ASAP (As Soon As Publishable)

The production of functional hierarchical architectures through the biomineralization of a continuously secreted protein matrix is prevalent in nature; however, it remains challenging to mimic this dynamic aspect of the biomineralization process, especially in biological systems. Here we report the use of dynamically generated supramolecular assemblies of peptides for in situ biomimetic mineralization in live cells. Specifically, by integrating enzymatic regulation of inorganic phosphate concentration and enzyme-instructed self-assembly, we demonstrate a phosphorylated tripeptide that self-assembles into dynamic supramolecular nanofibers via enzymatic dephosphorylation to template biomineralization with the inorganic phosphate. This biomimetic mineralization results in the formation of peptide–inorganic hybrid nanocrystals, with tunable crystal size and calcium-to-phosphorus (Ca:P) ratio, regulated by enzyme activity. Cellular enzymes can instruct in situ biomineralization around mammalian cells, inducing cell aggregation and osteogenic differentiation. This work presents a novel strategy for mimicking the dynamic biomineralization of a protein matrix and regulating biomimetic mineralization in live cells to control the cell fate.

Cleaving the C(sp³)–N bonds in unstrained cyclic monomers for ring-opening polymerization remains a formidable challenge in polymer chemistry. Here, we report a novel strategy that integrates the cascade aza-Michael/retro-aza Michael reaction with a chain growth polymerization mechanism. For the first time, this approach cleaves the C(sp³)–N bond in less-strained cyclic monomers under ambient conditions, yielding cinnamate-containing polyamines with controlled molecular weight, narrow dispersity, and unexpected cis-stereoselectivity. A linear relationship between the number-average molecular weight and the conversion, high chain-end fidelity, and efficient chain extension proved excellent control over the polymerization process. In addition, density functional theory calculations were conducted to clarify the origin of the observed stereoselectivity. The versatility of this polymerization was further demonstrated through the copolymerization with aziridine monomers and the synthesis of sequence-controlled polymers. This protocol provides a new C–N cleavage pattern for ring-opening polymerization and would lead to a more useful synthetic pathway to polymers with main-chain functionalities.

The rise of quantum information science has spurred chemists to prepare new molecules that serve as useful building blocks in quantum technologies of the future. Implementation of molecular spin-based qubits requires new methods to induce high spin polarization of samples. Herein, we report design criteria to develop axially symmetric spin-1/2 molecules amenable to optically induced magnetization (OIM), a technique using circularly polarized (CP) excitation to deliver spin polarization. We apply these criteria to develop a series of tungsten(V) chalcogenide complexes that are demonstrated to have large spin-sensitive responses to CP light using magnetic circular dichroism (MCD) that could allow up to ∼20% spin polarization through OIM. Pulsed electron paramagnetic resonance (EPR) spectra reveal these systems have improved relaxation times over molecules like K₂IrCl₆, a species recently investigated by OIM, and field-swept electron spin–echo (FS-ESE) experiments show they have a remarkable lack of anisotropy in their phase-memory T_m times. The design criteria are general and point toward future ways to improve OIM-initializable qubits.

Molecule-based magnetic materials have been identified as promising candidates for application in magnonic technologies, owing not only to their solution processability but also because they can exhibit narrow ferromagnetic resonance (FMR) linewidths and low Gilbert damping coefficients─crucial prerequisites for the transmission of coherent magnons over macroscopic distances. In particular, V(TCNE)₂, a compound with a three-dimensional network structure composed of vanadium(II) centers linked by tetracyanoethylene (TCNE^•–) radical anions, displays magnonic properties comparable to yttrium iron garnet, the quintessential magnonic material in the field. However, existing solution and chemical vapor deposition methods for synthesizing V(TCNE)₂ require the use of highly reactive zero-valent molecular vanadium precursors, stymying research on this important material. Herein, we report a facile electrochemical method for the deposition of thin films of V(TCNE)₂ using readily obtainable and stable divalent vanadium precursors and TCNE^•– anions generated by electrochemical reduction. Magnetization measurements reveal that the films exhibit ferrimagnetic ordering above room temperature, consistent with V(TCNE)₂ films synthesized via other methods. Moreover, the electrodeposited films exhibit narrow FMR linewidths as low as 17.5 G and a low Gilbert damping coefficient of 1.1 × 10^–3, values that are on par with some currently integrated metallic magnonic materials. More generally, these results demonstrate that electrodeposition can provide a straightforward means of generating high-performance magnonic materials using readily available molecular precursors.

The simultaneous construction of C–C and C–X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.

Classical empirical force fields have dominated biomolecular simulations for over 50 years. Although widely used in drug discovery, crystal structure prediction, and biomolecular dynamics, they generally lack the accuracy and transferability required for first-principles predictive modeling. In this paper, we introduce MACE-OFF, a series of short-range transferable force fields for organic molecules created using state-of-the-art machine learning technology and first-principles reference data computed with a high level of quantum mechanical theory. MACE-OFF demonstrates the remarkable capabilities of short-range models by accurately predicting a wide variety of gas- and condensed-phase properties of molecular systems. It produces accurate, easy-to-converge dihedral torsion scans of unseen molecules as well as reliable descriptions of molecular crystals and liquids, including quantum nuclear effects. We further demonstrate the capabilities of MACE-OFF by determining free energy surfaces in explicit solvent as well as the folding dynamics of peptides and nanosecond simulations of a fully solvated protein. These developments enable first-principles simulations of molecular systems for the broader chemistry community at high accuracy and relatively low computational cost.

Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since water is typically used as both a solvent and a proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during the carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water–water clusters lead to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22% in acetonitrile (χ_H2O = 0.2). In contrast, microhomogeneous systems–where water integrates into the solvents’ intermolecular binding network and has lower activity–primarily support the undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformation reactions beyond CO reduction, such as CO2RR and HER.

Antiaromatic compounds are of great interest due to their narrow highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps, high reactivity, and enhanced charge mobility, yet their role in single-molecule electronics is still not well understood. Using electrochemically controlled scanning tunneling microscopy break junction (ECSTM-BJ) measurements, we compared the energy-alignment-dependent conductance of the aromatic [10]cycloparaphenylene ([10]CPP) and the antiaromatic [4]cyclodibenzopentalene ([4]CDBP). While [10]CPP showed a single conductance state via the HOMO, [4]CDBP exhibited two distinct states involving both the HOMO and LUMO. Our analysis and DFT calculations attribute this dual-state behavior to unique anchoring mode and energy-level realignment within a narrow HOMO-LUMO gap. This property enables electron- and hole-dominated pathways that depend on the anchoring configuration and coexist at a fixed gate potential. This phenomenon, also observed in the [4]CDBP⊃C₆₀ structure, highlights the potential of antiaromatic molecules for advanced molecular electronics.

Mechanoluminescence (ML) materials with phosphorescent characteristics hold significant potential for applications in pressure sensing and material damage inspection. However, currently reported mechanophosphorescence (MP) materials suffer from low luminescence efficiency and insufficient brightness. Herein, we report a piezoelectric material, p-BPM, with an exceptionally high phosphorescence efficiency of 61.4%, which is the highest value among reported pure organic MP materials. Benefiting from its excellent ML performance, we have developed a display device using crystals that allow for clear observation of the written letter paths (letters M and L), which have promising prospects in pressure-sensitive display. Amazingly, we also observed that the crystals produce bright ultrasound induced luminescence in the medium at a low ultrasonic operating frequency (40 kHz). The composite films of crystal and poly(butylene adipate-co-terephthalate) (PBAT) polymer exhibit significant tensile strength while maintaining effective MP. The composite films show good piezoelectric energy harvesting properties with a maximum open-circuit voltage of 0.47 V and short-circuit current of 0.046 μA, demonstrating promise for precise sonic location. This work will facilitate the development of highly efficient organic MP materials, expanding the potential in stress-monitoring, imaging, and marine robotics.

Rechargeable Na/Cl₂ batteries were developed for the first time using multiwalled carbon nanotube (MWCNT) positive electrodes in SOCl₂-based electrolytes. At room temperature, these batteries delivered high cycling specific capacities up to 3500 mA h g^–1 (normalized to CNT mass) with ∼3.9 V discharge voltage at up to 2 C rates over >140 cycles. In situ Raman spectroscopy experiments combined with real-time optical microscopy imaging revealed reversible formation and reduction of SCl₂ and S₂Cl₂ species during battery operation, responsible for the additional plateaus to the main Cl^–/Cl₂ redox reactions. Cryo-TEM revealed NaCl nanocrystals inside the hollow inner space of CNTs through battery cycling, suggesting Cl^–/Cl₂ redox reactions reaching hollow CNTs likely through defects and open ends on MWCNTs. High-resolution electron energy loss spectroscopy (EELS) mapping revealed Cl uniformly distributed along CNTs in the charged state, suggesting CNTs as a novel carbon material to host Cl^–/Cl₂ redox and store chlorine for reversible conversion between NaCl and Cl₂ and battery rechargeability.

Iron-based superconductors have attracted much attention for their high superconducting temperatures and high upper critical fields, which make them promising candidates for application as well as fundamentally important for our understanding of superconductivity. One feature of these superconductors is their ability to intercalate and deintercalate species from between their iron-containing layers, something not available in cuprate high-temperature superconductors or niobium-based conventional superconductors used in technologies. This provides an opportunity for switchable changes in the superconducting properties as a function of chemical conditions, but the resulting structures are often hard to characterize due to loss of crystallinity and sometimes the formation of multiphase products. Here, we explore both the synthesis and decomposition of potassium and ammonia-intercalated iron selenide superconductors through in situ powder X-ray diffraction. We report a complete phase diagram including two new solution-stable ammonia-rich phases and several metastable forms. We give accurate characterization of the reported ammonia-poor forms using a combination of neutron and X-ray powder diffraction, using an innovative supercell approach to describe the phase breadth within the samples. These results give rare insight into stepwise changes occurring in solids along multiple reaction pathways, which demonstrate the importance of in situ diffraction techniques.

Ni-rich layered oxides have emerged as the most promising cathode materials for next-generation lithium-ion batteries due to their high energy densities. However, their strain-related instabilities, for example, microcracks and rock-salt phase formation, present a significant threat to battery performance. In this study, we successfully stabilize the structure of LiNi_0.8Co_0.1Mn_0.1O₂ using flexible TiO₆ octahedron units through high-concentration surface Ti doping. The TiO₆ octahedron can tolerate Jahn–Teller distortions of other neighboring structural units due to the absence of d electrons in Ti⁴⁺, allowing them to accommodate undesirable lattice distortions within the local domain and mitigate the lattice strain/changes. Compared with the conventional approach of increasing the rigidity of the layered structure, our strategy of using flexible TiO₆ structural units can fundamentally address the strain-related issues, contributing to significantly reduced lattice changes, especially along the c-direction (by 95.2%). This approach enables a high battery capacity (211.5 mAh g^–1 at 0.1 C) and long battery durability of Ni-rich cathodes, surpassing most commercial products on the market. The strategy of surface optimization using flexible structural units to stabilize Ni-rich layered oxides can be broadly applied to other battery materials to address performance issues due to the similarities among layered-structured cathode materials.

