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Research Article
Prebiotic Chemistry
Nonenzymatic Hydration of Phosphoenolpyruvate: General Conditions for Hydration in Protometabolism by Searching Across Pathways
- Version of Record online: 02 December 2024
Cover
Inside Back Cover: Programmable C–N Bond Formation through Radical-Mediated Chemistry in Plasma-Microdroplet Fusion
- Version of Record online: 02 December 2024
Non-thermal plasma discharge produced in the wake of charged microdroplets is found to facilitate catalyst-free radical mediated hydrazine cross coupling, as reported by Abraham K. Badu-Tawiah et al. in their Research Article (e202413122). Plasma–microdroplet fusion occurs online in a programmable reaction platform allowing direct process optimization and product validation via mass spectrometry.
Front Cover: Modular Design and Scaffold-Synthesis of Multi-Functional Fluorophores for Targeted Cellular Imaging and Pyroptosis
- Version of Record online: 02 December 2024
Building functional fluorophores from a simple scaffold. In their Research Article (e202415627), Lei Zhang, Su Jing, Thorben Cordes, and co-workers use the Ugi-4-component reaction to assemble fluorogenic dye molecules that selectively localize to mitochondria or lysosomes. The multifunctional fluorophores are not only fluorogenic but also induce pyroptosis in living cancer cells. The study shows the potential of scaffold-based synthesis for creation of new functional fluorophores.
Inside Front Cover: Subcellular Compartment-Specific Amplified Imaging of Metal Ions via Ribosomal RNA-Regulated DNAzyme Sensors
- Version of Record online: 02 December 2024
Spatially selective detection of metal ions in subcellular compartments has been achieved in the Research Article (e202412387) by Deyu Yi, Lele Li, and Mengyuan Li. This nanotechnology utilizes a specific ribosomal RNA to locally activate DNAzyme-based sensing function, driving multiple catalytic cleavage of molecular beacons for amplified metal-ion imaging in mitochondria.
Research Article
Heat Shock Proteins
Allosteric CDC37 Inhibitor Disrupts Chaperone Complex to Block CDK4/6 Maturation
- Version of Record online: 02 December 2024
MOF Sensors
Reversible and Ultrasensitive Detection of Nitric Oxide Using a Conductive Two-Dimensional Metal–Organic Framework
- Version of Record online: 02 December 2024
Highly crystalline two-dimensional conductive metal–organic framework, copper3(hexaiminobenzene)2 (Cu3(HIB)2), has been obtained through strategic synthetic modification. The Cu3(HIB)2 device shows ultrasensitive, highly selective, reversible, and low-power chemiresistive sensor for nitric oxide. Mechanistic investigation reveals the contribution of Cu-bis(iminobenzosemiquinoid) functionality of Cu3(HIB)2) for highly sensitive and reversible NO binding sites.
Phase Transition | Hot Paper
Spatial and Temporal Visualization of Polymorphic Transformations in Pharmaceutical Tablets
- Version of Record online: 02 December 2024
X-ray Diffraction Computed Tomography (XRD-CT) has been used to reveal pressure-induced phase transformations in pharmaceutical tablets of glycolide as a function of compaction pressure. Temporal analysis of the tablets, and subsequent identification using electron diffraction, revealed a hydrolysis reaction occurred on storage of the tablets. This reaction was enhanced in the presence of microcrystalline cellulose.
H2O2 Production | Hot Paper
A Chlorine-Resistant Self-Doped Nanocarbon Catalyst for Boosting Hydrogen Peroxide Synthesis in Seawater
- Version of Record online: 02 December 2024
Utilizing seawater as an electrolyte enables efficient hydrogen peroxide production for coastal applications. The NO-DC700 catalyst, synthesized via pyrolysis of silk, achieves 4997 mg L−1 h−1 H2O2 with a faradaic efficiency of 96.5 %, offering a sustainable and cost-effective method for on-site production in coastal region.
Cover
Inside Front Cover: Affecting Charges and Structures of {Bi6} Architectures by 12-Electron Transition Metal Fragments
- Version of Record online: 02 December 2024
The electron count affects the shape of Bi6q− units, from a regular prism in Bi62− (left) to a regular crown-type cycle in Bi66− (right). Such units were previously isolated in the coordination sphere of metal complexes, while the (less symmetric) intermediate with a −4 charge has only been predicted by theory. In their Research Article (e202417234), Florian Weigend, Stefanie Dehnen et al. isolated the Zintl cluster [Bi6{Zn(hmds)}2]2− (center), in which two 12-electron fragments are perfectly suited to stabilize the boat-type Bi64− unit, as confirmed by DFT calculations.
Inside Back Cover: Controlled Helical Organization in Supramolecular Polymers of Pseudo-Macrocyclic Tetrakisporphyrins
- Version of Record online: 02 December 2024
Supramolecular helical pseudo-polycatenane polymers with controlled handedness are formed via the self-assembly of chirally twisted pseudo-macrocyclic tetrakisporphyrin monomers developed by Takeharu Haino et al. in their Research Article (e202416770). The cover illustrates the supramolecular polymerization of pseudo-macrocyclic tetrakisporphyrin monomers.
Research Article
Thermally Activated Delayed Fluorescence
Declined S1 but Constant T1 Energy: Thermally Activated Delayed Fluorescence with Triplet Blocking Effect
- Version of Record online: 02 December 2024
We have demonstrated a new approach of ΔEST modulation via the triplet blocking effect, achieving decreased S1 but constant T1 energy level. The conflict between small ΔEST and large oscillator strengths is relieved. The results are crucial for fundamental photophysics as well as development of optoelectronic materials.
Communication
Chiral Warheads | Hot Paper
Synthesis and Functionalization of Sulfoximine-Bicyclo[1.1.0]butanes: Functionalizable, Tuneable and Cysteine-Selective Chiral Warheads
- Version of Record online: 02 December 2024
Sulfoximine substituted bicyclo[1.1.0]butanes are prepared in one-pot and then diversified through 3 vectors. N-Functionalization allows controlled variation in the electrophilicity of the BCB in strain release processes including in protein labelling under biocompatible conditions, and the proximal stereocenter allows stereoselective protein labelling.
Research Article
Ammonia Production | Hot Paper
Enhancing Low-Concentration Electroreduction of NO to NH3 via Potential-Controlled Active Site-Intermediate Interactions
- Version of Record online: 02 December 2024
Carbonyl Complexes | Hot Paper
Formally Zerovalent Bis(arene) Germylene Complexes of Zirconium and Hafnium
- Version of Record online: 02 December 2024
Bis(arene) coordination compounds of zirconium and hafnium have been synthesized in high yield by 4e reduction of tetrachloride adducts with a germylene phosphine Lewis pair. A puckered coordination mode of an arene moiety is discussed based on structural and spectroscopic data. Carbonyl complexes were synthesized. Dimethylbutadiene reacts under formation of a cyclohexadienyl and a triorganogermate ligand. This addition is reversible at room temperature in the zirconium case.
