Browse Articles

NRF2 Pathway Status and Maintenance Immunotherapy Exposure in EC-CRT-002

Dual‐Domain Coupling‐Driven Interface Remodeling Enables Ultra‐Dilute Flame‐Retardant Electrolytes for High‐Voltage, Wide‐Temperature Batteries

ABSTRACT The paradigm shift in electrolyte research is a critical driver for performance breakthroughs in sustainable batteries under extreme conditions. Ultra‐dilute electrolytes (UDEs) have attracted extensive attention due to their remarkable cost advantages and broad application prospects, yet excess free solvents cause trade‐offs among high‐voltage stability, wide‐temperature adaptability, longevity, and safety. In this work, we propose a dual‐domain coupling‐driven interface remodeling strategy to tailor bulk solvation and interfacial microenvironments via integrating hierarchically‐solvated carbonate ester, ether, and fluorinated cyclophosphazene. The designed UDE (0.05 M) features a more flexible solvation configuration with less restricted ion transport; concurrently, electric double layers on both electrode surfaces are regulated through molecular competitive adsorption and decomposition under electric field induction. Consequently, cross‐scale microenvironment remodeling is realized to essentially overcome the existing performance limitations. The UDE not only exhibits intrinsic flame retardancy but also significantly improves electrode compatibility (phosphate and oxide cathodes, metal anode) through a bidirectional interface stabilization mechanism. Remarkably, Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode achieves desirable durability over a wide temperature range (−40∼70°C). Furthermore, this strategy is extended to potassium‐ion batteries, enabling stable operation of KVPO 4 F cathode at 4.95 V. This work establishes a universal framework for multi‐scale interfacial molecular engineering, offering a promising advancement in extreme energy storage technologies.

Innovate or Be Left Behind: A Path to Prospective External Control Arms for Accelerated Oncology Drug Development

Supramolecular Strategies for Modulating Excited‐State Properties of Photosensitizers in Photodynamic Therapy

ABSTRACT The performance of photosensitizers (PSs) in photodynamic therapy (PDT) is determined not only by their intrinsic molecular structures but also by their spatial organization and environmental interactions. Supramolecular assembly enables precise control over molecular packing, local microenvironments, and intermolecular electronic coupling without altering the chromophore scaffold, thereby offering a versatile approach to modulate the photophysical and photochemical behavior of PSs through noncovalent interactions. In this Minireview, we summarize recent advances in supramolecular strategies for modulating the excited‐state properties of PSs in PDT. We focus on two central aspects: promoting intersystem crossing to enhance triplet‐state formation, and modulating excited‐state deactivation pathways to regulate ROS generation and bias Type‐I or Type‐II photodynamic processes. Representative examples are discussed to illustrate how supramolecular assembly can reduce singlet‐triplet energy gaps, introduce charge‐transfer (CT) mediators, suppress nonproductive decay, and facilitate electron or hydrogen atom transfer (HAT) reactions. Finally, we highlight the remaining challenges in mechanistic understanding, structural stability, and translational implementation, and outline future opportunities in bioadaptive assembly, simplified system design, and mechanism‐guided development of next‐generation supramolecular PSs.

Operando Reconstruction of NiB Precatalyst Into Adaptive Heterointerfaces for CO ₂ Photoreduction via Tandem Hydrogen Relay

ABSTRACT Photocatalytic CO 2 reduction is a transformative carbon neutrality technology, yet the electronic competition between water‐derived proton generation and CO 2 activation over intrinsic sites leads to parasitic H 2 evolution over a static catalytic surface. Here we demonstrate that crystalline nickel boride (NiB) precatalyst, previously unexplored for photocatalysis, undergoes spontaneous operando reconstruction under illumination to form adaptive Ni/B 2 O 3 /NiB heterointerfaces as the genuine catalytically active phases. The reaction‐driven reconstructed interfaces enable a tandem hydrogen relay across the NiB→Ni→B 2 O 3 interface, in which hydrogen species evolve sequentially from H 2 O to H 2 and are subsequently converted into surface‐active hydrogen (H 2 O→H 2 →H*) via Ni‐mediated dissociation and hydrogen spillover. The H* species assist CO 2 activation and hydrogenation on the electron‐deficient B 2 O 3 domains. This dynamic process progressively redirects the reaction pathway from water‐splitting‐dominated activity to highly efficient CO 2 ‐to‐CO conversion, achieving a CO evolution rate of 4.5 mmol·g −1 ·h −1 with promoted utilization of in situ formed hydrogen species, thus presenting an order‐of‐magnitude enhancement over reported photocatalytic systems. This work unlocks crystalline transition‐metal borides as an untapped material platform for photocatalytic CO 2 reduction and demonstrates that reaction‐driven interfacial reconstruction can establish adaptive hydrogen‐relay pathways to mitigate multi‐reaction competition in solar‐to‐chemical conversion.