Zeolites are highly sensitive to water, which significantly affects their acidity─a key factor in catalytic reactions. This study investigates the dynamic interactions between water and often overlooked active sites, specifically the “NMR-invisible” aluminum species (tricoordinated framework Al─FAL and cationic extra-framework Al─EFAL) in ultrastable Y (USY) zeolite under ambient conditions. Using solid-state NMR spectroscopy combined with theoretical calculations, we demonstrate that water readily undergoes dissociative adsorption on these “NMR-invisible” Al sites. This process transforms both FAL and EFAL into “NMR-visible” Al species. The formation of new Brønsted acid sites on tetra-, penta-, and hexa-coordinated FAL results in an increase of over 60% in the BAS concentration in the USY zeolite. The hydrolysis of EFAL cations leads to the formation of Brønsted/Lewis acid synergistic sites, significantly improving the catalytic activity of USY zeolite. This enhancement is evident in the improved conversion of diethyl ether to ethene in the presence of moisture.

Generating stimulus-responsive allosteric signaling de novo is a significant challenge in protein design. In natural systems like bacterial histidine kinases (HKs), signal transduction occurs when ligand binding initiates a signal that is amplified across biological membranes over long distances to induce large-scale rearrangements and phosphorylation relays. Here, we ask whether our understanding of protein design and multidomain, intramolecular signaling has progressed sufficiently to enable engineering of a HK with tunable de novo components. We generated de novo metal-binding sensor domains and substituted them for the native sensor domain of a transmembrane HK, affording chimeras that transduce signals initiated from a de novo sensor. Signaling depended on the designed sensor’s stability and the interdomain linker’s phase and length. These results show the usefulness of de novo design to elucidate the biochemical mechanisms and principles of transmembrane signaling.

Rhenium(I) tricarbonyl complexes fac-[Re(bpy)(CO)₃(L)]ⁿ⁺ are the classic examples of self-sensitized photocatalysts capable of the dual roles of light absorption and catalysis. In this work, a series of dicationic halido or tricationic solvento complexes fac-[Re(bpy²⁺)(CO)₃X]ⁿ⁺ (PF₆)_n (where X = Cl^– or I^– (n = 2), or CH₃CN (n = 3) and bpy²⁺ is bipyridine modified by two −CH₂–(NMe₃)⁺ tetra-alkylammonium cations) have been investigated as self-sensitized and sensitized CO₂ reduction photocatalysts. Four structural isomers differing in the cation position have been tested in N,N′-dimethylacetamide solvent (DMA) using 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (BIH) as the electron donor, and the position of the cationic pendants has a significant impact on the catalyst turnover number and quantum efficiency (ϕ). Up to 455 self-sensitized turnovers of CO and a high photon efficiency (ϕ_CO) of 22% have been achieved. Time-resolved infrared spectroscopy and theoretical calculations were used to characterize the catalytic cycle including the ligand exchange between one-electron reduced (OER) halido and solvento species as well as the binding of CO₂ to the putative two-electron reduced (TER) species. The CO₂-reactive TER catalyst was formed by disproportionation or intramolecular electron transfer between two forms of the OER catalyst as indicated by the formation of the fully oxidized catalyst concurrent with CO₂ binding. When [Ru(bpy)₃]²⁺ was used as a sensitizer, catalyst durability improved, and the selectivity toward formate increased as high as 3.3:1 over CO (total TON = 1370) due to acidification of the reaction, which promotes formation of the hydride intermediate, as BIH was consumed and deprotonated.

Photoelectrochemical (PEC) chloride oxidation reaction offers a green and sustainable approach for the synthesis of chlorinated chemicals, pesticides, pharmaceuticals/drugs, etc. However, until now, efficient PEC chloride activation remains highly challenging, primarily due to the lack of effective catalytically active reaction sites on the developed photoanodes. Herein, we construct a high-performance photoanode for PEC C–H chlorination by controllably embedding Pt single atoms onto positively charged TiO₂ nanorod arrays (denoted as Pt₁-p-TiO₂ NRAs). The one-dimensional single-crystalline TiO₂ nanorods not only create a rapid electron transport pathway but also orthogonalize the light absorption and hole transport directions, effectively suppressing photogenerated electron–hole recombination. Furthermore, the positively charged TiO₂ nanorod surface induced by electrochemical reduction can facilitate the anchoring of single Pt atoms as C–H chlorination active sites onto TiO₂ and at the same time modulate the charge carrier dynamics. Consequently, high selectivity (up to 87%) and Faradaic efficiency (close to 60%) toward chlorination of organics are achieved over Pt₁-p-TiO₂ NRAs using NaCl as the chlorine source under light illumination. PEC experiments and mechanistic investigations demonstrate that the single Pt atoms on TiO₂ nanorods can help to effectively separate photoexcited charge carriers and induce preferable chloride ions’ adsorption as well as electron transfer from Pt single atoms to TiO₂ nanorods to generate reactive chloride radicals (Cl•), which play a key role in PEC C–H chlorination.

Unraveling the mechanism of zeolite crystallization, especially in a complex system containing dual-template agents, remains a critical challenge. In this work, we introduced, for the first time, novel operando two-dimensional (2D) solid-state NMR spectroscopy under extreme conditions of high temperature and high pressure, allowing for observations with atomic-level spatial and temporal resolution, thereby enabling unprecedented insights into the crystallization of SAPO-34 zeolite. By utilizing operando 2D ³¹P{¹H} HETCOR, ²⁷Al{¹H} HMQC NMR techniques, we clarified the intricate cooperative and competitive interactions of dual-template agents and highlighted the synergistic effect between templates and hydroxyl groups during CHA zeolite crystallization. Furthermore, operando ¹H, ²⁷Al, and ³¹P MAS NMR revealed a previously unreported induction period, which precedes intermediate formation. This innovative approach advances the understanding of molecular dynamics, crystallization mechanism, and synthesis method for zeolites, representing a significant leap forward in the field of operando two-dimensional solid-state NMR spectroscopy.

Peptide natural products (PNPs) are important sources of bioactive compounds. Recent studies have shown that oligopeptides or pseudopeptides can be synthesized by amide-bond-forming enzymes such as ATP-grasp enzymes and amide-bond synthetases (ABSs). By focusing on ATP-grasp enzymes as part of a conserved biosynthetic enzyme ensemble, genome mining of PNPs was performed on three biosynthetic gene clusters (BGCs) from diverse fungi, including Coccidioides immitis RS, the causative agent of valley fever. We demonstrate that the conserved enzymes synthesize a common dipeptide fragment, l-leucine-l-O-isoindolinone-homoserine (l-Leu-l-Isd), which is modified and diversified into three PNPs (1–3) by associated enzymes in the three pathways. Pathway reconstitution and enzymatic assays led to the characterization of six ATP-grasp enzymes and ABSs that catalyze di-, tri-, and tetrapeptide formation. From the C. immitis BGC, a flavoenzyme catalyzing the direct oxidation of l-tryptophan to l-oxindolylalanine was discovered. Our work validates ATP-grasp enzymes and ABSs as leads to mine new PNPs and further showcases the biocatalytic potential of these enzymes in catalyzing amide-bond formation.

The reliance of modern technology growth on lanthanides presents dual challenges: securing sustainable sources from natural or recycled materials and reducing environmental harm from waste discharge. However, the similar ionic radii, oxidation states, and binding affinities of Ln³⁺ ions hinder their nondestructive detection in mixtures. Furthermore, the overlap of spectroscopic signals and the inapplicability for opaque solutions limit the harness of luminescent sensors for differentiating one Ln³⁺ from another. Here, we introduce ¹⁹F-paramagnetic guest exchange saturation transfer magnetic resonance fingerprinting (¹⁹F-paraGEST MRF), a rapid signal acquisition, encoding, and analysis approach for detecting specific Ln³⁺ in mixtures. Based on a small-sized experimental ¹⁹F-paraGEST data set, we generated a de novo dictionary of ∼2500 combinations of Ln³⁺ mixtures, resulting in ∼7,000,000 simulated ¹⁹F-paraGEST MRF patterns of different Ln³⁺ concentrations. This dictionary was later used for computational pattern recognition of experimental NMR signal evolutions (“fingerprints”), utilizing a rapid computational approach executable on a standard laptop within seconds. Hence, fast and reliable multiplexed lanthanide detection in complex mixtures was enabled. Demonstrated through the analysis of lanthanides’ content of permanent magnets from a hard disk drive, this MR-based method paves the way for broader applications of lanthanide detection in murky, nontransparent mixtures and further exploration of supramolecular sensors in diverse scenarios.

The energy-intensive distillation currently used for C₃H₆/C₃H₈ separation─challenged by their small boiling point difference─could be improved via adsorption. However, most porous materials face a trade-off among C₃H₆ adsorption capacity, selectivity, and kinetics. Herein, we report the synthesis and characterization of a novel metal–organic framework, denoted NiPz₄Bim, constructed from a weak Lewis-base pyrazole-based ligand Pz₄Bim and the weak Lewis-acid Ni²⁺, featuring 3D pore structures with nanocavities (∼1 nm) connected by very narrow apertures (∼5 Å). This framework enables efficient C₃H₆/C₃H₈ separation by combining selective adsorption with enhanced diffusion kinetics for C₃H₆. Specifically, adsorption capacities at 298 K and 1 bar were recorded as 3.24 mmol g^–1 for C₃H₆ and 2.74 mmol g^–1 for C₃H₈, with selectivity ratios of up to 2.42. Kinetic uptake analysis using the effective diffusion coefficient (D′) revealed a significant difference in the adsorption rates of the two gases, corresponding to a kinetic selectivity of 51.96. Neutron powder diffraction, coupled with grand canonical Monte Carlo simulations and density functional theory calculations, directly visualizes the binding domains of adsorbed gases and the dynamics and energetics of the host–guest interactions. These studies reveal that the unique nanosized cavities with narrow apertures in NiPz₄Bim facilitates van der Waals and π-π interactions with C₃H₆, enabling selective trapping over C₃H₈. Crucially, NiPz₄Bim exhibits high stability and reusability in multicycle tests, demonstrating its practical viability. This work highlights the importance of pore-geometry engineering in framework materials for the efficient separation of structurally similar molecules, with immediate implications for sustainable olefin production.

While the chemical vapor deposition (CVD) process promises high-quality films of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), strategic approaches are limited. Here we report a new strategic approach to synthesizing imine-linked COF films through acid-amine salt films by CVD. Acids are known to catalyze imine condensation between amines and aldehydes in the solution phase and have been believed to do the same in the vapor phase reaction. Upon the attempts to synthesize COF-LZU1 thin films using p-phenylenediamine, 1,3,5-triformylbenzene, by CVD, highly crystalline and smooth COF-LZU1 films are obtained only in the presence of p-toluenesulfonic acid, proving the conventional role of acid during vapor phase imine condensation. The COF-LZU1 film has a mixed orientation according to the structure analysis by grazing-incidence wide-angle X-ray scattering. In contrast, amorphous films with a face-on orientation were obtained in the absence of an acid. The role of acid in modulating structure is confirmed from the reaction using a different acid, benzenesulfonic acid, which results in the COF-LZU1 film having an edge-on orientation. The control experiments using benzoic acid and succinic acid that failed to make either acid-amine salt or COF films explain that the acid-amine-salt film formation is crucial to the formation of imine-linked COF films by CVD. Our findings not only explain the limited kinds of active acids for imine condensation in the vapor phase but also widen the field for the facile synthesis of highly crystalline COF films by CVD and the structure control of COF films through the combination of an acid-amine salt.

The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene (iPP) has gained increasing attention due to their ability to improve the recycling of incompatible mixed polyolefin waste feed streams. Herein, we report a new radical grafting process that yields HDPE-g-iPP copolymers from HDPE and iPP by using a commercially available peroxide. Tensile testing of brittle 70/30 HDPE/iPP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and iPP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE-g-iPP copolymers that compatibilize HDPE and iPP blends at loadings as low as 2.5 wt %. The versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated postconsumer waste plastics.