Supramolecular Chemistry
Using a New Pt(II) Source to Make Pt(II) Lantern-Shaped Cages, Including Low-Symmetry, Heteroleptic, and Multicavity Examples
- Version of Record online: 02 December 2024
Hydrogen Oxidation Reaction | Hot Paper
An Interstitial Boron Inserted Metastable Hexagonal Rh Nanocrystal for Efficient Hydrogen Oxidation Electrocatalysis
- Version of Record online: 02 December 2024
The metastable hexagonal Rh nanocrystal catalyst is synthesized via interstitial boron insertion for alkaline hydrogen oxidation reaction (HOR). The insertion of boron atoms into Rh lattice not only induces phase transition from face-centered cubic to hexagonal close-packed, but also optimized adsorbed behaviors of reaction intermediates, leading to improved connectivity of hydrogen-bond networks and enhanced HOR performance.
Organic Solar Cells | Hot Paper
Examining the Impact of 3D Multi-Arm Small Molecules on PM6 : Y6 Blend Reveals the Key Requirements for Their Electronic Properties
- Version of Record online: 02 December 2024
Combining molecular dynamics simulations and density functional theory calculations, we inspected the molecular-scale impact that a benzotriazole-based 3D four-arm small molecule has on the local morphology and electronic properties of PM6 : Y6 blends. Detailed examination of these aspects allowed us to highlight key requirements that the electronic properties of 3D multi-arm small molecules need to fulfill in order to improve device efficiency.
Ring-Opening Metathesis Polymerization
Ring-Opening Metathesis Polymerization of 1,2-Dihydroazete Derivatives
- Version of Record online: 02 December 2024
An exploration of 1,2-dihydroazetes in ring-opening metathesis polymerization (ROMP) is reported. The 4-membered rings readily polymerized using the Hoveyda-Grubbs 2nd generation initiator and maintained living chain-ends for block polymer synthesis. This study gives new insights into the reactivity and limitations of enamine derivatives in metathesis processes, while also offering a new approach to degradable metathesis materials with tunable properties.ROMP1,2-DihydroazeteDegradationRegio-selectivity
Communication
Photocatalysis
Benzylic C(sp3)−H Phosphonylation via Dual Photo and Copper Catalysis
- Version of Record online: 02 December 2024
A method for direct benzylic C(sp3)−H phosphonylation of non-specialized alkylarenes is reported. This dehydrogenative C−P bond formation method features high step economy and takes place under mild reaction conditions, which enables good functional group tolerance. Mechanistic studies indicate that the reaction proceeds via intermolecular hydrogen atom abstraction and operates by a radical pathway.
Research Article
Sodium-Ion Batteries
Multiple Redox-Active Centers in An Azatriangulenetrione-Based Covalent Organic Framework for High-Capacity, High-Rate and Ultra-Stable Sodium-Ion Batteries
- Version of Record online: 02 December 2024
G-quadruplex | Hot Paper
Locking up G-Quadruplexes with Light-Triggered Staples Leads to Increased Topological, Thermodynamic, and Metabolic Stability
- Version of Record online: 02 December 2024
A photochemical method for “stapling” G-quadruplex (G4) and intercalated motif (IM) structures enhances their stability, locks their topology, and increases enzymatic resistance while preserving biological activity. This method, applied to the Thrombin Binding Aptamer (TBA) model and other G4- and IM-prone sequences, shows promise for future therapeutic applications, including more stable aptamers and molecular decoys in biological systems.
Photomechanical Crystals | Hot Paper
Distinctive Photomechanical Shape Change of p-Phenylenediacrylic Acid Dimethyl Ester Single Crystals Induced by a Spatially Heterogeneous Photoreaction
- Version of Record online: 02 December 2024
The photoreaction dynamics of p-phenylenediacrylic acid dimethyl ester in single crystals were examined, revealing a reaction front propagation from the edge to the center. As the photoreaction progresses, the crystal undergoes a distinctive shape transformation, changing from a parallelogram to a distorted “fluttering flag” shape and eventually becoming a rectangle. Density functional theory calculations predict the post-reaction crystal structure, explaining this unique shape change through the spatially heterogeneous nature of the photoreaction.
RNA Damage
A Direct Chemical Repair of Etheno-Type RNA Damages
- Version of Record online: 02 December 2024
This study identifies PS9, a synthetic flavin derivative, as the first chemical repair agent for etheno-type RNA damages. PS9 effectively removes ϵA and ϵC modifications in RNA via cycloaddition with singlet oxygen under blue light, presenting a novel approach distinct from traditional protein-mediated repair. This discovery highlights potential applications in understanding RNA damage repair and its implications for RNA biology and therapeutic development.
Minireview
Photoimmunotherapy
Photon-Driven Dye Induction Pyroptosis: An Emerging Anti-Tumor Immunotherapy Paradigm
- Version of Record online: 02 December 2024
Research Article
Acid Catalysis
Triflic Acid-Catalyzed Dehydrative Amination of 2-Arylethanols with Weak N-Nucleophiles in Hexafluoroisopropanol
- Version of Record online: 02 December 2024
We report a catalytic deoxyamination of 2-arylethanols in hexafluoroisopropanol, which directly installs various amino groups, including sulfonamides, amides, ureas and anilines. The transformation relies on the intermediacy of a phenonium ion, whose formation was rationalized by mechanistic experiments and DFT calculations.
Heterogeneous Catalysis | Hot Paper
Molecular-level Modulation of N, S-Co-Doped Mesoporous Carbon Nanospheres for Selective Aqueous Catalytic Oxidation of Ethylbenzene
- Version of Record online: 02 December 2024
A facile emulsion-assisted interface self-assembly method is observed to synthesize nitrogen and sulfur co-doped mesoporous carbon nanospheres with controllable active heteroatom species at molecular level. It is proposed that the doping of pyridinic-N and thiophene-S can notably change the charge and spin densities, promoting the chemical reactivity of adjacent carbon atoms and reducing the reaction energy barrier effectively.
Communication
Organic Semiconductors | Hot Paper
Dicyanocarbene-Induced Metal-Free Efficient Quinoidization for the Development of Fused N-Type Organic Semiconductors
- Version of Record online: 02 December 2024
A new quinoidization reaction has been developed based on 2-(dimethylsulfaneylidene)malononitrile (DMSM). This reaction avoids the reliance on halogenated substrates and has unique reactivity to the electron-rich fused aromatics. Various new quinoidal compounds were synthesized, and one of them exhibits a high electron mobility up to 1.33 cm2 V−1 s−1. Our results provide a new synthetic method to expand the library of high-performance n-type organic semiconductors.
Organometallic Chemistry
Development and Applications of an Amide Linchpin Reagent
- Version of Record online: 02 December 2024
Amide/NCO linchpin: A linchpin reagent for the synthesis of amides is disclosed using rhodium-catalyzed electrophilic amination followed by Grignard addition. The sequence proceeds with high chemoselectivity and provides secondary and tertiary amides through atypical bond construction. The formation of lactams and unsymmetrical ureas demonstrates extension to other NCO systems.