Stability‐Enhanced Therapeutic Artificial Cells Based on a Lipid–Polymer Integrated Architecture

ABSTRACT Current artificial cells often lack robustness in the face of the complex physiological milieu. Additionally, the strategies for mimicking natural cargo exchange mostly rely on biological techniques, which involve integrating native channel proteins or adopting intact natural cell membranes. Herein, we propose a rational chemical design strategy to construct artificial mini cells (MCs) based on a lipid–polymer integrated architecture. Our MCs show three key merits, including robust structural stability, controllable metabolic reactions, and convenient surface functionalization for diverse biomedical applications. MCs adopt a lipid–polymer integrated architecture, where a cross‐linked zwitterionic polymer in situ grown on the phospholipid membrane acts as the conceptually synthesized cytoskeleton mimic, ensuring structural stability and easy functionalization. Azobenzene‐gated lipids are incorporated to act as light‐responsive channel protein mimics, enabling spatiotemporal regulation of membrane permeability and metabolic reactions. As a proof of concept, therapeutic artificial MCs with tumor tropism, surface‐immobilized aPDL1 proteins, and internally encapsulated glucose oxidase–catalase (GOx–Cat) multi‐enzyme system were rationally designed, named aPDL1‐Tt‐MC(GOx + Cat). aPDL1‐Tt‐MC(GOx + Cat)s possess zwitterionic ionizable pyridine carboxybetaine moieties for tumor tropism, the GOx–Cat system for light‐controlled glucose‐to‐O 2 conversion to drive deep tumor infiltration, and surface‐immobilized aPDL1 to block PD‐1/PD‐L1 recognition for enhanced antitumor efficacy.

Assembly of Bioactive Superstructures via Metal–Phenolic Complexation for Blood Purification

ABSTRACT Hyperbilirubinemia, which stems from bilirubin accumulation caused by liver failure, can lead to jaundice, multi‐organ damage, and mortality. Hemoperfusion is the most effective detoxification approach, and its efficacy critically depends on the adsorbent system. However, most developed adsorbents exhibit poor hemocompatibility, posing risks of coagulation and bacterial infection. Herein, we report a facile and highly biocompatible strategy to fabricate bioactive superstructures for blood purification, enabling toxin removal. The formation of the bioactive superstructures is mediated by the assembly of polydopamine/Zn II networks on natural polymer templates, followed by surface modification with human serum albumin. The obtained superstructures enable rapid bilirubin clearance owing to the synergistic effects of metal coordination and polyphenol‐mediated noncovalent interactions (hydrogen bonding and hydrophobic and electrostatic interactions). Furthermore, these bioactive superstructures exhibit excellent antibacterial efficacy, achieving > 99.9% killing efficiency of both Escherichia coli and Staphylococcus aureus , while enhancing anticoagulant performance by 2.6‐fold (compared to the control) through inhibition of platelet adhesion/activation and modulation of the intrinsic coagulation pathway. This work expands our understanding of metal–phenolic‐mediated superstructure assembly. Furthermore, the efficient toxin removal, antibacterial protection, and anticoagulant activity of the developed bioactive superstructures are expected to underpin the rational design of blood‐contacting materials based on metal–phenolic complexation.