Electrocatalytic water splitting, comprising the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), provides a sustainable route for hydrogen production. While low-cost metal oxides (MOs) are appealing as alternatives to noble metal electrocatalysts, their application in acidic media remains challenging. However, the dynamic nature of some MO surface structures under electrochemical conditions offers an opportunity for rational catalyst design to achieve bifunctionality in acidic OER and HER. Here, we present a closed-loop framework that integrates potential catalyst exploration (front-end), synthesis and electrochemical tests (mid-end), and advanced characterizations (back-end). This framework combines crucial steps in electrocatalyst exploration, including data mining, surface state analysis, microkinetic modeling, and proof-of-concept experiments to identify stable and cost-effective MO catalysts for acidic water splitting. Using this approach, RbSbWO₆ is identified as a promising bifunctional catalyst for the first time, with experimental validation demonstrating its exceptional stability and performance under acidic OER and HER. Notably, RbSbWO₆ outperforms many other reported non-noble stoichiometric MO catalysts that have not undergone major modifications for acidic water splitting. These findings, derived from our Digital Catalysis Platform (DigCat), establish RbSbWO₆ as a highly effective non-noble stoichiometric bifunctional MO catalyst and underscore the power of our closed-loop workflow for accelerating catalyst discovery. This framework begins with the DigCat platform, concludes with experimental validation, and feeds into the platform, demonstrating its potential for designing electrocatalysts in other systems such as metal nitrides or carbides. This study demonstrates the importance and high efficiency of data-driven approaches as a new scientific discovery paradigm.

Understanding and overcoming the chemomechanical failures of polycrystalline inorganic solid-state electrolytes (SSEs) are critical for next-generation all-solid-state batteries. Yet, so far, the nanoscale origin of SSEs’ chemomechanical failure under operation conditions remains a mystery. Here, by using in situ electron microscopy, we decipher the nanoscale origin of the soft-to-hard short-circuit transition─a conventionally underestimated failure mechanism─caused by electronic leakage-induced Li⁰ precipitation in SSEs. For the first time, we directly visualize stochastic Li⁰ interconnection-induced soft short circuits, during which the SSEs undergo the transition from a nominal electronic insulator to a state exhibiting memristor-like nonlinear conduction (electronic leakages), ultimately evolving into hard short circuits. Furthermore, we first capture intragranular cracking caused by Li⁰ penetration, demonstrating that fully wetted Li⁰ can fracture polycrystalline oxide SSEs via a liquid-metal embrittlement-like mechanism. Guided by these insights, we show that incorporating an electronically insulating and mechanically resilient 3D polymer network into an inorganic/polymer composite SSE effectively suppresses Li⁰ precipitation, interconnection, and short circuits, significantly enhancing its electrochemical stability. Our work, by elucidating the soft-to-hard short-circuit transition kinetics of SSEs, offers new insights into their nanoscale failure mechanisms.

Materials in which atoms are arranged in a pyrochlore lattice have found renewed interest, as, at least theoretically, orbitals on that lattice can form flat bands. However, real materials often do not behave according to theoretical models, which is why there has been a dearth of pyrochlore materials exhibiting flat band physics. Here, we examine the conditions under which ideal “pyrochlore bands” can exist in real materials and how to have those close to the Fermi level. We find that the simple model used in the literature does not apply to the bands at the Fermi level in real pyrochlore materials. However, surprisingly, we find that certain oxide compounds that have oxygen orbitals inside the pyrochlore tetrahedra do exhibit near-ideal pyrochlore bands near the Fermi level. We explain this observation by a generalized tight-binding model, including the oxygen orbitals. We further classify all known pyrochlore materials based on their crystal structure, band structure, and chemical characteristics and propose materials to study in future experiments.

An accurate understanding of the mechanism of the oxygen evolution reaction (OER) is crucial for catalyst design in the hydrogen energy industry. Despite significant advancements in microscopic pH detection, selective, sensitive, speedy, and reliable detection of local pH gradients near the catalysts during the OER remains elusive. Here, we pioneer an electrochemiluminescence (ECL) method for local pH detection during the OER. For this purpose, a new class of ECL emitters based on ECL resonance energy transfer was theoretically predicted and facilely synthesized by grafting functional fluorescent dyes onto noble 2D carbon nitride. By positioning one of the as-prepared ECL emitters with pH-responsibility neighboring the OER catalysts, local pH gradient generation near the catalysts could be qualitatively measured in real-time with a subsecond resolution. It provided details of the reaction mechanism of the OER and unveiled the catalyst degrading pathway caused by proton accumulation. Besides, the average proton generation rate on the catalyst was also extractable from the local pH measurement as a quantitative descriptor of the OER reaction rate. Owing to the high designability of the grafting method, this study opens up new strategies for studying reaction mechanisms and detecting intermediates.

Electrocatalytic C–N reductive coupling offers a sustainable and eco-friendly approach to producing value-added oximes. The challenge lies in the overstrong chemisorption of N-containing intermediates and carbonyl compounds on metal-based catalysts, which causes low Faradaic efficiency and yield rates, as well as undesired byproducts. Here, we propose a multiple secondary bond-mediated strategy for C–N coupling toward benzaldoxime on a nitrogen-doped graphene-like carbon catalyst (NC). Integrating theoretical and experimental analyses, we demonstrate that the graphitic-N–C sites in NC promote nitrite reduction into hydroxylamine via weak electrostatic interaction. Moreover, the hydrogen bonds and π–π stacking interactions among NC, hydroxylamine, and benzaldehyde synergistically enrich the key intermediates on the catalyst surface and inhibit the side reactions, leading to a highly selective C–N coupling process. Remarkably, the NC catalyst achieves a high Faradaic efficiency of 73 ± 1% and a yield rate of 6.8 ± 0.1 mol h^–1 m^–2 for benzaldoxime electrosynthesis at an economically viable current density of 0.1 A cm^–2, as revealed by technoeconomic analysis. Our results demonstrate an appealing route for high-performance C–N coupling with enhanced economic feasibility.

Current amplification plays an essential role in electrochemistry by improving the productivity of the electrochemical production of industrial materials and enhancing the sensitivity of environmental and biomedical sensing. Various approaches have been explored to enhance steady-state current, such as thin-layer reactors, microelectrodes, and rotating-disk electrodes. Thin-layer reactors have several advantages, including the ability to generate larger currents using bulk-sized electrodes and simple fabrication processes. In this study, we developed a thin-layer reactor using boron-doped diamond (BDD) electrodes with an interelectrode distance of several tens of micrometers, which is comparable to the thickness of a diffusion layer. The use of BDD electrodes enabled reversible redox cycling in the thin-layer reactor, resulting in more than 2-fold current amplification compared to conventional thin-layer reactors. This effect was observed only when BDD electrodes were used for both the working and counter electrodes, and the interelectrode distance was 200 μm and below. Based on the experimental results of the present study, we propose a novel concentration profile model and reaction mechanism for BDD thin-layer reactors that cannot be explained by conventional thin-layer reactor models. The model involves a three-step reversible redox cycle: (1) consumption of reduced species and generation of oxidized species at the working electrode, (2) regeneration of reduced species at the counter electrode, and (3) resupply of reduced species to the working electrode. The BDD thin-layer reactor also demonstrated twice the sensitivity, and a detection limit one-tenth those of the conventional bulk-reactor in electrochemical detection based on the proposed model.

The use of water as a solvent to facilitate supramolecular self-assembly and polymerization is well-documented; however, it is rare that water acts as a monomer that undergoes polymerization. We report the formation of nanosheets composed of water and a saddle-shaped porphyrinoid macrocycle, carpyridine, which allows for linearly stacked, eclipsed columns within formed 2D structures. Self-assembling carpyridine monomers from solutions with different extents of wetness permit the formation of nanosheets that appear identical by microscopy. Structural analysis through electron diffraction reveals fundamental changes in the local organization. Under dry conditions, carpyridine stacks are formed through π–π interactions between curved surfaces, whereas in solutions containing greater quantities of water, a hydrogen-bonded water-to-carpyridine-core network is propagated throughout perfectly linear columns. The observed wet phase can be interconverted to a dry one through vapor annealing, indicating an accessible energy surface of polymorphism.

Small differences in molecular or solid-state structure can afford significant differences in properties. Here, a diene derivative, 1,3-bis((E)-2-bromostyryl)benzene (2Brm), is synthesized and crystallized into two unique solid-state forms, each exhibiting a different π–π stacking geometry, which imparts distinct reactivity and photoresponsivity. Upon exposure of the two solids to UV–Vis light, a [2 + 2] photocycloaddition occurs to afford regioisomeric products due to the difference in the stacking geometries of the dienes. From a single molecular precursor, we further demonstrate that under different wavelengths of light, the chemical functionality can be programmed into discrete and distinct products containing one, two, or three cyclobutane rings as well as oligomeric/polymeric products. Moreover, the two initial solid forms exhibit wavelength-dependent photomechanical behaviors (i.e., photosalience). This work demonstrates a rare, template-free, self-assembly-based strategy that enables access to a suite of discrete and oligomeric/polymeric products via regiocontrolled solid-state photocycloadditions and further presents potential routes toward the design of photoactuating materials.

Currently, ether- and carbonate-based electrolytes have been extensively studied for applications in harsh conditions; however, it is difficult to develop a suitable electrolyte system that is compatible with both high and low temperatures. Herein, for the first time, a cyclic sulfite-based electrolyte is formulated to successfully achieve the wide-temperature operation of sodium-ion batteries (SIBs) from −60 to 60 °C. By precisely modulating ion–dipole interactions, the dominant ion coordination states are screened directionally to accelerate the desolvation process and simultaneously maintain sufficient electrostatic constraints, laying the foundation for high- and low-temperature compatibility. And the coordinated anions and additives synergistically decompose to enable inorganic-rich interphases with robustness and favorable ion diffusion, extending the voltage window and temperature range. As a result, Na₃V₂(PO₄)₂O₂F demonstrates 58 mA h g^–1 at −50 °C while stably cycling at 60 °C for 300 cycles with 80% capacity retention. Additionally, Na₃V₂(PO₄)₃ and NaFe_1/3Ni_1/3Mn_1/3O₂ cathodes also exhibit discharge specific capacities of 50 and 65 mA h g^–1 at −60 °C. Eventually, the Ah-class pouch cell displays 0.64 A h with 56% capacity retention at −40 °C. In short, the introduced electrolyte formulation enhances the wide temperature operation of SIBs, shedding light on the development of all-weather systems.

Garnet-type solid electrolyte cubic Li₇La₃Zr₂O₁₂ (c-LLZO) emerges as a promising candidate for establishing reliable and high-performance lithium-ion batteries. Its extreme sensitivity to electron irradiation poses a significant challenge in atomically resolving its structure using conventional transmission electron microscopy (TEM) techniques. We demonstrate that the combination of low-dose four-dimensional scanning TEM (4D-STEM) with multislice ptychographic retrieval methodology manages to achieve a sub-Angstrom resolution and the direct visualization of lithium atoms within c-LLZO. The distribution of lithium in depth direction is also obtained. This work provides atomic-scale insights into the distribution of light elements within irradiation-sensitive dense crystals, paving the way for investigating the microstructure–property relationship.