Research Article
Organic Materials | Very Important Paper
Pressure-Engineered Through-Space Conjugation for Precise Control of Clusteroluminescence
- Version of Record online: 02 December 2024
Through-space conjugation in a series of tetraphenylalkanes-based nonconjugated clusteroluminogens is engineered via high-pressure structural regulation. Abnormal blue shift and remarkable emission enhancement are realized, exhibiting distinct structural factors. Intense white-light emission is realized after high-pressure treatment, disrupting the typical excited-state even-odd effects in ambient study.
H2O2 Production
Hydrogen Radical Enabling Industrial-Level Oxygen Electroreduction to Hydrogen Peroxide
- Version of Record online: 02 December 2024
An enhanced two-electron ORR performance was achieved by a rationally designed system incorporating cobalt (II) clusters onto oxidized carbon nanotube composites. This enhancement is attributed to the cooperative dual-active sites and high local proton availability, and enables effective conversion of ethylene glycol to oxalic acid by coupling with an electro-Fenton process.
Batteries | Very Important Paper
Shielding Fluoride Ion Basicity through Diurea Coordination for Nonaqueous Fluoride Shuttle Batteries
- Version of Record online: 02 December 2024
The strong basicity of fluoride ions leads to detrimental side reactions on organic cations and solvents, converting “naked” F− into bifluoride (HF2−) ions. In this work, dual 1,3-diphenylurea (DPU) ligands shield the Lewis basicity of F− through hydrogen bonding, providing long-term chemical stability across a wide range of aprotic solvents and sustaining improved electrochemical performance in nonaqueous fluoride ion batteries.
Hydrogen Evolution | Very Important Paper
Screened d-p Orbital Hybridization in Turing Structure of Confined Nickel for Sulfion Oxidation Accelerated Hydrogen Production
- Version of Record online: 02 December 2024
The constructed Turing structure, composed of lamellar stacking carbon-confined nickel nanosheets, screens the direct d-p orbit coupling between TM and S2− and activates optimized p-p orbit hybridization between electron-injected carbon and S2−, enabling exceptional catalytic activity and stability for sulfion degradation and energy-efficient yet value-added H2 production.
Total Synthesis
Total Synthesis of (−)-Cordycicadin D and 3,4-trans-Cordycicadins A and B: Entry to the 3,4-trans-Fused Cordycicadin Framework
- Version of Record online: 02 December 2024
Cordycicadins A−D are C20 polyketides, all containing a γ-lactone fused to a 10-membered lactone. The proposed biosynthesis for the cordycicadins anticipates the formation of two more natural products which are unisolated. We report the total synthesis of (–)-cordycicadin D and the two anticipated natural products.
Highlight
Proteins
Structure Prediction and Computational Protein Design for Efficient Biocatalysts and Bioactive Proteins
- Version of Record online: 02 December 2024
The Nobel Prize for Chemistry 2024 was jointly awarded to David Baker for computational protein design and to Demis Hassabis and John Jumper for protein structure prediction. This highlight showcases the impact of the Nobel prize laureates’ contributions and summarizes the history, state of the art, applications and future directions of these methods.
Research Article
Biocatalysis
Bienzymatic Dynamic Kinetic Resolution of Secondary Alcohols by Esterification/Racemization in Water
- Version of Record online: 02 December 2024
A two-enzyme-catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols in water—a ′Holy Grail of DKR′—was accomplished using an engineered alcohol dehydrogenase (ADH) for racemization through a hydrogen-borrowing sequence and variants of the acyltransferase from Mycobacterium smegmatis (MsAcT) for enantioselective acylation.
Photochemistry
Bicyclo[2.1.1]hexanes via Intramolecular Formal (3+2)-Cycloaddition
- Version of Record online: 02 December 2024
Zinc-Air Batteries | Hot Paper
Self-Organized Integrated Electrocatalyst on Oxygen Conversion for Highly Durable Zinc-Air Batteries
- Version of Record online: 02 December 2024
A bifunctional electrocatalyst (Co3O4/CoNGDY) with integrated Janus structure for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is in situ constructed through a self-organized method. The active sites and mechanism are confirmed by in situ characterizations and theoretical calculations. Aqueous zinc-air batteries with ultra-long stability and recoverable modularized cylindrical solid-state zinc-air batteries are achieved.
Oxygen Evolution Reaction
Ligand-Tuning Metallic Sites in Molecular Complexes for Efficient Water Oxidation
- Version of Record online: 02 December 2024
Heterogenized molecular complexes were designed via coordinating Fe−Ni sites with four aromatic carboxylate ligands for electrocatalytic oxygen-evolving. In situ characteristics and theoretical analysis verify that the ligands-tuning strong π-π stacking interaction between molecular complexes and carbon support renders the charge accumulation on Fe−Ni sites through fast electron transfer, following by the reconstruction of active Fe−O−Ni centers.
Communication
Carbenes
A Photochemical Strategy towards Michael Addition Reactions of Cyclopropenes
- Version of Record online: 02 December 2024
A photochemical strategy for organic-base-catalyzed Michael addition to cyclopropenes generated in situ is disclosed. In this metal-free approach, a diverse range of nitrogen nucleophiles, including drugs and bioactive molecules, are well tolerated to provide the triple substituted cyclopropanes, which have been used to access cyclopropane carboxylic acids—a new class of promising FABP-4 inhibitors.
Research Article
Ammonia-Fueled Engine | Hot Paper
A Scenario for a Carbon-Neutral Ammonia-Fueled Engine Mediated by Catalytic NH3 Cracking and CO2 Hydrogenation
- Version of Record online: 02 December 2024
The direct use of ammonia as engine fuel faces challenges like low flame velocity and high NOx emissions. We propose a novel scenario for converting a conventional “CH4-fueled” engine to “NH3-fueled” engine. Specifically, CH4 is used to power the internal combustion engine and release CO2 as the exhaust which then reacts with NH3 to generate N2 and CH4 for enclosing the carbon cycle.
Smart Organic Crystals
Combining Simple Deformations to Elicit Complex Motions and Directed Swimming of Smart Organic Crystals with Controllable Thickness
- Version of Record online: 02 December 2024
We report a water-assisted precipitation method to prepare crystals with various thicknesses that respond to ultraviolet light with simple mechanical effects, including bending, splintering, and rotation. The resulting crystal-based robots exhibit motions reminiscent of sailing and humanoid movements.
Covalent Organic Frameworks
Three-Dimensional Covalent Organic Frameworks Based on Linear and Trigonal Linkers for High-Performance H2O2 Photosynthesis
- Version of Record online: 02 December 2024
Three-dimensional covalent organic frameworks based on low-connectivity linear and trigonal linkers were constructed by the steric hindrance. The efficiency of the photocatalytic production of hydrogen peroxide was markedly enhanced by regulating of the skeleton from two-dimensional to three-dimensional configuration.