Orbital Engineering via Double‐Exchange Interaction in a Bimetallic MOF for Electrocatalytic C─S Coupling of CO ₂ and Sulfate

ABSTRACT Guided by molecular orbital theory, we have designed and synthesized a novel bimetallic metal‐organic framework (BTC‐Co‐O‐Cu‐BTA) for the electrocatalytic C─S coupling of CO 2 and sulfate. The integration of edge/corner‐sharing CoO 6 octahedra and CuO 5 square pyramids establishes a robust double‐exchange interaction (DEI). This interaction effectively modulates the spin states of the cobalt and copper sites while optimizing their electronic configurations. This tailored electronic environment disrupts the hyperconjugation symmetry of the S─O bonds in sulfate, enabling the simultaneous activation of both CO 2 and sulfate. Consequently, the catalyst achieves highly efficient C─S coupling with a remarkable Faradaic efficiency of 17.43% under a pure CO 2 atmosphere, significantly outperforming conventional systems. Through in‐situ FTIR, NMR, and electrochemical impedance spectroscopy, we demonstrate that this bimetallic synergy substantially lowers the reaction energy barrier and allows for the capture of key dynamic intermediates. Furthermore, magnetic measurements reveal a DEI‐induced transition from an antiferromagnetic to a ferromagnetic electronic state, successfully validating our proposed orbital engineering mechanism. This work provides a novel strategy for activating inert chemical bonds and establishes fundamental principles for the design of high‐performance electrocatalysts.

Orthosteric Control of Acidity Through Sulfate Binding in a Neutral Cyclo[8]pyrrole

ABSTRACT Acid–base equilibria can be shifted when binding events alter the local electrostatic and hydrogen‐bonding environment of an ionizable site. Implementing such binding‐linked acidity changes in a discrete synthetic system would enable regulation of proton activity without changing molecular composition or solvent. Here we describe a new naphthalimide‐fused analogue of cyclo[8]pyrrole in which anion recognition dramatically shifts protonation equilibria. Whereas established cyclo[8]pyrroles preferentially form globally aromatic dications, the electron‐deficient macrocycle shows an unusual preference for a persistent neutral redox state, while simultaneously revealing exceptionally high Brønsted acidity in organic solvents. The neutral macrocycle retains key anion‐recognition characteristics of dicationic cyclo[8]pyrroles, including strong sulfate affinity. Sulfate binding increases the effective first p K a in DMSO by roughly four units, providing an orthosteric, anion‐actuated acid switch and expanding the design space of switchable acidity beyond host–guest p K a shifts and light‐addressable photoacids.

Molecular‐Level Modulation of Mass Transfer Kinetics in Trinuclear Copper Cluster–Based COFs Enables Efficient Electrocatalytic Nitrate Reduction

ABSTRACT Electrocatalytic nitrate reduction (NO 3 RR) provides a sustainable route for ammonia synthesis while mitigating nitrate pollution, yet catalyst design has largely overlooked mass transfer kinetics. Herein, we report a series of vinylene‐linked trinuclear copper cluster–based covalent organic frameworks (COFs; CuDB‐TMT, CuDA‐TMT, and CuDA‐TMB) synthesized via Knoevenagel condensation, enabling precise modulation of the catalytic microenvironment. Systematic structural variation reveals that steric hindrance and pore architecture critically govern substrate accessibility and interfacial kinetics. CuDB‐TMT, bearing methyl‐substituted copper clusters, exhibits suppressed activity due to hindered mass transfer, whereas CuDA‐TMB, featuring enlarged pores and an unobstructed active site environment, achieves a high ammonia Faradaic efficiency of 95.36% and a yield rate of 10.26 mg h −1 cm −2 in 50 mM nitrate, outperforming most reported NO 3 RR electrocatalysts. Combined experimental and theoretical studies identify mass transfer regulation as a key determinant of catalytic performance. Moreover, CuDA‐TMB functions effectively as a cathode for Zn‐nitrate batteries. This work highlights molecular‐level kinetic control as a viable strategy for designing high‐performance porous electrocatalysts.