Antimicrobial resistance is an urgent global health challenge, and compounds that address this issue have attracted significant attention. In particular, bioderived molecules that possess natural antimicrobial properties can be useful to prepare active macromolecules that are degradable. In this work, a 4-(methyl/allyl/benzyl)oxy-6-(H/alkyl)-2-oxy-benzoate-co-lactide-based polymer library was designed and studied for antimicrobial activity. The monomer precursors were heterologously produced and purified from an engineered fungal host, chemically modified with 4-(methyl/allyl/benzyl)oxy substituents, and ring-closed to form the 3-methyl-5H-benzo[e][1,4]dioxepine-2,5(3H)-diones. The polymers were synthesized by ring-opening polymerization using a 3-O urea/1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine catalytic system and 3-methyl-butan-1-ol as the initiator. Polymers at different degrees of polymerization were prepared by varying the [monomer]/[initiator] (M/I = 5–30) and tested for activity against the pathogen Staphylococcus aureus. Polymers were identified that were antimicrobial and disrupted biofilms while maintaining good in vitro biocompatibility. The degradability of the polymers was confirmed. Overall, these results demonstrate the power of utilizing a combination of synthetic biology and chemistry to produce functional and degradable polymers that are potent inhibitors of the Gram-positive bacterium S. aureus, with potential applications in medicine.

Endogenous phospholipids influence the conformational equilibria of G protein-coupled receptors, regulating their ability to bind drugs and form signaling complexes. However, most studies of GPCR–lipid interactions have been carried out in mixed micelles or lipid nanodiscs. Though useful, these membrane mimetics do not fully replicate the physical properties of native cellular membranes associated with large assemblies of lipids. We investigated the conformational equilibria of the human A_2A adenosine receptor (A_2AAR) in phospholipid vesicles using ¹⁹F solid-state magic angle spinning NMR (SSNMR). By applying an optimized sample preparation workflow and experimental conditions, we were able to obtain ¹⁹F-SSNMR spectra for both antagonist- and agonist-bound complexes with sensitivity and line widths closely comparable to those achieved using solution NMR. This facilitated a direct comparison of the A_2AAR conformational equilibria across detergent micelle, lipid nanodisc, and lipid vesicle preparations. While antagonist-bound A_2AAR showed similar conformational equilibria across all membrane and membrane mimetic systems, the conformational equilibria of agonist-bound A_2AAR exhibited differences among different environments. This suggests that the conformational equilibria of GPCRs may be influenced not only by specific receptor-lipid interactions but also by the membrane properties found in larger lipid assemblies.

Sulfur-based metal–organic frameworks (MOFs) and coordination polymers (CPs) are an emerging class of hybrid materials that have received growing attention due to their magnetic, conductive, and catalytic properties with potential applications in electrocatalysis and energy storage. In this work, we report a high-throughput virtual screening protocol to predict the synthesizability of candidate metal–sulfur MOFs/CPs by computing the thermodynamically stable structures resulting from a particular combination of metal cluster, linker, cation, and synthetic conditions. Free energies are computed by using all-atom classical mechanical thermodynamic integration. Low-free-energy structures are refined using ab initio density functional theory, and pair distribution functions and powder X-ray diffraction patterns are calculated to complement and guide experimental structure determination. We validate the computational approach by retrospective predictions of the stable structure produced by experimental syntheses, and a subsequent screen predicts Fe₄S₄-BDT–TPP as a new thermodynamically stable one-dimensional (1D) CP comprising a redox-active Fe₄S₄ cluster, a 1,4-benzenedithiolate (BDT) linker, and a tetraphenylphosphonium (TPP) countercation. This material is experimentally synthesized, and the 1D chain structure of the crystal is confirmed using microcrystal electron diffraction. The computational screening pipeline is generically transferable to neutral and ionic MOFs/CPs comprising arbitrary metal clusters, linkers, cations, and synthetic conditions, and we make it freely available as an open source tool to guide and accelerate the discovery and engineering of novel porous materials.

Recently, liquid|liquid and liquid|gas interfaces have been implicated in driving unexpected chemistries, including dramatic rate enhancement and spontaneous redox reactions. Given such studies, new methods are necessary to observe and implicate such reactive species. Tris(2,2'-bipyridyl)ruthenium(II) ([Ru(bpy)₃]²⁺) is a common luminophore for photoluminescence and electrochemiluminescence (ECL) studies. In this work, we demonstrate that the electro-oxidation of [Ru(bpy)₃]²⁺ in water produces light without the addition of sacrificial coreactants. We have studied this by confining [Ru(bpy)₃]²⁺ to an aqueous droplet adhered to both a tin-doped indium oxide electrode and, separately, a glassy carbon inlaid disc macroelectrode (d = 3 mm). We also generalized the method to the observation of light at larger electrodes. The light intensity is higher in the absence of O₂, diminishes when adding H₂O₂, and disappears in the presence of a well-behaved, one-electron oxidant (hexaammineruthenium(III)). Our results indicate that a powerful reducing agent is present during the electro-oxidation of [Ru(bpy)₃]²⁺. This reducing agent is at least energetic enough to create the excited state, [Ru(bpy)₃]^2+*, giving a minimum energy of ∼2 eV. Chemiluminescence persists as [Ru(bpy)₃]³⁺ diffuses into solution, indicating that the strong reducing agent may exist natively in water and at low abundance. These observations have significant fundamental ramifications because they elucidate a new pathway for the [Ru(bpy)₃]²⁺ ECL and allow real-time visualization of highly reactive species.

A novel writhed Möbius nanobelt was synthesized using a helical building block derived from [7]helicene and a C-shaped building block derived from pyrene. These two building blocks were connected through nucleophilic aromatic substitution to form an oxanorbornene-containing macrocycle, which was then converted to the nanobelt by reductive aromatization and subsequent oxidation. The structure of the Möbius nanobelt was confirmed with X-ray crystallography. Both the nanobelt and its macrocyclic precursor exhibit C₂ symmetry, but this symmetry is only reflected by the ¹H NMR signals for the tetra(4-t-butylphenyl)dinaphthopyrene moiety in the nanobelt, not in its precursor. This difference is attributed to the distinct arrangements of the pendent 4-t-butylphenyl groups, caused by the crowdedness and restricted rotation of the C–C single bonds in the nanobelt. Theoretical calculations suggest that the nanobelt does not exhibit global ring currents but has localized aromatic ring currents. Additionally, when an enantiopure form of the [7]helicene derivative was used, the nanobelt was obtained in an enantiopure form, showing an absorption dissymmetry factor of 4 × 10^–3.

Carbon dots are remarkable nanomaterials with many applications, but the sources of their emission are still uncertain. Carbon dots exhibit complex behaviors such as excitation-dependent emission due to their heterogeneous composition and structure. Most studies have been carried out on the ensemble level, where sample heterogeneity remains hidden. Understanding the complex emission of carbon dots requires single-particle measurements. Here, we determined that for red-emitting carbon dots made from two bottom-up precursors, there is a significant population of dots with more than one emitting moiety. Polarization-resolved, single-dot emission microscopy revealed subpopulations of carbon dots based on their emission intensity and polarization. For the multichromophoric carbon dots, we found an average of about four emitters. Single-particle spectroscopy, acquired in parallel to the emission trajectories, and molecular dynamics simulations furthermore established that the countable chromophores in the carbon dots are chemically similar, considering the rather narrow room-temperature emission line width and the absence of significant spectral diffusion.

To engineer biotherapeutics that can specifically target glioma, a highly lethal and recurrent type of brain tumor, we created a class of recombinant chimeric proteins containing multiple functional modules, such as a blood–brain barrier (BBB)-penetrating domain and an immune checkpoint blockade (ICB) agent, PD-L1 nanobody, through fusion protein engineering. The recombinant proteins that could prolong circulation time, cross the BBB, target brain tumors, penetrate cell membranes, and release PD-L1 nanobody were demonstrated. Further, by covalently linking doxorubicin (DOX), an inducer of immunogenic cell death (ICD), to the recombinant proteins, we endow the recombinant protein-drug conjugates (RPDCs) with a combining capacity to induce ICD and block immune checkpoints in cancer cells, achieving significant inhibition of glioma growth and prolonging the survival time of orthotopic glioma-bearing mice by enhancing intratumoral dendritic cell maturation and T-cell activation. In addition, the RPDC also improves the intratumoral immune-suppressive microenvironment, reduces excess extracellular matrix, and alleviates tumor hypoxia. Our work not only offers a new opportunity for glioma treatment but also establishes the groundwork for the design of multifunctional and multitargeting protein-based therapeutics.

Two-dimensional (2D) tin (Sn²⁺)-based perovskites have emerged as promising p-type semiconducting materials for (opto)electronic devices due to their favorable balance of electrical performance and structural stability. While previous studies on 2D perovskites predominantly investigated Ruddlesden–Popper (RP) perovskites with monoammonium spacers, Dion–Jacobson (DJ) perovskites with diammonium spacers have recently sparked attention in the research community. The strong hydrogen bonds at both ends of the diammonium spacer, connecting neighboring inorganic octahedral layers, promote structural stability and efficient charge transport in DJ perovskites. This study systematically investigates a series of 2D DJ Sn²⁺ perovskites, [H₃N-(CH₂)_m-(NH)₃SnI₄] (m = 3–8), to explore the influence from the length of spacer chains on lattice structures, film crystallinity, and charge transport properties. Our findings reveal that DJ perovskites with even-numbered chains (m = 4, 6, 8) exhibit well-ordered layered structures, whereas those with odd-numbered chains (m = 3, 5, 7) disrupt the formation of 2D structures. Furthermore, we reveal that the precursor stoichiometry can govern the phase evolution along with the role of spacer parity. Among the even-numbered 2D DJ Sn²⁺ perovskites, 1,4-butanediammonium tin iodide (BDASnI₄, m = 4) exhibits optimal lattice formation and superior charge transport properties. Moreover, the introduction of an additional self-assembly monolayer ([2-(3,6-diiodo-9H-carbazol-9-yl)ethyl]phosphonic acid, I-2PACz) between the dielectric and channel layers further enhances the interface quality and reduces the trap density. The optimized transistor exhibits significantly reduced hysteresis and boosted field-effect mobility up to 1.45 cm² V^–1 s^–1.

The limited lifespan of enzyme-powered micro/nanomotors (MNMs) hinders their biomedical applications due to the easy deactivation in tumor microenvironments. In this study, by taking advantage of hydrogen bond-rich metal-organic frameworks (MOFs), we design anti-biopassivated urease-powered MOF motors (Ur-MOFtors) with sustained motility for bladder cancer therapy. Such reticular Ur-MOFtors exhibited an exceptionally long locomotion lifespan exceeding 90 min in highly concentrated urea, which was an 18-fold enhancement compared with urease-adsorbed MOFs, resulting in excellent anti-biopassivation of MOFtors. The underlying molecular mechanism of persistent motion involves hydrogen bonding interaction between the MOF skeleton and the catalytic product, as identified by in situ infrared spectroscopy and density functional theory. Based on the preserved enzymatic activity comparable to native urease, the self-propulsion pathway of Ur-MOFtors is driven by ionic self-diffusiophoresis with the positive chemotactic motion toward urea. Benefiting from the persistent motion of Ur-MOFtors in physiological urea, a rapid bladder cancer therapy was achieved with few instillation sessions and short treatment cycles during intravesical administration. This hydrogen bond-rich framework presents a promising anti-biopassivated approach to overcoming the short lifespan and easy deactivation of enzymatic motors for advanced therapeutic robotics.