Aqueous Zinc Batteries
Bridging Electrolyte Bulk and Interfacial Chemistry: Dynamic Protective Strategy Enable Ultra-Long Lifespan Aqueous Zinc Batteries
- Version of Record online: 29 November 2024
A superior service lifespan aqueous Zn battery was built by taking advantage of the biomass-derived chitin nanocrystals colloid electrolyte to bridge electrolyte bulk and interfacial chemistry for achieving dynamic protective strategy. This unique strategy not only enables continuous optimization of electrolyte bulk and interfacial chemistry within the battery but also facilitates self-repairing of mechanical damages both internally and externally, resulting in building comprehensive, persistent, and dynamic protection for aqueous Zn batteries.
Analytical Chemistry
On-Site Portable Lithium Detection in Mining and Recycling Industries Based on a DNAzyme Fluorescent Sensor
- Version of Record online: 29 November 2024
Novel applications of a DNAzyme sensor have been developed for the on-site detection of lithium in the lithium-ion battery (LIB) industry. Simple methods to detect lithium in brine and rock mining applications, and in LIB recycling applications, have been designed and successfully implemented using the highly selective lithium DNAzyme sensor and portable fluorometers.
DNA Nanotechnology | Very Important Paper
Tandem-Controlled Dynamic DNA Assembly Enables Temporally-Selective Orthogonal Regulation of cGAS–STING Stimulation
- Version of Record online: 29 November 2024
An endogenous and exogenous tandem-regulated DNA assembly strategy is designed to achieve on-demand orthogonally controlled stimulation of cGAS–STING signaling. The approach utilizes an engineered DNA motif with an enzymatically responsive moiety and a photocleavable linker into DNA motif, enabling enzyme-mediated activation and light-triggered termination of cGAS stimulation through dynamic DNA assembly.
Zinc-Iodine Battery
Polymeric Iodine Transport Layer Enabled High Areal Capacity Dual Plating Zinc-Iodine Battery
- Version of Record online: 29 November 2024
The capacity of zinc-iodine battery is limited by the low conductivity of iodine. In this work, a polymeric conductive PVA hydrogel cathode was proposed. The unique “confined transport” of iodide/polyiodides ions in the hydrogel can effectively enhance the areal capacity with suppressed polyiodide shuttle effect.
Communication
Stable Radicals | Hot Paper
Propeller-Shaped Blatter-Based Triradicals: Distortion-Free Triangular Spin System and Spin-State-Dependent Photophysical Properties
- Version of Record online: 29 November 2024
The synthesis and properties of propeller-shaped C3v- and Cs-symmetric triradicals are described. The triradicals were antiferromagnetic equilateral triangle spin systems with J/kB~−120 K, leading to the thermal equilibrium of the doublet/quartet states at room temperature. The spin-state-dependent absorption feature, spin-selective excitation, and spin-dependent excited-state dynamics are discussed.
Research Article
Artificial Light Harvesting | Hot Paper
Chiral Rotaxane-Branched Dendrimers as Relays in Artificial Light-Harvesting Systems with Boosted Circularly Polarized Luminescence
- Version of Record online: 29 November 2024
A chiral artificial light-harvesting system that shows sequentially amplified circularly polarized luminescence (CPL) performances has been constructed from chiral rotaxane-branched dendrimers. This approach not only leads to efficient amplification of the CPL performances but will also allow the construction of novel chiral luminescent materials.
Lysine Proteome
Global Profiling Lysine Reactivity and Ligandability with Oxidant-Triggered Bioconjugation Chemistry
- Version of Record online: 29 November 2024
An oxidant-induced bioconjugation method has been developed for studying small molecule-lysine interactions. Various advantages have been demonstrated including real-time controllable labeling, excellent amino acid selectivity and labeling efficiency, in-depth lysine profiling capability and high stability. A suite of new ligandable lysines have been characterized, thus offering insights for exploring new functional and targetable residues.
Perovskite Solar Cells
Halogen Radical-Activated Perovskite-Substrate Buried Heterointerface for Achieving Hole Transport Layer-Free Tin-Based Solar Cells with Efficiencies Surpassing 14 %
- Version of Record online: 29 November 2024
The highly active halogen radicals simultaneously modified the ITO surface and chemically bridged the ITO/perovskite heterointerfaces for largely reducing the interfacial energy barrier and optimizing the interfacial carrier dynamics in hole transport layer-free Sn perovskite solar cells, achieving a record efficiency of 14.20 %.
Communication
Bent Conjugated Systems
Self-Assembled Bent Perylenediimides
- Version of Record online: 29 November 2024
A series of bent perylenediimides (B-PDIs) with systematically varied bending angles were designed and synthesized by modulating the lengths of linear alkyl chains bridging the two nitrogen atoms of each PDI. This study unveils the curvature-dependent self-assembly and excited-state decay behavior of these B-PDIs.
Research Article
Photocatalysis | Very Important Paper
Dual Regulation of Sensitizers and Cluster Catalysts in Metal–Organic Frameworks to Boost H2 Evolution
- Version of Record online: 29 November 2024
A photosensitizer/catalyst dual regulation strategy was proposed based on POM@MOF molecular platform to construct the highly efficient catalysts for photocatalytic H2 evolution. Impressively, the resulting Ni−Sb9@UiO−Ir−C6 can efficiently drive water splitting into H2 with a TON of 326923, representing a record value among all the POM@MOF composites.
Review
Photocatalytic Polymerization
Better Together: Photoredox/Copper Dual Catalysis in Atom Transfer Radical Polymerization
- Version of Record online: 29 November 2024
A combination of Cu-ATRP catalysis with photocatalysts (PCs) that absorb visible and/or NIR light exhibits synergistic action at the ppm/ppb concentration level. It leads to very well-defined polymers with rates depending on the amount and quantum efficiency of PC but controlled polymer architecture defined by the Cu-catalysts. Thus, they can act much better together, providing robustness, oxygen tolerance, and access to new materials.
Introducing …
Graeme Howe
- Version of Record online: 29 November 2024
“The most exciting thing about my research is the vast amount of genetic information available in public databases whose biocatalytic potential remains untapped… If I won a million dollars in the lottery I would pay my team what they deserve, while focusing more on science and less on fundraising…” Find out more about Graeme Howe in his Introducing… Profile.
Corrigendum
Corrigendum: Enzyme-Mediated In Situ Self-Assembly Promotes In Vivo Bioorthogonal Reaction for Pretargeted Multimodality Imaging
- Version of Record online: 29 November 2024
Research Article
Biomass Conversion
Binary Iron-Manganese Cocatalyst for Simultaneous Activation of C−C and C−O Bonds to Maximally Utilize Lignin for Syngas Generation over InGaN
- Version of Record online: 29 November 2024
Host–Guest Systems
Confinement Microenvironment Regulation of Carbon Dots in Zeolite for Multi-Mode Time-Dependent Phosphorescence Color Evolution
- Version of Record online: 29 November 2024
A novel matrix-controlling strategy is presented in CDs-in-zeolite system to regulate the microenvironment of CDs by doping limited Mn2+ in zeolite. Mn-coordinated CDs (C-CDs) induce green phosphorescence, and non-coordinated CDs (NC-CDs) exhibit temperature-related blue or red phosphorescence due to energy transfer. Finally, multi-mode time-dependent phosphorescence color evolution with temperature variation in a single system is achieved.
