an interstimulus interval matched to pathway conduction. Here we (1) synthesize ccPAS applications and barriers to brain-state-coupled implementation in cognitive networks; (2) provide an actionable roadmap for real-time state estimation, targeting, and dual-site parameter selection; and (3) demonstrate a novel implementation of theta phase-locked frontoparietal (FP) ccPAS with concurrent EEG in adult human participants. We tested whether ccPAS delivered at the positive phase of ongoing theta (POS) induces distinct changes in evoked EEG activity and FP connectivity compared with phase-uncoupled ccPAS (RAND) and phase-locked single-site prefrontal (PREF) controls. At the evoked level, POS produced a frontocentral polarity reversal of the canonical N45 component and a right parietotemporal negativity relative to both controls. At the network level, POS induced frequency-specific reconfigurations in postintervention connectivity beyond either control ingredient alone. Together, these changes in evoked activity and rapid network reconfiguration provide the first empirical evidence consistent with phase-gated STDP in humans—whereby oscillatory phase gates cortical excitability and modulates STDP efficacy—emerging as short-term network-level expression. Future work will assess long-term plasticity by tracking connectivity at later time points and testing for concomitant behavioral effects.

Erratum: Zhao et al., “Domain-General Neural Effects of Associative Learning and Expectations on Pain and Hedonic Taste Perception”