Tuning the surface strain is a powerful strategy to enhance the catalytic activity of metal nanocatalysts, yet an atomically precise catalyst with intramolecular strain to unlock the atomic-level strain-structure–activity relationship is still highly desired. Herein, we report the synthesis, structural anatomy, and catalytic performance toward cyclohexanone oxime electrosynthesis of an atomically precise Ag₁₆Cu₁₈(C≡C-C₆H₁₁)₂₄ (Ag₁₆Cu₁₈) nanocluster, which has a Cu₆ ring in the center. The Cu–Cu distance in the Cu₆ ring is only 1.616 Å in a single crystal, the shortest Cu–Cu bond in Cu nanomaterials to date. Furthermore, once Ag₁₆Cu₁₈ was loaded onto carbon paper, the ultrashort Cu–Cu bond elongated to ∼2.40 Å, still showing strong intramolecular compressive strain. Ag₁₆Cu₁₈ exhibited excellent catalytic activity toward oxime electrosynthesis, manifested by a maximal Faradaic efficiency, yield, and yield rate of cyclohexanone oxime reaching 47.4%, 95.4%, and 2.66 mmol·h^–1·cm^–2 at –0.35 V, respectively. In-situ attenuated total reflection surface-enhanced infrared spectroscopy revealed that the Cu sites adjacent to the Ag atoms primarily reduce NO and stabilize it at the *NH₂OH stage, while the Cu sites with compressive strain provide H* for NO reduction and adsorb cyclohexanone to react with *NH₂OH, forming cyclohexanone oxime simultaneously. Density functional theory calculations confirmed the presence of compressive strain in the Cu₆ ring, which facilitates H* formation and cyclohexanone adsorption, hence significantly contributing to oxime generation. This study not only reports a case of atomically precise clusters with intramolecular compressive strain but also provides an atomic-level understanding for employing bimetallic nanocluster-based catalysts toward the electrosynthesis of valuable organic molecules.

Polymorphism, where the same composition adopts different structures, is abundant in perovskites, with numerous phase transitions occurring as a function of temperature and pressure. The APbX₃ perovskites (A = monovalent cation; X = Cl^–, Br^–, I^–) show such phase transitions near ambient conditions, significantly impacting their optoelectronic device performance and stability. Herein, we show that the recently reported organochalcogenide-halide perovskites (RCh)PbX₂ (RCh = ⁺NH₃(CH₂)₂S^–, ⁺NH₃(CH₂)₂Se^–; X = Cl^–, Br^–) featuring an organic A-site cation that is covalently linked to the inorganic framework, show no phase transitions with temperature from 4 to 423 K and with pressure from 0 to 40 GPa. Furthermore, the RCh-perovskites remain crystalline even at 40 GPa, in striking contrast to AMX₃ (M = Pb, Sn) perovskites that rapidly become amorphous at pressures above ca. 5 GPa. By alloying RCh or the similar-sized ethylammonium as impurities into a (CH₃NH₃)PbBr₃ host, we find that the enhanced phase integrity of the RCh-perovskites may be attributed mostly to the covalent attachment of the A-site cation, which impedes octahedral tilting, a primary avenue for phase transitions. We also track the rotational isomerization of the RCh ligands with pressure, finding that the trans-to-gauche isomerization enables a shrinking A-site cavity volume, without drastic changes to the inorganic framework. Unlike the dynamic disorder seen in hybrid perovskite A-site cations, this static rotational isomerism appears to be unaffected by temperature from 93 to 373 K. The exceptional structural integrity of the RCh-perovskites motivates the design of similar strategies to impede phase transitions in technologically important perovskite compositions.

Disrupting the charge distribution equilibrium in catalysts is an effective strategy for the polarization and cleavage of small molecules during the electrocatalytic process. To achieve effective C–C bond cleavage in multicarbon molecules, such as glycerol, integrating the advantages of defect sites while creating spatially asymmetric sites that modulate the local electronic perturbations is both promising and challenging. In this study, spatially asymmetric defect pairs were engineered by partially refilling sulfur atoms into spinel CuCo₂O_x with a high oxygen vacancy density (H_Vo-S). These oxygen defect-refilled S pairs (Vo-S) enhance the local charge transfer, reduce the energy barrier for glycerol adsorption, and create thermodynamically favorable conditions for the second C–C bond cleavage, whereas the high density of oxygen vacancies further amplifies the local electronic perturbations. Exploiting the spatial effects of asymmetric defect sites, H_Vo-S demonstrated superior performance compared to H_Vo without Vo refilling, achieving Faradaic efficiencies (FE) of 98.5% and 75.3% at 1.36 V vs RHE for formic acid in the glycerol oxidation reaction (GOR), respectively. Significantly, this strategy also promotes C–C bond cleavage during the electrooxidation of ethylene glycol and glucose, further confirming its broad applicability in activating C–C bonds in polyol substrates. This study elucidates the role of the spatial effects of localized asymmetric defect sites in the GOR process, providing new insights for the design of novel electrocatalysts aimed at promoting C–C bond cleavage in polyol molecules.

Poly(1,3-dioxolane) (PDOL)-based electrolyte has gained wide attention due to its high compatibility with the lithium metal anode, intimate contact with electrodes, and high ionic conductivity. However, its application in high-voltage batteries is limited because the residual DOL monomers are prone to oxidation at high voltage. Here, we report that LiDFOB-initiated in situ polymerization stabilizes these residual monomers, thus overcoming the oxidation-related limitations of PDOL-based electrolytes. This approach promotes the formation of a thermodynamically stable Li⁺–DOL–DFOB^– solvation structure and DOL–PDOL clusters, reducing the oxidative decomposition of the residual DOL monomers and extending the electrochemical stability window up to 5.0 V vs Li⁺/Li. It also enhances ionic conductivity (4.39 mS cm^–1), and facilitates the formation of a uniform, F-rich cathode-electrolyte interphase. Electrochemical tests and computational simulations reveal that the reduced Li⁺–PDOL interactions in the designed PDOL promote higher ionic mobility and electrochemical stability. Consequently, Li||LiCoO₂ cells using the designed PDOL exhibit remarkable cycling performance, maintaining 80% capacity retention over 760 cycles at a cut-off voltage of 4.35 V. These findings establish PDOL as a transformative electrolyte for high-voltage lithium metal batteries.

N-Heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They are used to stabilize a wide range of motifs, including clusters and nanoparticles, based in particular on coinage metals─Cu, Ag, and Au. Notably, the carbene ¹³C NMR isotropic chemical shift (δ_iso) of NHC-coinage metal complexes varies significantly across these elements, reflecting the nuanced interplay of electronic and structural factors. Here, we study the carbene carbon chemical shift in NHC-Au(I)-X complexes (X = H, OH, halides, CN, N₃, and neutral ligands such as pyridine and NHC) compared to the Cu and Ag congeners. Density functional theory calculations are used to analyze the chemical shielding tensor components, revealing that stronger σ-donor X-ligands lead to greater deshielding of δ_iso through enhanced paramagnetic contributions and, for Au, spin–orbit contributions of comparable magnitude. Moreover, a correlation between the spin–orbit contribution to the chemical shift (σ_so) and the Au-carbene bond distance highlights the critical role of trans-influence in modulating spin–orbit coupling and the overall chemical shift. Analysis of σ_so shows that stronger σ-donor ligands, associated with a greater trans-influence and elongated Au-carbene bond, lead to a higher-lying NHC-Au σ-bond and lower-lying π*-orbital, ultimately yielding greater deshielding and higher ¹³C chemical shift. This work provides insight into how structural and electronic factors govern carbene chemical shifts in NHC-based Au complexes and clusters, establishing a direct link between NMR spectroscopic descriptors and electronic structure, thus opening avenues for developing structure–activity relationships in catalysis and materials science.

The development of novel high-performance hypergolic fuels is crucial for the advancement of the aerospace industry. Although hydride-containing compounds offer excellent combustion properties and a short ignition delay time, their inherent instability and strong reducing nature have hindered their widespread application. Herein, we report the synthesis and characterization of an energetic, atomically precise copper hydride cluster, Cu₁₁H₃(5N-dpf)₆(OAc)₂, denoted as Cu₁₁H₃. This cluster exhibits exceptional hypergolic performance and good stability. When paired with high-test peroxide (HTP, >90% H₂O₂), Cu₁₁H₃ demonstrates a short ignition delay time of 16 ms and achieves a high specific impulse of 254 s. Both experimental and theoretical studies suggest that the hydrides play a pivotal role in the ignition process through interactions with protons from H₂O₂, leading to hydrogen evolution and accelerated combustion. This research provides valuable insights for the design and development of novel, environmentally benign solid hypergolic fuels for propulsion applications.

Although discrete self-assembled cage compounds with single-metal centers mimicking natural bioreactors for catalysis have been extensively investigated, studies on those with multimetal active centers, i.e., cluster active centers (CACs), have been less explored. Herein, we present the design and synthesis of a novel cluster-based supramolecular reaction pump (CSRP-1) featuring four CACs that facilitate catalysis. CSRP-1 holds a cationic supramolecular tetrahedral structure, comprising four WS₃Cu₃ clusters, each positioned at one vertex and interconnected by dipyridyl linkers. Substrates, including aryl iodides or primary or secondary amines, enter the cage cavity by replacing N,N-dimethylformamide at the CACs through weak Cu···I/N interactions. This design leverages the coordinatively unsaturated Cu centers within each CAC to activate the substrates, resulting in efficient catalytic amination. CSRP-1 works like a dynamic pump, and upon completion of the reaction, the amine product is expelled from the cavity, allowing the catalytic cycle to repeat with maintained efficiency. Theoretical calculations complement the experimental findings, providing key insights into the catalytic mechanism and the synergistic role of the clusters and linkers. This work offers a new catalysis paradigm with broad applicability to various organic reactions.

Carbonic anhydrase IX (CAIX) is a membrane protein that is highly expressed in clear cell renal cell carcinoma (ccRCC) and in hypoxic tumors. Being virtually absent in most healthy tissues, CAIX became an attractive target for the selective delivery of diagnostic and therapeutic payloads. Here, we report the discovery and characterization of DNA-encoded chemical library (DEL)-derived CAIX ligands for radionuclide-based imaging applications. Methods: DELs were screened against CAIX and CAII to prioritize hits based on their selectivity and enrichment against CAIX. In vitro characterization of hits was performed by fluorescence polarization (FP), surface plasmon resonance (SPR), and flow cytometry. In vivo biodistribution studies of Lutetium-177 and Gallium-68-radiolabeled compounds were performed in SK-RC-52 tumor-bearing mice. Results: DEL-based CAIX ligands with different affinities and selectivities could be identified. Selectivity and high affinity toward the target correlated with higher tumor-to-organ ratios and improved tumor retention. The best candidate, named OncoCAIX, reached up to ∼55% injected dose per gram in SK-RC-52 lesions at early time points with very low healthy organ uptake (tumor-to-kidney ratio of >23). Conclusion: OncoCAIX demonstrated rapid and selective tumor uptake, which is a key feature for the development of radionuclide-based imaging agents for early and late-stage ccRCC and hypoxic tumors.

Reduction or oxidation reactions at colloidal semiconductor nanocrystal quantum dot (QD) surfaces are critical mechanistic steps for charge trapping or for photoinduced charge transfer. However, measuring and controlling the redox potentials of the surface is nontrivial. Here, monoanionic metal carbonyl complexes are used as electronically tunable X-type ligands for CdSe and CdS QD surfaces. IR spectroscopy of the frequencies of the C–O stretching vibrations of the anionic metal carbonyl species enable quantitative measurement of anion dissociation correlated to QD surface reduction. Spectral redox titration and spectroelectrochemical experiments show that coordination of more Lewis basic anions shifts the surface reduction potentials to more negative values, spanning a range of more than 1 V. Based on these results, complexation energies are a critical factor in controlling surface charge storage. This concept extends generally to other types of QD supporting ligands and to other QD materials. As proof-of-concept, anion exchange was used to control chemical surface reduction and photochemical electronic doping in CdSe QDs.