Metal-Organic Frameworks
Skeletal Nitrogen Functionalization of Isostructural 2D Conjugated MOFs for Enhancement of the Dual-Ion Storage Capacity
- Version of Record online: 29 November 2024
A skeletal nitrogen introduction strategy has been developed to fine-tune the dual-ion storage properties of isostructural 2D conjugated metal–organic frameworks (2D c-MOFs). The faradaic charge storage in isostructural MOFs can be improved by introducing additional aromatic nitrogen sites which synergistically act as cation adsorption sites and favor anion-adsorption to the metal sites energetically.
Communication
Cross-Coupling
Iodide Anion Enables a Reductive Cross-Electrophile Coupling for Preparing Tertiary Amines
- Version of Record online: 29 November 2024
We describe a cross-electrophile coupling of iminium ions with a range of electrophilic substrates to prepare tertiary amines. This reaction is mediated by the underexplored single-electron reducing power of the iodide counter anion, which is investigated both experimentally and through quantum chemical calculations.
Research Article
Energy Storage
Hypercrosslinked Metal-Organic Polyhedra Electrolyte with High Transference Number and Fast Conduction of Li Ions
- Version of Record online: 29 November 2024
A type of hypercrosslinked MOP (HCMOP) solid-state electrolyte was prepared using cationic MOPs, PEI macromonomer and polyelectrolyte units. Owing to the three-component synergistic effect, Li-HCMOP has excellent mechanical strength and can realize a high Li-ion conductivity, a high Li-ion transference number and a low activation energy. This work highlights an effective idea of high-performance MOP-based solid-state electrolytes applied in LMBs.
Ethylene Purification | Hot Paper
Ethane Triggered Gate-Opening in a Flexible-Robust Metal-Organic Framework for Ultra-High Purity Ethylene Purification
- Version of Record online: 29 November 2024
We report a flexible-robust MOF Zn(ad)(min) that features a unique localized flexible gate to priority adsorb the cross-section well-matched ethane molecules, thus achieving the unprecedented ethane adsorption capacity (62.6 cm3 g−1), ethane/ethylene uptake ratio 3.34 (298 K and 0.1 bar), and the remarkable ultra-high purity ethylene (>99.995 %) productivity up to 39.2 L/kg at ambient condition.
Energy Storage | Hot Paper
Azopyridine Polymers in Organic Phase Change Materials for High Energy Density Photothermal Storage and Controlled Release
- Version of Record online: 29 November 2024
The meta-azopyridine polymer (3-PAZOPY with an unprecedented untra-high energy density of 430 J/g forms a stable uniform two-phase hybrid composite system with the organic phase change material octanoic acid (OA) through a combination of hydrogen bonding and van der Waals interactions. This system, serving as a noval solar photothermal fuels (STFs), is capable of simultaneously storing both photochemical and phase change energy, which holds significant potential for applications in household consumers energy distribution and utilization systems, as well as in photothermal-assisted insulation strategies.
Gold Recovery | Hot Paper
Nano-Springe Enriched Hierarchical Porous MOP/COF Hybrid Aerogel: Efficient Recovery of Gold from Electronic Waste
- Version of Record online: 29 November 2024
Oxygen Activation
Activating Oxygen via the 3-Electron Pathway to Hydroxyl Radical by La−O4 Single-atom on WO3 for Water Purification
- Version of Record online: 29 November 2024
A selective oxygen activation to hydroxyl radicals via 3 e− pathway using single atomically dispersed La based on WO3 fabricated with oxygen vacancies to weaken La−O coordination strength (denoted as LaO4−WOv) is achieved. Rapid and complete removal of tetracycline realizes over LaO4−WOv with 0.077 min−1 of rate constant. This work builds a catalyst for manipulating oxygen activation towards water purification as a representative application.
Main-Group Chemistry | Hot Paper
Zwitterionic 2-Phosphaethene-thiolates [(LC)P=CS(LC/P)]+ as PCS Building Blocks (LC=NHC, LP=PR3)
- Version of Record online: 29 November 2024
PCS building blocks: This work presents the facile synthesis of zwitterionic salts [(LC)P=CS(LC/P)][OTf], which function as convenient, regioselective and multifaceted synthons of the PCS moiety. DFT calculations support a zwitterionic composition with a negative PCS moiety and two cationic P- and C-bound substituents. Depending on the nature of the C-bound substituent, different reactivity can be addressed in cycloaddition and reduction reactions.
Communication
C-H Activation
T-shaped 14 Electron Rhodium Complexes: Potential Active Species in C−H Activation
- Version of Record online: 29 November 2024
Two T-shaped Rh(I) complexes with PNP pincer ligands have been isolated. They react with C−H bonds of unactivated substrates such as ethylene and benzene, leading to the oxidative C−H addition products. Depending on the size of the alkyl groups on the phosphorus atom, the reactivity towards C−H bonds can be fine-tuned.
Research Article
Unactivated Allenes
Palladium-Catalyzed, Regio-/Stereo- and Enantiospecific Anti-Carboxylation of Unactivated Internal Allenes
- Version of Record online: 29 November 2024
A directing group-controlled, palladium-catalyzed, regio-, stereo-, and enantiospecific anti-carboxylation of unactivated, internal allenes has been developed via the synergistic interplay of a rationally designed bidentate directing group, palladium catalyst, and a multifunctional acetate ligand. The corresponding trans allyl ester was obtained in excellent yields with exclusive δ-regioselectivity and anti-carboxypalladation stereocontrol.
Introducing …
Prince Nana Amaniampong
- Version of Record online: 29 November 2024
“The most important factor in the choice of my current research topic was its potential to make a meaningful impact on sustainable energy and chemical solutions. The idea of using sonocatalysis to drive reactions with less energy, near-ambient temperatures and fewer pollutants really resonated with me… My favorite time of day is early morning, just as the sun rises…” Find out more about Prince Nana Amaniampong in his Introducing… Profile.
Obituary
Vijay Nair (1941–2024): A Beacon of Wisdom
- Version of Record online: 28 November 2024
Vijay Nair, one of India's most prominent organic chemists, passed away on April 12, 2024 at the age of 82. After a distinguished research career in the U.S. pharmaceutical industry, he returned to India to lead what was to become the National Institute for Interdisciplinary Science and Technology (NIIST). During this second phase of his career, he made fundamentally important contributions to the art of organic synthesis and mentored a number of organic chemists.