Orchestrating Reactive Intermediates: Unlocking Near‐Complete Oxidant Utilization in Electrochemical‐Thermal Cascade Oxime Synthesis

ABSTRACT Oxime synthesis via hydroxylamine is the preferred route and is conventionally achieved by ammoxidation of ammonia with hydrogen peroxide. Yet, in alkaline environments, the simultaneous presence of ionic hydroperoxide (OOH − ) and molecular H 2 O 2 severely constrains oxidant efficiency. Here, we introduce a life cycle control strategy that coordinates the generation, stabilization, transport, and consumption of OOH − to concentrate it into a centralized OOH − population. Implemented in a continuous electrochemical‐thermal cascade operating in weakly protic methanol, this approach enables efficient oxime production directly from ammonia and offers a route to reengineer traditional manufacturing. Detailed mechanistic studies show that the centralized OOH − population yields an oxidant utilization efficiency of up to 96.8% and a 60.3% enhancement in oxime synthesis rate versus conventional thermocatalysis. By establishing a paradigm for regulating the population of a key reactive intermediate, this work delivers guiding principles for the rational design of advanced cascade catalytic systems.

Delocalization‐Driven Activation of Inert Imine Linkages in Covalent Organic Frameworks for Reversible Magnesium Storage

ABSTRACT Imine‐linked covalent organic frameworks (COFs) are promising cathodes for rechargeable magnesium batteries (RMBs), yet their abundant imine linkages (C═N) typically remain electrochemically inert, serving merely as structural connectors. Here, we reveal that the redox inactivity of imine linkages arises from insufficient π‐electron delocalization, and we demonstrate that enhancing local delocalization can switch these bonds into highly reversible redox centers. Through precise fluorine substitution in a triazine‐based COF, we achieve localized π‐delocalization without disrupting the overall conjugated framework. This delocalization‐driven activation lowers the LUMO level and stabilizes the reduced state of imine linkages (C–N − ), enabling a reversible C═N ⇄ C–N − conversion—a function never realized before in magnesium batteries. The activated imine sites become kinetically preferred Mg 2+ migration channels, cutting the diffusion barrier by half (from 1.61 to 0.81 eV) and switching the transport pathway from triazine to imine. Consequently, the optimized COF cathode delivers a high specific capacity of 203.6 mAh g −1 , outstanding rate capability, and exceptional cycling stability (72.9% retention after 9000 cycles). This work establishes π‐delocalization engineering as a general strategy and a redox switch to unlock latent redox functions in organic frameworks, providing a mechanistic blueprint for activating inert bonds in multivalent energy storage systems beyond magnesium batteries.

Modulating Local Coordination in Single‐Atom Catalysts: From Fundamental Concepts to Emerging Breakthroughs in Electrocatalysis

ABSTRACT Single‐atom catalysts (SACs) have attracted significant interest due to their maximized atom efficiency, structural precision, and unique catalytic properties. While the central metal atom in SACs serves as the primary active site, its catalytic behavior is strongly influenced by the surrounding environment. The local coordination sphere plays a critical role in modulating the electronic structure and reaction pathway, thereby governing the overall activity, selectivity, and stability of SACs. Consequently, precise regulation of this coordination environment through rational engineering strategies is essential for optimizing the performance of SACs. Despite growing interest, comprehensive reviews systematically analyzing local coordination environments and metal‐support interactions via electronic descriptors remain scarce, unlike synthesis/application‐focused ones. In this review article, we provide an atomic‐level, descriptor‐driven analysis of coordination effects on the electrocatalytic performance of SACs, emphasizing the synergistic interplay between central metal atoms and their coordination spheres in activating key intermediates in reactions such as water splitting and oxygen/carbon dioxide reduction. We also highlight the unique features of advanced synthetic strategies for SACs, alongside the critical role of spectroscopic and microscopic techniques in elucidating structure–activity relationships, with particular focus on integrating operando investigations and theoretical calculations. Finally, recent advances, remaining challenges, and future opportunities in coordination‐regulated SAC electrocatalysis are discussed.