Organic room-temperature phosphorescence (RTP) materials hold significant promise for applications in optoelectronics, information security, and bioimaging. Recently, significant progress has been made in RTP materials and vacuum-deposited organic light-emitting diode (OLED) devices. However, the performance of solution-processed OLEDs is seriously lagging behind due to the lack of RTP molecular strategies that balance exciton stability and solution processability at the single-molecule scale. In this work, we propose an acceptor dendronization strategy for designing RTP materials and successfully achieving highly efficient and stable RTP emissions. This strategy can simultaneously enhance the various processes involved in RTP emission at the single-molecule level: increase the intersystem crossing channels, enhance the spin–orbit coupling constants between T₁ and S₀, and suppress molecular motion. Consequently, it promotes intersystem crossing and triplet radiative transition while inhibiting nonradiative transition, thereby efficiently enhancing RTP emission. A proof-of-concept acceptor-dendronized dendrimer exhibits long phosphorescence lifetimes in the millisecond range in ambient solution and near 100% photoluminescent quantum yields in the doped films. This is the first reported RTP dendrimer to date. An OLED fabricated using this dendrimer in a sky-blue emission achieves an external quantum efficiency of 25.1%, which represents the state-of-the-art efficiency based on solution-processed RTP-OLEDs to date. Our findings offer definitive guidelines for the molecular engineering of RTP materials and pave the way for innovative RTP systems in diverse optoelectronic applications.

Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) represent a promising class of electrode materials for potassium-ion batteries (PIBs), attributed to their superior conductivity, large specific surface area, high charge carrier mobility, and tunable active sites. However, most reported 2D c-MOF-based cathode materials for PIBs usually encounter challenges, such as low specific capacity and inadequate cycling stability. In this context, we herein designed and synthesized a new hexahydroxy salicylamide ligand (6OH-HBB) via a straightforward two-step synthesis with a high yield of 93%, which was subsequently utilized to construct a 2D Cu-HBB-MOF with multiple active sites through an in situ metal coordination-induced planarization strategy. Thanks to its abundant active sites and large specific surface area, the Cu-HBB-MOF demonstrated an outstanding high initial capacity of 228.1 mA h g^–1 at 0.2 A g^–1, surpassing most reported porous material-based PIBs. Furthermore, even at 5.0 A g^–1, the Cu-HBB-MOF exhibited a large reversible specific capacity of 103.6 mA h g^–1 after 2500 cycles, simultaneously maintaining a low-capacity loss of only 0.011% per cycle and achieving a Coulombic efficiency up to 100%, demonstrating good long-term cycle stability. This work provides fundamental insights into engineering 2D c-MOFs with multisite functionality, charting a new course for developing high-performance MOF-based cathodes in next-generation energy storage systems.

Inositol phosphates control many central processes in eukaryotic cells including nutrient availability, growth, and motility. Kinetic resolution of a key modulator of their signaling functions, the turnover of the phosphate groups on the inositol ring, has been hampered by slow uptake, high dilution, and constraining growth conditions in radioactive pulse-labeling approaches. Here, we demonstrate a rapid (seconds to minutes) and nonradioactive labeling strategy of inositol polyphosphates through ¹⁸O-water in yeast, human cells, and amoeba, which can be applied in any media. In combination with capillary electrophoresis and mass spectrometry, ¹⁸O-water labeling simultaneously dissects the in vivo phosphate group dynamics of a broad spectrum of even rare inositol phosphates. The good temporal resolution allowed us to discover vigorous phosphate group exchanges in some inositol polyphosphates and pyrophosphates, whereas others remain remarkably inert. We propose a model in which the biosynthetic pathway of inositol polyphosphates and pyrophosphates is organized in distinct, kinetically separated pools. While transfer of compounds between those pools is slow, each pool undergoes rapid internal phosphate cycling. This might enable the pools to perform distinct signaling functions while being metabolically connected.

Decoding how amino acid sequences determine structure facilitates the design of functional proteins, advanced biomaterials, and selective, low-side-effect drugs. The rippled β-sheet, theorized by Pauling and Corey in 1953, has only recently begun to gain experimental support. However, research on rippled β-sheets remains limited, leaving gaps in our understanding of when and how they occur. To understand the relationship between sequences and rippled β-sheet formation propensities, we carried out molecular dynamics (MD) and density functional theory (DFT) simulations to predict the energetics for six systems of forming either a rippled or pleated β-sheets that are ordered either parallel or antiparallel. Notably, among these four possible structures of each system, the structure predicted to have the lowest energy agrees with the single case observed experimentally! To understand why this form is favored, we investigate the local structures of all six systems, with particular attention to the role of hydrogen bonds (H-bonds) in stabilization. In each system, the peptide consistently adopts a motif that allows it to form the maximum number of H-bonds between backbones, even when amidated, and composed of a single-component with mixed chirality or a cyclic peptide. We find that an achiral glycine–glycine bridge acts as a spacer between valine residues, effectively reducing steric hindrance between side chains. Furthermore, we conclude that the structures of cyclic peptides are stabilized by intramolecular H-bonds in an anhydrous environment. Our findings provide deeper insights into how sequences influence β-sheet conformations, enabling us to propose guidelines for the preferred structures of novel peptides.

SARS-CoV-2, the virus responsible for the COVID-19 pandemic, encodes several accessory proteins, among which ORF6, a potent interferon inhibitor, is recognized as one of the most cytotoxic. Here, we investigated the structure, oligomeric state, and membrane interactions of ORF6 using NMR spectroscopy and molecular dynamics simulations. Using chemical-shift-ROSETTA, we show that ORF6 in proteoliposomes adopts a straight α-helical structure with an extended, rigid N-terminal part and flexible C-terminal residues. Cross-linking experiments indicate that ORF6 forms oligomers within lipid bilayers, and paramagnetic spin labeling suggests an antiparallel arrangement in its multimers. The amphipathic ORF6 helix establishes multiple contacts with the membrane surface with its N-terminal residues acting as membrane anchors. Our work demonstrates that ORF6 is an integral monotopic membrane protein and provides key insights into its conformation and the importance of the N-terminal region for the interaction with the membrane.

The correlation of individual conformational changes in dynamic protein complexes remains challenging as most structural methods rely on averaged information over a large number of molecules. Single molecule FRET is a powerful tool for monitoring such conformational changes. When performed using three distinct probes, it enables the correlation of domain movements by providing up to three simultaneous distance measurements with high temporal resolution. Nevertheless, a major challenge lies in the site-specific attachment of three probes to unique positions within the target protein. Here, we propose an orthogonal triple-labeling strategy that is not compromised by native, reactive amino acid functionalities. It combines genetic code expansion and bioorthogonal labeling of two different noncanonical amino acids with an enzymatic self-labeling SNAP tag. We demonstrate its application by establishment of a 3-color sensor on the human metabotropic glutamate receptor 2, a dimeric, multidomain G protein-coupled neuroreceptor, and describe a previously unknown conformational intermediate state using 3-color single molecule FRET.

As predicted by the Hume-Rothery rules, forming solid solutions of rutile IrO₂ with other metal oxides that have different crystal structures is thermodynamically challenging. Consequently, achieving high solubility of foreign elements in Ir-based solid-solution oxides has been significantly limited. We demonstrate that hexagonal-perovskite BaIrO₃ can serve as a flexible matrix oxide capable of incorporating a wide spectrum of (post)transition-metal cations with different electronic structures, ranging from d⁰ to d¹⁰ configurations. Among 12 cation solutes, Ta⁵⁺, Nb⁵⁺, and Zr⁴⁺ are found to be stable without substantial leaching during the oxygen evolution reaction (OER) under acidic condition. Acceptor-type trivalent cations, including Sc³⁺, In³⁺, and Fe³⁺, are identified to leach out gradually from the particle surface while enhancing the OER catalytic activity. Both X-ray absorption spectroscopy and ab initio molecular dynamics simulations consistently show that the robust face-sharing [IrO₆] octahedral framework of the solid solutions remains unperturbed unless electrochemical leaching rapidly occurs. As a result, notably high S-numbers, on the order of 10⁶, are achievable at pH = 1. Although our work focuses on single-element incorporation, it is suggested that the solid-solution methodology is an effective strategy for developing stable, long-lasting OER catalysts with further reduced Ir usage for acidic water oxidation.

The synthesis of homochiral two-dimensional covalent organic frameworks (2D COFs) from chiral π-conjugated building blocks is challenging, as chiral units often lead to misaligned stacking interactions. In this work, we introduce helical chirality into 2D COFs using configurationally stable enantiopure and racemic [5]helicenes as linkers in the backbone of 2D [5]HeliCOFs as powders and films. Through condensation with 1,3,5-triformylbenzene (TFB) or 1,3,5-triformylphloroglucinol (TFP), our approach enables the efficient formation of a set of homochiral and racemic 2D [5]HeliCOFs. The resulting carbon-based crystalline and porous frameworks exhibit distinct structural features and different properties between homochiral and racemic counterparts. Propagation of helical chirality into the backbone of the crystalline frameworks leads to the observation of advanced chiroptical properties in the far-red visible spectrum, along with a less compact structure compared with the racemic frameworks. Homogeneous thin films of [5]HeliCOFs disclosed photoluminescent properties arising from the controlled growth of highly ordered π-conjugated lattices. The present study offers insight into general chiral framework formation and extends the Liebisch–Wallach rule to 2D COFs.

Ineffective control of alkene adsorption on a palladium membrane (PM) and the flux of active hydrogen (H*) diffusing from the aqueous side to the organic side through the PM cause low selectivity and Faradaic efficiency (FE) of alkynes to alkenes in a PM reactor. Here, a PM with a phenylthiolate-modified palladium sulfide thin layer coupled with pulsed electrolysis is reported to enable alkyne-to-alkene electrosynthesis with up to 98% selectivity and 80% FE. Electrochemical in situ Raman spectra reveal weak alkene adsorption and specific σ-alkynyl adsorption rather than flat adsorption of alkynes on the modified PM, accounting for the high alkene selectivity and functional group tolerance. Pulsed electrolysis causes reduced H* generation and restricted H* diffusion to the organic side, which better balances the generation and utilization of H*, suppresses H₂ evolution, and improves the FE. The high alkene selectivity and FE in a wide potential and current range, over 50 examples of (deuterated) alkenes with functional group tolerance and deuterated drug applications (d₂-naftifine, d₂-cinarizine, d₂-bucinnazine, d₂-artemisinin derivative, and d₂-estradiol derivative), and scalable electrosynthesis of deuterated styrene for deuterated polystyrene with improved thermal stability demonstrate potential utility.

N-Alkyl imines are prevalent in dynamic-covalent chemistry and self-assembled structures, yet their E/Z photochromism is often overlooked due to the high-energy light required for isomerization. Here, we present a simple strategy to enhance their photoswitching properties, achieving switching wavelengths and photostationary state distributions comparable to azobenzene. Moreover, we demonstrate that these N-alkyl imines undergo photoisomerization in the condensed phase and exhibit isomer-dependent fluorescence. We anticipate that this study will inspire the design of photoresponsive architectures that operate directly at the dynamic-covalent bond, eliminating the need for dedicated photoswitchable motifs.