Communication
Asymmetric Catalysis
Copper(I)-Catalyzed Asymmetric 1,4-Hydroarsination of α,β-Unsaturated Compounds
- Version of Record online: 28 November 2024
Electrocatalytic O2 Evolution
Applicable Descriptors under Weak Metal-Oxygen d–p Interaction for the Oxygen Evolution Reaction
- Version of Record online: 28 November 2024
New descriptors are presented for the oxygen evolution reaction (OER) in ionic systems. Through first-principles calculations, the limitations of the most widely used and crucial descriptors d-band center and charge transfer energy, are demonstrated. Novel descriptors, λ1 and λ2, are proposed for more accurate OER performance predictions. Their application to multi-component and high-entropy oxides offers insights into designing more efficient catalytic materials.
Research Article
Photodynamic Therapy
A Microrobotic System Based on Engineered Bacteria for Targeted Self-Driven Photodynamic Therapy
- Version of Record online: 28 November 2024
A platform composed of engineered bacteria is developed to perform photochemical reactions for photodynamic therapy in a self-driven manner. One E. coli strain was genetically modified to produce 5-ALA and KatG, enabling the generation of PpIX and oxygen within tumors. Another E. coli strain was engineered to autonomously emit bioluminescence under the regulation of quorum sensing, to excite the photosensitizer formed in tumors.
Molecular Electrocatalysts | Very Important Paper
Subtle Modifications in Interface Configurations of Iron/Cobalt Phthalocyanine-Based Electrocatalysts Determine Molecular CO2 Reduction Activities
- Version of Record online: 28 November 2024
Molecular strain has an adverse or conducive effect on catalytic activity. Strained cobalt tetraaminophthalocyanine improves *CO binding for subsequent hydrogenation, attaining methanol Faradaic efficiency up to 52 %. However, strained iron phthalocyanine exacerbates *CO poisoning, leading to inferior CO production. We proposed *CO binding strength as an indicator for activity prediction.
Supramolecular Chemistry
Electrostatically Dominated Pre-Organization in Cyclodextrin Metal–Organic Frameworks
- Version of Record online: 28 November 2024
Electrostatic interactions have been found to dominate the pre-organization of carboxylate anionic guests inside the tunnels of cyclodextrin metal-organic frameworks. These interactions are so strong that they override the influence of all other noncovalent bonding interactions present in the tunnels.
Peroxo Complexes | Very Important Paper
Structural Snapshots, Trajectory and Thermodynamics of the Reversible μ-1,2-Peroxo/μ-1,1-Hydroperoxo Dicopper(II) Interconversion
- Version of Record online: 28 November 2024
Detailed information is obtained for the reversible H+-transfer interconverting reactive μ1,2-peroxodicopper(II) and μ1,1-hydroperoxodicopper(II) species, including the structural characterization of H-bond donor adducts and a DFT mapping of the correlated H+-transfer and μ1,2-peroxo→μ1,1-peroxo rearrangement. This establishes a mechanistic basis for a key component of the proton-coupled electron transfer (PCET) reactivity involving biorelevant Cu2/O2 intermediates.
Black Phosphorus Photocatalyst
Modulating the Band Structure of Two-Dimensional Black Phosphorus via Electronic Effects of Organic Functional Groups for Enhanced Hydrogen Production Activity
- Version of Record online: 28 November 2024
We demonstrate that organic functional groups can modulate the band structure of two-dimensional black phosphorus (BP). By modifying BP′s surface, these groups alter charge density and shift band-edge positions, enabling continuous tuning of BP's valence and conduction bands. This approach achieves high hydrogen evolution reaction rates under visible light, offering a flexible, cost-effective strategy for enhancing BP-based photocatalysts.
Batteries | Hot Paper
Single Atomic Cu-C3 Sites Catalyzed Interfacial Chemistry in Bi@C for Ultra-Stable and Ultrafast Sodium-Ion Batteries
- Version of Record online: 28 November 2024
Single atom Cu regulated Bi@C with Cu–C3 sites have been innovatively designed by the simple pyrolysis of metal-organic framework. The Cu–C3 sites can serve as both a modulator to catalyze the formation of inorganic-rich and powerful solid electrolyte interphase and a promoter to facilitate the adsorption and diffusion of Na+, which endow the sample with high-efficient sodium ion storage performance.
Communication
Organic Materials | Hot Paper
A C156 Molecular Nanocarbon: Planar/Rippled Nanosheets Hybridization
- Version of Record online: 28 November 2024
A new hybrid nanocarbon composed of dissimilar naonosheets, has been synthesized. This hybrid possesses electronic properties similar to its components and exhibits a highly curved structure with configurational stability. This curved structure was found to accommodate C60 with a binding constant as high as 105 M−1. Moreover, this hybrid displays unusual anti-Kasha fluorescence emission and undergoes singlet fission in the thin film.
Research Article
Biomaterials
Engineered Metal–Organic Framework with Stereotactic Anchoring and Spatial Separation of Porphyrins for Amplified Ultrasound-Mediated Pyroptosis and Cancer Immunotherapy
- Version of Record online: 28 November 2024
A dual-solvent strategy was employed to synthesize a porphyrin-based nanoscale metal–organic framework (Fe(TCPP)-MOF) with novel crystal structure and unique morphology. The exquisite configuration ensured the orderly anchoring and precise spatial separation of porphyrin molecules, effectively circumventing the aggregation-caused quenching (ACQ) effect and suppressing non-radiative transitions. This unique structural design endows Fe(TCPP)-MOF with excellent reactive oxygen species (ROS) generation capabilities, and under ultrasound activation, it can effectively induce tumor cell pyroptosis and activate immune responses.
Review
Cancer Therapy
Nanomaterials-Induced PANoptosis: A Promising Anti-Tumor Strategy
- Version of Record online: 28 November 2024
In this review, we delve into the foundational concept and underlying mechanisms of PANoptosis, emphasizing its pivotal role in oncology. We subsequently outline the most recent advancements in nanomedicine pertaining to PANoptosis-driven anticancer therapies. Furthermore, we explore the existing challenges and potential future directions for the clinical translation of PANoptosis-based treatments.
Communication
Porphyrins
High Charge Carrier Mobility in Porphyrin Nanoribbons
- Version of Record online: 28 November 2024
Time-resolved terahertz (THz) spectroscopy experiments show that charge carriers, generated by an optical pulse (hν), on a π-conjugated porphyrin nanoribbon are exceptionally mobile. The porphyrin nanoribbons are polydisperse polymers synthesized by nickel(0)-mediated Yamamoto coupling followed by oxidative planarization, and have an average degree of polymerization of up to 37 repeat units (length 31 nm).
Research Article
Photosensitizers
Electron Transfer Mediator Modulates Type II Porphyrin-Based Metal–Organic Framework Photosensitizers for Type I Photodynamic Therapy
- Version of Record online: 28 November 2024
An effective and universal electron transfer-based strategy is introduced to modulate the reactive oxygen species (ROS) generation in porphyrin-based metal–organic frameworks (MOFs). This approach enables the conversion of existing Type II MOFs into Type I MOFs with hypoxic tolerance to function effectively under low-oxygen conditions, providing new insight into the development of Type I MOFs.