Dynamic Fluorescence Visualization of Nonequilibrium Supramolecular Assembly Regulated by a Proton Reservoir

ABSTRACT Living systems sustain nonequilibrium supramolecular assemblies through continuous energy input and concomitant dissipation, with adenosine triphosphate (ATP) serving as a universal chemical fuel that regulates dynamic processes by coupling hydrolysis to downstream chemical or conformational changes. Biomimetic recreation of this behavior remains challenging because fuel‐mediated regulation in artificial assemblies is typically coupled to building‐block structure, limiting independent control over assembly dynamics and real‐time monitoring. Here we report amphiphile‐based fluorescent assemblies regulated by a time‐programmable proton reservoir, where the fuel‐consuming esterification–hydrolysis cycle is decoupled from the building blocks and controls assembly through programmed acid availability. The amphiphilic building blocks undergo stimulus–responsive assembly with fluorescence color tunable from blue to green, yellow, and white, and quantum yields spanning 1.7%–71.9%. The proton reservoir temporarily holds acid in hydrolysable esterified forms and subsequently regenerates acid over prescribed timescales; by molecular design, the acid‐masking period is tuned from 0 to 250 min and acid regeneration from 10 to 120 min. Coupling this cycle to the fluorescent assembly regulates nonequilibrium organization, enables catalytic nucleophilic reactions, and provides an intrinsic optical signal for visualizing fuel consumption and assembly transformation in real time.

Outside Front Cover: Uncovering Aggregation‐Induced Emission in Carbon Dots for Color‐Changing Hydrogels and Information Encryption

2‐CF ₂ H(D)‐Imidazolium Salts: A Reagent Platform for Bis(Deuterio)Difluoromethylation of Alkenes Under Copper/Photoredox Dual Catalysis

ABSTRACT The difluoromethyl group (–CF 2 H) has emerged as a privileged motif in modern drug design due to its ability to modulate lipophilicity and metabolic stability. Its deuterated analogue, the (deuterio)difluoromethyl group (–CF 2 D), offers further potential for enhancing metabolic stability and enabling distinct intermolecular interactions. Molecules bearing vicinal difluoromethyl or (deuterio)difluoromethyl groups can serve as potential bioisosteres of pharmacologically important vicinal diols and amino alcohols. Consequently, the direct and simultaneous installation of two difluoromethyl and (deuterio)difluoromethyl groups across alkenes represents an important synthetic target. To address current limitations, we herein introduced 2‐CF 2 H(D)‐imidazolium salts as a robust, user‐friendly reagent platform for both bis(difluoromethylation) and bis(deuterio)difluoromethylation of a broad range of alkenes, including aryl‐substituted and less reactive alkyl derivatives. The synthetic utility of this method is demonstrated through late‐stage functionalization and gram‐scale synthesis of complex molecules. Preliminary mechanistic studies revealed their distinct behavior in copper and photoredox catalysis. As such, this work establishes these reagents as a versatile platform for the simultaneous formation of C─CF 2 H and C─CF 2 D bonds, representing a significant advance in the synthesis of valuable fluorinated and deuterated compounds.

Dynamic Heterovalent Dual‐Cu Sites for O═O Cleavage in Electrocatalytic Oxygen Reduction Reaction

ABSTRACT Activation and cleavage of the inert O═O bond represent a central challenge in energy electrochemistry. Here, the Cu dual‐atom catalyst (Cu‐DAC) is constructed via bottom‐up pre‐coordination assembly and post‐encapsulation pyrolysis. The resulting Cu‐DAC features a well‐defined Cu–Cu distance (∼3.31 Å) with switchable Cu 1+ /Cu 2+ states, enabling dynamic dual‐site coordination with O 2 . Cu‐DAC achieves 0.87 V RHE half‐wave potential for oxygen reduction reaction (ORR), a near‐unity 4e − selectivity, and outstanding stability. Multiple operando spectroscopic characterizations and ab initio dynamic simulations (AIMD) reveal that the dynamic heterovalent [Cu 1+─ O─O · − ─Cu 2+ ] unit elongates the O–O bond and promotes its cleavage via dual‐site confinement and electron donation. By specifically elucidating how these dual‐atom sites dynamically evolve to facilitate O─O bond cleavage, we provide vital atomic‐level principles for the rational design of dynamically active catalysts.