Despite the symmetric, achiral atomic lattices typically found in binary semiconductor nanocrystals, we show that during their early formation stages, especially in the magic-size cluster (MSC) regime, chirality can be present in these metastable, transient species, which are capable of further self-assembling into high-level chiral superstructures. Through a cation exchange process operating at room temperature, a structurally symmetrical copper sulfide cluster has been successfully converted into a pair of enantiomeric cadmium sulfide MSCs, formulated as Cd₂₈S₁₇I₂₂(PEt₃)₁₂ (abbreviated as (+)/(−)-[Cd₂₈S₁₇]). The atomic structures of these two MSCs were established by single-crystal X-ray crystallography. It is revealed that the [Cd₂₈S₁₇] MSCs feature an antisupertetrahedron configuration which has never been observed in reported CdS structures. Remarkably, rather than crystallizing into a racemic mixture, (+)/(−)-[Cd₂₈S₁₇] MSCs naturally crystallize out in an enantiomerically biased manner, sufficiently rendering distinctly opposite chiroptical responses. This behavior reflects genuine circular dichroism activity, which can be directly attributed to the chiral atomic structure of this well-known quantum photonic nanomaterial.

The advancement of immunotherapy aims to achieve complete tumor eradication. However, several critical challenges hinder the efficacy of conventional phototherapy-mediated immune responses, including insufficient immunogenicity and the presence of an immunosuppressive tumor microenvironment. Nonprogrammed cell death, as a highly immunogenic pathway, offers a promising strategy to enhance immune responses. Herein, a membrane-anchored photodynamic immunotherapy agent, PNBSe, was developed by conjugating a selenium-substituted benzophenothiazine photosensitizer with a pyrazolone group, enabling membrane targeting via pyrazolone–protein interactions. Upon light irradiation, PNBSe induced rapid and intense cell necrosis characterized by significant cell membrane rupture, organelle swelling, and content leakage. Further investigations demonstrated that PNBSe activated inflammatory signaling pathways, induced immunogenic cell death, and reshaped the immunosuppressive tumor microenvironment, ultimately promoting systemic antitumor immune responses in vivo. This membrane-anchored small molecule provides a novel perspective for promoting cancer photodynamic immunotherapy.

Multicarbon alcohols produced through photochemical and electrochemical CO₂ reduction reactions (CO₂RR) are promising alternatives to fossil fuels; however, their selectivity and efficiency remain low due to the high energy barrier for C–C coupling and the competition from hydrocarbon production. Here, we present a strategy to enhance ethanol efficiency and selectivity via cooperative catalysis in porous structures for photoelectrochemical (PEC) CO₂RR. Using a coordination-templated strategy, we synthesized single crystals of MOF-COF (MOCOF) hybrids with metalloporphyrins, with their structures determined by single-crystal 3D electron diffraction. The porous frameworks featuring adjacent confined metalloporphyrins efficiently capture and cooperatively activate CO₂, achieving outstanding PEC CO₂-to-ethanol conversion. Particularly, the Pt-MOCOF delivers a Faradaic efficiency (FE) of 83.5% at −1.0 V with 91.7% carbon selectivity, surpassing state-of-the-art COF or MOF catalysts and ranking it among the top-performing catalysts. The catalyst system displays remarkable stability, maintaining 95% of its activity after 100 h of continuous operation. Experiments and theoretical calculations revealed that the cooperative catalyst enriches and stabilizes intermediates in the channels, guiding the reaction pathway toward ethanol production.

The chemical conjugation of poly(ethylene glycol) (PEG) to therapeutic agents, known as PEGylation, is a well-established strategy for enhancing drug solubility, chemical stability, and pharmacokinetics. Here, we report on a class of supramolecular polymeric prodrugs by utilizing oligo(ethylene glycol) (OEG) to modify the hydrophobic anticancer drug camptothecin (CPT). These OEGylated prodrugs, despite their low molecular weight, spontaneously self-assemble into therapeutic supramolecular polymers (SPs) with a tubular morphology, featuring a dense OEG coating on the surface. By designing biodegradable linkers with varying chemical stabilities, we investigated how the release kinetics of CPT influence the in vitro and in vivo performance of these SPs. Our findings demonstrate that self-assembling prodrugs (SAPDs) with a self-immolative disulfanyl-ethyl carbonate (etcSS) linker exhibit a faster drug release rate than those with a reducible disulfanyl butyrate (buSS) linker, leading to higher potency and significantly improved antitumor efficacy. Notably, two stable tubular SPs, Tubustecan (TT) 1E and TT 7E, outperformed irinotecan─a clinically approved CPT prodrug─in a colon cancer model, achieving enhanced tumor growth inhibition and prolonged animal survival. These results highlight the potential of supramolecular OEGylation as an important strategy for engineering drug-based supramolecular polymers and underscore the critical role of chemical stability vs supramolecular stability in optimizing supramolecular prodrug design.

Subtle structural variations among fatty acids significantly influence their biological roles and health effects. However, molecular recognition of their long, flexible, and chemically inert hydrocarbon chains remains a challenge. Inspired by natural fatty acid-binding proteins (FABPs), we designed and synthesized nanotubular metallo-cavitands, termed metal–organic pillars, through the coordination-driven assembly of pillararene-derived ligands with Ag(I) salts. These biomimetic hosts feature continuous interior channels exceeding 2.6 nm, selectively binding long-chain fatty acids through precise size and shape complementarity. Saturated and trans fatty acids, with linear conformations, are effectively encapsulated and stabilized by C–H···π and van der Waals interactions. In contrast, coiled cis-polyunsaturated fatty acids, such as docosahexaenoic acid (DHA), cannot be accommodated due to structural incompatibility. This work highlights the ability of artificial receptors to emulate the recognition capabilities of natural proteins, enabling the targeting of “bad” fatty acids associated with adverse health effects.

α,α-Disubstituted α-amino acids such as α-aminoisobutyric acid (Aib), in their polymeric structures, are known to form a 3₁₀-helical conformation rather than an α-helical conformation, which is usually adopted by polymeric α-monosubstituted α-amino acids. Even α-helically folded Aib oligomers are unprecedented, although they have been predicted by theoretical calculations. In the present paper, we report the first α-helically folded Aib oligomer found in the course of our study on the construction of a metal–peptide framework, ^AibMOF-1. This MOF was synthesized by Zn²⁺-mediated complexation of a pyridyl-functionalized Aib hexamer, Py-Aib₆-Py, and 5-nitroisophthalate (nip^2–). Single crystal X-ray diffraction of ^AibMOF-1 ([Zn(nip)(Py-Aib₆-Py)]_n) revealed that Py-Aib₆-Py in ^AibMOF-1 carried a C═O_i → NH_i+4 hydrogen bonding array characteristic of α-helices, which is distinct from Py-Aib₆-Py alone adopting a 3₁₀-helical conformation with a C═O_i → NH_i+3 hydrogen bonding array. The α-helical Py-Aib₆-Py units in ^AibMOF-1 assembled into a superhelical nanotubular architecture with a porous framework. When just the nitro group of the coligand nip^2– was changed to a tert-butyl group, an MOF (^AibMOF-2) with a completely different structure formed, where the constituent Py-Aib₆-Py units adopted only the 3₁₀-helical conformation, just like Py-Aib₆-Py in its crystalline structure.

Addressing the spatial organization of high-performance single-molecule magnets (SMMs) and achieving stimuli-responsive switching of their magnetic bistability are pivotal challenges in molecular memory technologies, paving the way for advanced opto-magnetic devices. Herein, we utilize the photosensitive ligand 4,4′-bipyridine (BPy) as a linker to incorporate typical pentagonal-bipyramidal SMMs as nodes into a two-dimensional metal-organic framework (MOF), formulated as {[Dy_1.5(OPh)₂Cl(BPy)₃(THF)_1.5][(BPh₄)_1.5]·0.5THF}_n (1). The precise synthesis facilitates axial coordination of PhO^– and equatorial alignment of BPy, enforcing perpendicular orientations of the principal magnetic axes of Dy³⁺ ions across all Kagomé layers. Compound 1 exhibits photochromic behavior upon exposure to ultraviolet irradiation at room temperature, driven by a photoinduced electron transfer process that generates radicals. The resulting 1uv displays overall faster relaxation dynamics compared to 1, characterized by shorter relaxation times at identical temperatures within the 12–70 K range, a lower diverging temperature in field-cooled and zero-field-cooled curves (9 K for 1 vs. 6 K for 1uv), and reduced energy barriers from 1048(17)/822(46) K for 1 to 1000(9)/641(34) K for 1uv. Notably, the coercive field decreases dramatically from 4500 Oe for 1 to 1300 Oe for 1uv at 2 K, while the hysteresis loop opening temperature decreases from 20 K for 1 to 14 K for 1uv. These photoinduced changes are due to the formation of photogenerated radicals and alterations in crystal packing. This work achieves an MOF that integrate high-performance SMM behavior with magnetic coercive photomodulation, providing a design paradigm for engineering advanced SMM-MOFs with tailored photomagnetic switching.

Several fluorescent proteins, when expressed in E. coli, are sensitive to weak magnetic fields. We found that mScarlet3 fluorescence in E. coli reversibly decreased by 21% in the presence of a 60 mT magnetic field, the largest magnetic field effect (MFE) reported in any fluorescent protein. Purified mScarlet3 did not show an MFE, but the addition of flavin mononucleotide (FMN) and simultaneous illumination with blue and yellow light restored the MFE. Through extensive photophysical experiments, we developed a quantitative model of the giant MFE in mScarlet3-FMN mixtures. The key reaction step involved electron transfer from fully reduced FMNH₂ to triplet-state mScarlet3 to form a triplet spin-correlated radical pair. The magnetic field then controlled the branching ratio between singlet recombination vs triplet separation. Our quantitative model of the mScarlet3-FMN photocycle provides a framework for the design and optimization of magnetic-field-sensitive proteins, opening possibilities in fluorescent protein-based magnetometry, magnetic imaging, and magnetogenetic control.

Modulation of electron density localization on periodic crystal solids through electron transfer from interstitial cations can directly influence the bonding configurations of small-molecule intermediates at the catalyst binding site. This study presents the microwave-assisted solid-state synthesis of four heterointercalant Chevrel-phase (CP) sulfides with varying metal cation intercalants with compositional and electronic structure investigations of the electron density redistribution as a result of intercalation. The heterointercalant CP sulfides, with the general formula Cu_xM_yMo₆S₈ (where M = Cr, Mn, Fe, Ni; x, y = 1.5–2.5), are presented here for the probe reaction of electrochemical CO₂ reduction. A change in product selectivity is observed toward the production of methanol at low overpotentials of −0.5 V vs reversible hydrogen electrode (RHE), as a result of the intercalant combination present within the CP interstitial cavity. Structural confirmation of all materials was examined through Rietveld refinement of the powder X-ray diffraction (PXRD) data, high-resolution transmission electron microscopy (HR-TEM), and selected-area electron diffraction (SAED). Electron transfer from the intercalated metal cations to the Mo₆S₈ cluster was investigated via X-ray photoelectron spectroscopy (XPS) of the intercalated metal cations and the chalcogenide cluster. Electron transfer was further confirmed through X-ray absorption analysis (XAS) of the K-edges of Mo and intercalants. Intermediate studies of electrochemical reduction of formaldehyde to methanol resulted in a faradaic efficiency of ∼78% methanol production on Cu_xNi_yMo₆S₈. The results presented herein identify distinct principles for materials design that can be utilized in other compositional spaces within the broad families of periodic crystal solids.