Communication
Macrocyclic Compounds
Fluorinated Squareimines for Molecular Sieving of Aromatic over Aliphatic Compounds
- Version of Record online: 28 November 2024
Squareimines are a new class of electron-deficient macrocycles with a unique rectangular structure that facilitates interactions with the electron-deficient panels, enabling selective separation of aromatic hydrocarbons from aliphatic mixtures. By using dynamic covalent imine chemistry, crystalline material NDI2F42 is obtained in high yields, with this material demonstrating rapid adsorption and high selectivities for the sieving of aromatic compounds.
Research Article
Polymer Chemistry | Very Important Paper
Mechanics-Photophysics Correlation in Tough, Stretchable and Long-Lived Room Temperature Phosphorescence Ionogels Deciphered by Dynamic Mechanical Analysis
- Version of Record online: 28 November 2024
We employ dynamic mechanical analysis (DMA) spectra to establish mechanics-DMA-photophysics correlation for ionogels. This resembles parallel and sequential processing of human brain from sensation to cognition. This work provides an enabling strategy towards the early indication of performance of ionogels without laborious characterization.
Perovskite Films | Hot Paper
Idealizing Air-Processed Perovskite Film Competitive by Surface Lattice Etching-Reconstruction for High-Efficiency Solar Cells
- Version of Record online: 28 November 2024
We propose a novel in situ lattice etching-reconstruction strategy enabled by hot organic esters with low polarity to idealize air-processed perovskite films for competitive solar cells regardless of humidity. Arising from the dynamic dissolution of nanoimpurities and selective recrystallization of Br-rich phase on the defective perovskite surface, we deliver a champion PCE of 15.37 % for all-air-processed carbon-based CsPbI2Br cell with excellent stability.
Tandem CO2 Hydrogenation–Carbonylation | Hot Paper
Shape-Selective Zeolites for Tandem CO2 Hydrogenation-Carbonylation Reactions
- Version of Record online: 28 November 2024
A zeolite-based compartmentalized approach for one-step carbonylation reactions with CO2 is developed. We show that zeolite shape-selectivity is key to impede unwanted hydrogenation of olefinic substrates and that our catalytic tandem concept enables an equilibrium shift of the low temperature reverse water-gas shift (RWGS) reaction, ultimately resulting in the efficient formation of aldehydes, esters and amides.
Communication
Synthesis of Aziridine Phosphines
Manganese(I)-Catalyzed Access to Enantioenriched Chiral Aziridine Phosphines
- Version of Record online: 28 November 2024
A highly enantioselective hydrophosphination of 2H-azirines is reported based on a newly discovered Mn(I) catalyst that plays an important role in both the reactivity and stereoselectivity of the process. Various valuable aziridine phosphines can now be accessed in high yields and enantiopurities. DFT calculations provide mechanistic insights.
Research Article
Ligand Desymmetrization in MOFs
Leveraging Ligand Desymmetrization to Enrich Structural Diversity of Zirconium Metal–Organic Frameworks for Toxic Chemical Adsorption
- Version of Record online: 28 November 2024
Synthetic Biology | Very Important Paper
Ligand-Responsive Artificial Protein–Protein Communication for Field-Deployable Cell-Free Biosensing
- Version of Record online: 27 November 2024
A ligand-responsive artificial protein–protein communication (LIRAC) was developed by redefining the connection between transcription factors (TFs) and CRISPR/Cas enzymes that do not have natural interactions. LIRAC immediately transduces target-induced TF allostery into fast activation of CRISPR/Cas enzymes within a homogeneous system, allowing for rapid response, tunable dynamic range, tristate logic, and portable detection.
Fluorescent Probes
GlutaR: A High-Performance Fluorescent Protein-Based Sensor for Spatiotemporal Monitoring of Glutamine Dynamics In Vivo
- Version of Record online: 27 November 2024
Visualization of the metabolism of glutamine in vivo: Glutamine is the most abundant amino acid in human blood and muscle. GlutaR, a genetically encoded fluorescence sensor of glutamine, displays excellent selectivity and sensitivity, which enable to report dynamic and precise changes of glutamine levels in cells, live mice, and quantification of free subcellular organelle glutamine concentrations with high spatiotemporal resolution.
Supramolecular Chemistry | Hot Paper
Simultaneous Fabrication of P and M Helices in One-Component Chiral System by Methanol-Water Mediated Dual Assembly Pathway
- Version of Record online: 27 November 2024
We report a methanol-water mediated dual assembly pathway strategy for simultaneous construction of P and M helices in one-component chiral system. The conformation of L-phenylaniline derivates (LBpyF) is controlled to folded state in CH3OH. Addition of H2O into above CH3OH solution of LBpyF results in the simultaneous occurrence of two self-assembly pathways, due to the synchronous process of 1) self-assembly of folded LBpyF into M-helices and 2) H2O induced unfolding of folded LBpyF molecules followed by self-assembly of them into P-helices.
Graphene Nucleation
Unconventional Near-Equilibrium Nucleation of Graphene on Si-Terminated SiC(0001) Surface
- Version of Record online: 27 November 2024
Graphene nucleation on Si-terminated hexagonal-SiC(0001) surface is elucidated. The stable carbon clusters, preferential nucleation sites and nucleation pathways are revealed, and a nucleation diagram is established. Contradictory experimental observations on graphene growth on SiC(0001) surface are explained. Nucleation on terraces instead of near step edges is proposed to be crucial for producing high-quality graphene on SiC(0001) surface.
Communication
Electrocatalysis
Metal-Phthalocyanine-Based Two-Dimensional Conjugated Metal-Organic Frameworks for Electrochemical Glycerol Oxidation Reaction
- Version of Record online: 27 November 2024
Exploring 2D c-MOFs for Electrocatalytic Glycerol Oxidation Reaction(GOR): This work introduces a novel class of two-dimensional conjugated metal–organic frameworks (2D c-MOFs), M2[NiPcS8] with various metal center based on octathiolphthalocyaninato nickel (NiPc(SH)8). Focusing on glycerol oxidation reaction (GOR), theoretical and experimental analyses reveal the superior performance of the CoS4 site in Co2[NiPcS8] among the family of 2D c-MOFs M2(M'PcX8) (M/M’=Cu/Ni/Co, X=S/O/NH). The electrocatalytic tests demonstrate that Co2[NiPcS8] supported by carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm−2, which contributes to excellent overall water-electrolysis-voltage reduction by 0.27 V from oxygen evolution reaction to GOR.
Research Article
Protein Modification | Hot Paper
One-Step Maleimide-Based Dual Functionalization of Protein N-Termini
- Version of Record online: 27 November 2024
Maleimides can target the N-termini of proteins instead of cysteine by the use of 2-pyridinecarboxaldehyde and copper(II) salt under non-denaturing conditions. The methodology requires no mutagenesis of proteins and enables the high-yield attachment of various functional groups to proteins with various N-terminal amino acids through a simple operation using commercially available maleimides.