Shaping Water Adsorption and Desorption in Multivariate Metal–Organic Frameworks for Optimized Ultralow‐Temperature‐Driven Refrigeration

ABSTRACT Ultralow‐temperature‐driven water‐sorption refrigeration provides an energy‐saving and eco‐friendly solution to realize near‐zero‐carbon cooling applications. Current water sorbents mainly focused on improving low‐pressure water uptakes for boosting cooling efficiency, while often hindered by cooperatively increasing desorption energy to show the opposite effect. Herein, we report a strategy of finely shaping water adsorption and desorption properties simultaneously in multivariate MOFs to maximize cooling efficiency. With broadly regulating the ratio of hydrophobic and hydrophilic linkers within UiO‐66, a series of multivariate MOFs [UiO‐66‐(BDC) x (PzDC) 1‐x ] were designed and synthesized, featuring a high tunability on both water uptake at P/P 0 = 0.2 and desorption energy. These high manipulations allow us to realize the optimal UiO‐66‐(BDC) 0.4 (PzDC) 0.6 with the most balance between water adsorption and desorption, as proven by its high water uptake of 0.4 g g −1 at P/P 0 = 0.2 and low desorption temperature down to 63°C for 90% desorption ratio. This maximizes its coefficient of performance (0.86) and working capacity (0.18 g g −1 ) for refrig‐2 applications achieved by an ultralow driving temperature of 63°C, outperforming the previously benchmark MIP‐200 (0.69 and 0.12 g g −1 ) and EMM‐8 (0.85 and 0.16 g g −1 ). The water‐sorption regulatory mechanisms were systematically elucidated by water‐loaded crystal structures.

A Polyzwitterionic “Ion‐Sponge” Interphase via In Situ Self‐Polymerization for Ultradurable Zinc Batteries

ABSTRACT Aqueous zinc batteries hold great potential for grid storage applications; however, their practical deployment is severely limited by parasitic side reactions and uncontrollable dendrite formation. Herein, we design a polyzwitterionic “ion‑sponge” interphase via an in‑situ self‑polymerization strategy. Specifically, under electric‑field induction, zwitterion monomers polymerize into an ultrathin polyzwitterion layer that electrostatically enriches anions (OTf − , SO 4 2 − ) and excludes water at the interface. This unique microenvironment enables the in‑situ reductive conversion of anions into ZnF 2 and ZnS. The resulting polyzwitterion–ZnF 2 /ZnS hybrid SEI enhances both the uniformity of Zn 2 + deposition and the Zn 2 + migration rate. The interfacial Zn 2 + diffusion coefficient reaches 1.9 × 10 − 4 cm 2 s − 1 (100 times higher than the bulk). Consequently, Zn||Zn symmetric cells stably cycle for over 1000 h at 5 mA cm − 2 and 5 mAh cm − 2 , and also for over 5500 h at −20 °C. Full cells with V 2 O 5 cathode achieve a high average capacity of 339 mAh g − 1 and 99.9% Coulombic efficiency over 1900 cycles, along with stable low‑temperature operation. This polyzwitterionic “ion‑sponge” interphase concept provides in‑depth insights into interfacial ion transport regulation for high‑performance aqueous zinc batteries.

Host Dearomatization for Prolonging Room‐Temperature Phosphorescence

ABSTRACT Host–guest doping has emerged as a powerful platform for constructing organic room‐temperature phosphorescence (RTP) materials, owing to its structural tunability and facile fabrication. However, molecular design has largely focused on guest molecules, while host screening lacks systematic theoretical guidance. Here, we propose a host dearomatization strategy that prolongs the afterglow of doped systems. By converting the benzene ring into a cyclohexane structure in the host, the RTP lifetimes of the doped systems are significantly prolonged, with the maximum enhancement reaching a 58.65‐fold increase. Mechanistic studies indicate that the extended lifetime arises from enhanced triplet‐triplet energy transfer and electronic coupling, enabled by the reduced intermolecular distance upon dearomatization. This strategy exhibits universality across diverse host and guest systems. These doped systems are further applied in time‐resolved information encryption systems and switchable adhesive materials. Starting from the host molecular framework, this study provides a universal and efficient strategy for the rational design of organic RTP materials.