Phenalenyl chemistry has flourished for decades but currently faces bottlenecks related to synthetic challenges and stability issues. In this study, we introduced an iterative protection–oxidation–protection (POP) strategy to synthesize stabilized phenalenyl radicals (PRs) with multiple substitutions at the α-positions. The applicability of this POP strategy was verified using triisopropylsilylthyl and phenyl substituents to generate trisubstituted PR1 and hexasubstituted PR2. In particular, both oxidation and dimerization were observed during the synthesis involving phenyl substituents. Both PR1 and PR2 were bench-stable, with half-lives in solution of up to 46 d and thermal decomposition temperatures of up to 300 °C. X-ray crystallographic analysis revealed that PR1 existed as a distinct 12-center-2-electron π-dimer, whereas PR2 existed as a monomer. The properties associated with monomer–dimer equilibrium both in the solid state and in solution were systematically investigated via variable-temperature spectroscopy, and the results revealed a small singlet–triplet energy gap and concentration-dependent absorption and electrochemical behaviors. Remarkably, both PR1 and PR2 formed biocompatible nanoparticles, with the latter capable of depleting reactive oxygen species in liver cells. This study thus demonstrated the applicability of the POP strategy for the construction of stable, functionalized PR derivatives with practical applications as spin functional materials.

As emerging electroactive materials, the controlled synthesis of highly ordered two-dimensional (2D) conjugated coordination polymer (c-CP) films ensuring the long-range π-electron delocalization is essential for advancing high-performance (opto-)electronics. Here, we demonstrate the growth of highly crystalline 2D c-CP thin films on inert substrates by chemical vapor deposition with the assistance of ammonia (NH₃) for the first time, leveraging its deprotonation effect on ligands and competing effect as additional coordinating species. The resulting Fe-HHB (HHB = hexahydroxybenzene) films exhibit large-area uniformity and a 2 order-of-magnitude increase in crystal grain size, which translates into significant improvements in electrical conductivity (from 0.002 to 3 S/cm), charge mobility, elastic modulus, and hardness. To verify the generality of this NH₃-assisted synthesis, the contrast Cu-HHB and Cu-BHT (BHT = hexathiolbenzene) 2D c-CP thin films are also prepared and deliver significantly improved electrical conductivities from 51 to 113 and from 595 to 905 S/cm, respectively. The greatly improved crystallinity, combined with the high compatibility of the developed synthetic strategy with current device integration technologies, paves the way for developing c-CP-based electronics.

Direct methane conversion to value-added chemicals under mild conditions presents a promising route toward net-zero carbon emissions. However, this process encounters significant challenges in efficiently activating inert C–H bonds and preventing excessive oxidation to CO₂. Herein, we propose a coverage-dependent strategy that leverages the correlation between methane coverage and C–C coupling selectivity, thereby enhancing both the activity and selectivity. By tuning the Lewis acidity of a well-defined atomic 3d transition metal-modified ceria, from weak to moderate, it boosts methane adsorption capacity and promotes its dissociative activation. Additionally, incorporating a nickel cocatalyst improves the charge separation through efficient hole extraction. The optimal noble-metal-free catalyst (Ni₁-CeO₂) delivers exceptional room-temperature performance, achieving a production rate of 243 μmol·g^–1·h^–1 with approximately 90% ethane selectivity over an ultralong test (>350 h), outperforming previously reported noble-metal-free catalysts. This work provides new insights into selectivity regulation via optimization of chemisorbed methane coverage and paves the way for the design of advanced noble-metal-free catalysts.

Consecutive asymmetric hydrogenation offers a direct and convenient approach to synthesizing complex C(sp³)-enriched products with multiple chirality. Herein, we report an asymmetric synthesis of chiral 1,2,3,4-tetrahydroquinolines (THQs) and tetrahydroquinoxalines bearing both endo- and exocyclic vicinal chirality through the consecutive transfer hydrogenation of easily accessible C2-acylated quinolines and quinoxalines. The method features mild conditions, easy operation, broad substrate scope (42 examples), and excellent asymmetric control (generally >90% ee and 20/1 dr). The key to success is the use of a water-soluble chiral aminobenzimidazole Ir catalyst. Mechanistic experiments support that the reaction involves the sequential reduction of the carbonyl group and then the quinoline core, with the asymmetric control of each step dominated by the catalyst. Remarkably, a diastereodivergent synthesis of all four stereoisomers of a chiral THQ has been successfully implemented.

Proteolysis-Targeting Chimeras (PROTACs) represent a transformative therapeutic platform for targeted protein degradation across diverse disease indications. However, their potent catalytic activity in normal tissues raises significant concerns regarding off-target toxicity. Here, we present a novel supramolecular self-assembly platform for the bioorthogonal control of PROTAC prodrug activation, enabling tumor-specific protein degradation with minimized systemic toxicity. By exploiting the overproduction of reactive oxygen species (ROS) in pancreatic cancer cells, the supramolecular self-assembly approach selectively accumulates bioorthogonal reaction triggers within the targeted malignant cells, which subsequently facilitates the spatiotemporally controlled activation of the bioorthogonally caged PROTAC. This tumor-selective activation mechanism demonstrates enhanced degradation efficiency in pancreatic cancer cells compared to normal cells. In vivo studies reveal potent tumor growth inhibition with complete preservation of major organ histology, confirming the therapeutic index enhancement achieved through a controllable activation strategy. This biomimetic activation platform establishes a generalizable framework for safer PROTAC-based therapies by integrating tumor-specific microenvironmental cues with bioorthogonal reaction engineering.

“Computation-ready” metal–organic framework (MOF) databases provide essential raw data for high-throughput computational screening (HTS) and machine-learning approaches to materials discovery. However, the structural fidelity of these databases remains largely unquantified. We introduce MOSAEC, an algorithm that detects chemically invalid structures based on metal oxidation states. MOSAEC was manually validated against 14,796 MOF structures from the popular CoRE database and found to flag erroneous structures with 96% accuracy. Examination of 14 leading experimental and hypothetical MOF databases containing >1.9 million structures reveals structural error rates exceeding 40% in most cases. Analysis of 8 recent HTS studies which highlighted top-performing candidates shows that 52% of these structures were chemically invalid.

C–H bond activation is a fundamental challenge in organic synthesis, and various routes have been explored. Among them, halogenation has played an important role in producing valuable intermediates. We report a novel photoelectrochemical (PEC) tandem C–H chlorination using a Ti-doped Fe₂O₃ (Ti:Fe₂O₃) photoanode in a two-phase electrolyte system consisting of natural seawater and a chloroform organic phase. This system enables the in situ generation of Cl₂ via the chlorine evolution reaction (CER) with near 100% Faradaic efficiency (FE) while suppressing the competing oxygen evolution reaction (OER). The generated Cl₂ undergoes photolytic cleavage, forming chlorine radicals that selectively chlorinate sp³ C–H bonds in toluene, cyclohexane, and ethylbenzene with 100% regioselectivity. This work demonstrates the feasibility of seawater-based PEC halogenation and provides a sustainable strategy for selective C–H functionalization in organic synthesis.

Sn–Pb narrow-bandgap perovskites are indispensable for achieving highly efficient all-perovskite tandem solar cells as bottom subcells. However, facile oxidation of Sn²⁺ into Sn⁴⁺ leads to the poor precursor stability, which largely hinders the development of Sn–Pb perovskite solar cells (PSCs). Herein, we present a novel strategy to synthesize SnI₂·xDMSO intermedium adducts in situ utilizing a mild one-to-one reaction between molecular SnI₄ and metallic Sn. This approach avoids the formation of low-coordinated SnI₂·xDMSO clusters (x ≤ 2), yielding highly coordinated SnI₂·xDMSO (x = 3) adducts with enhanced antioxidation ability. The resultant precursor showed outstanding stability and reproducibility. The aged precursor for 7 days maintains its initial properties. Consequently, the resulting Sn–Pb PSCs deliver an impressive efficiency of 22.64% and retain ∼ 90% of their initial value after maximum power point operation under simulated one-sun illumination in air for 530 h under encapsulation. Our finding provides an effective pathway to enhance the intrinsic antioxidant capacity of Sn²⁺ in perovskite precursors, paving a way for the development of efficient and reproducible Sn–Pb PSCs.

Nonlinear optical (NLO) materials are of fundamental interest in laser technologies, yet achieving high-performing NLO crystals remains a substantial challenge due to the inherent trade-offs in critical performance metrics. Here, we report a new quasi-zero-dimensional (0D) tellurite molybdate NLO crystal, Ca₇(TeO₃)₆(MoO₄) (CTMO), engineered via a module-oriented dimensionality reduction strategy. The identification of a record isolated Te–O to Mo–O group ratio of 6 in tellurite molybdates underscores an unparalleled structural configuration. Notably, CTMO exhibits the shortest UV cutoff edge of 266 nm accompanied by a record-breaking bandgap of 4.66 eV among all reported acentric molybdates, which endows CTMO with a high laser-induced damage threshold 42 times higher than that of AgGaS₂. Moreover, it demonstrates the strongest second harmonic generation (SHG) response of approximately 8.6 × KDP among molybdates with bandgaps exceeding 4 eV, a desirable birefringence value of 0.092@1064 nm for an effective phase matching process, and an extended IR absorption edge beyond 7.0 μm. Structural and theoretical analyses reveal that the well-balanced activities of CTMO arise from the synergistic effects of densely packed [TeO₃] trigonal pyramids and well-aligned [MoO₄] modules. The discovery of CTMO facilitates the utilization of acentric oxides as mid-IR NLO crystals, and it provides a straightforward and effective approach toward the rational design of novel NLO crystals with enhanced overall performance.

Replication of molecular information in nature is based on the synthesis of the backbone of the copy strand by polymerization of monomers bound to a template. An alternative strategy is to use a preassembled polymer backbone devoid of sequence information as the copy strand and to attach side chains in a sequence determined by binding to a template, i.e., base-filling. Base-filling strategies were investigated for template-directed synthesis of recognition-encoded melamine oligomers (REMO) using H-bond base-pairing interactions between 4-nitrophenol and phosphine oxide side chains. A template with three 4-nitrophenol H-bond donor recognition units was used with a blank copy strand equipped with three aldehyde groups for the reversible attachment of amine recognition units via dynamic imine chemistry. Equilibration of the template and blank strands in dichloromethane in the presence of benzylamine and a phosphine oxide recognition unit equipped with an amine resulted in selective incorporation (79%) of the phosphine oxide recognition unit into the resulting copy strand. Covalent attachment of the blank strand to the template with a diester linker increased the selectivity of the base-filling process to 85%, and carrying out the experiment in toluene further increased the selectivity to 92%. The imines in the copy strand were trapped by reduction, and cleavage of the ester linkages allowed recovery of the template strand along with the kinetically stable tris-phosphine oxide copy. Fidelity of templating is determined by the concentration of the template strand, the association constant for the base-pairing interaction, and the effective molarities of the intramolecular interactions in the duplex.

Activating the oxygen anionic redox presents a promising avenue for developing highly active oxygen evolution reaction (OER) electrocatalysts for proton-exchange membrane water electrolyzers (PEMWE). Here, we engineered a lattice-confined Ru single atom dispersed on a lamellar manganese oxide (MnO₂) cation site. The strong Ru–O bond induced an upward shift in the O 2p band, enhancing metal–oxygen covalency and reshaping the OER mechanism toward lattice oxygen oxidation pathway with increased activity. In situ spectral characterization combined with density functional theory (DFT) calculations revealed that electron transfer from Mn to Ru alleviates the Jahn–Teller effect within the MnO₆ octahedral structure, stabilizing the lattice. The layered Ru/MnO₂ architecture also promotes the rapid replenishment of oxygen vacancies, preventing structural collapse. As a result, the optimized Ru/MnO₂ electrocatalyst achieves an OER overpotential of only 179 mV at 10 mA cm^–2 in 0.5 M H₂SO₄, along with exceptional durability over 1000 h at 100 mA cm^–2. Moreover, the Ru/MnO₂-based PEM device requires only 1.71 V to reach 1 A cm^–2 and shows a durability of 500 h at 500 mA cm^–2.