Oxygen Reduction | Very Important Paper
Meso/Microporous Single-Atom Catalysts Featuring Curved Fe−N4 Sites Boost the Oxygen Reduction Reaction Activity
- Version of Record online: 27 November 2024
A novel ZnO-assisted ZIF derivation approach is developed to synthesize an atomically dispersed meso/microporous Fe−N/C catalyst with curved Fe−N4 active sites onto the tubular carbon walls, showing excellent oxygen reduction performance in both acidic and alkaline media. When used in proton exchange membrane fuel cells and Zn-air batteries, it demonstrates outstanding cell/battery performance.
Graphene Nanoribbons | Hot Paper
An Expeditious Synthesis of Near-Infrared-Absorbing Imide-Based Graphene Nanoribbons and Their Photothermal Properties
- Version of Record online: 27 November 2024
CO2 Reduction
Interface-Engineering-Induced C−C Coupling for C2H4 Photosynthesis from Atmospheric-Concentration CO2 Reduction
- Version of Record online: 27 November 2024
Loading highly active metal clusters on a semiconductor nanosheet can enable the introduced metal atom and the metal atom in substrate materials to construct the heteroatom pair sites. Having two different metal atoms on the interface as active sites may effectively accelerate C−C coupling to form C2H4 for CO2 photoreduction.
Communication
Diagnosis and Therapy | Very Important Paper
Rapid, Non-Invasive, Accurate Diagnosis and Efficient Clearance of Metastatic Lymph Nodes
- Version of Record online: 27 November 2024
A versatile theranostic nanosystem (FLAGC) is reported for rapid, non-invasive, accurate diagnosis and efficient clearance of metastatic lymph nodes. FLAGC is easily drained to sentinel lymph nodes (SLNs) for precise localization. FLAGC is then specifically lit up by the low pH and over-expressed myeloperoxidase (MPO) in the tumor microenvironment (TME), resulting in an accurate diagnosis of metastatic SLNs by chemical resonance energy transfer (CRET) luminescence in the second near-infrared window. Further, the tumor was efficiently eradicated through Ce6-mediated photodynamic therapy (PDT). Our findings offer a new paradigm for identifying and eliminating clinically positive lymph nodes.
Research Article
MXenes for Batteries | Hot Paper
Ultra-rapid Synthesis of High-entropy MAX Phases and Their Derivative MXenes for Battery Electrodes
- Version of Record online: 27 November 2024
We synthesized high-entropy MAX phases within 15 minutes, including a new phase (Ti0.2V0.2Cr0.2Nb0.2Mo0.2)4AlC3 and three 413-type phases. The varied stacking modes among MX slabs in high-entropy MAX phases and the distinct topological transformations to their derivative MXenes were observed. TiVNbMoC3 electrode demonstrates superior lithium-ion storage capabilities with 725 mAh g−1 after 1000 cycles at 1 A g−1, triggering the edification to the application of high-entropy MXenes for energy domain.
Li-Storage | Hot Paper
Hubbard Gap Closure-Induced Dual-Redox Li-Storage Mechanism as the Origin of Anomalously High Capacity and Fast Ion Diffusivity in MOFs-Like Polyoxometalates
- Version of Record online: 27 November 2024
Dual-redox Li-storage mechanism is first decoded as the origin of anomalously high capacity and fast diffusivity in MOFs-like POM electrode, where enhanced V-t2g orbital occupation, Hubbard gap closure and interlayer conjugated configuration essentially contribute to the high capacity, accelerated rate capability and superior cycle stability.
Strained Molecules
Stereoselective Radical Acylfluoroalkylation of Bicyclobutanes via N-Heterocyclic Carbene Catalysis
- Version of Record online: 27 November 2024
We have realized the stereoselective acylfluoroalkylation of bicyclobutanes via radical N-heterocyclic carbene (NHC) catalysis, which constitutes a practical method to assemble fluoroalkyl-substituted cyclobutanes. It is noteworthy that the covalent-based organocatalytic strategy achieved diastereoselective radical-radical cross coupling, with dispersion and electrostatic interactions playing a crucial role in stereoinduction.
COFs for Zinc Batteries | Hot Paper
Freestanding Phosphonium Covalent Organic Frameworks with Efficient Hydroxide Conduction for Zinc–Air Batteries
- Version of Record online: 27 November 2024
Alkaline-stable phosphonium-based covalent organic frameworks (COFs) work as durable and efficient hydroxide conductors for zinc–air battery applications. Especially, the COFs with a minimal ion exchange capacity of 1.17 mmol g−1 resulted in 126 mS cm−1 at 80 °C, and batteries with the COF electrolytes demonstrated stable operation over 2,300 min.
Photocatalytic Urea Synthesis
Enhanced Photocatalytic Synthesis of Urea from co-Reduction of N2 and CO2 on Z-Schematic SrTiO3-FeS-CoWO4 Heterostructure
- Version of Record online: 27 November 2024
The Z-schematic SrTiO3-FeS-CoWO4 catalyst is efficient for urea photosynthesis from CO2 and N2 reduction. It has dual active sites for adsorption and activation of CO2 and N2 and the accelerated kinetics for C−N coupling reaction. The energy barrier of rate-determining step is reduced on SrTiO3-FeS-CoWO4.
Organic Semiconductors
Quinoline Substituted Anthracene Isomers: A Case Study for Simultaneously Optimizing High Mobility and Strong Luminescence in Herringbone-Packed Organic Semiconductors
- Version of Record online: 27 November 2024
The structure–property relationship in high mobility emissive materials was revealed that a centroid distance of about 7–7.5 Å along CH-π direction and 6–6.5 Å along π–π direction is beneficial for achieving high mobility and strong emission in herringbone-packed aggregates simultaneously based on four quinoline-anthracene isomers. This relationship also demonstrates the broad applicability and universal potential in other organic semiconductors.
CO2 Hydrogenation | Hot Paper
Low-temperature CO2 Hydrogenation to Olefins on Anorthic NaCoFe Alloy Carbides
- Version of Record online: 27 November 2024
A highly active (FexCoy)5C2 structure is developed through the synergistic effect of electronic (sodium) and structural (cobalt) promoters. This strategy facilitates the hydrogenation of carbon dioxide into olefins at a low temperature of 240 °C, achieving the highest STY of olefins at low temperatures, even better than a significant proportion under high-temperature operating conditions. Additionally, it retains the capability to synthesize olefins at 180 °C.
Communication
Homogeneous Catalysis
Nickel-Catalyzed Difluoroalkylation of β,γ-Unsaturated α-Amino Nitrile Derived Lithium Reagents
- Version of Record online: 27 November 2024
A nickel-catalyzed difluoroalkylation of β,γ-unsaturated α-amino nitrile derived lithium reagents with various difluoroalkyl bromides has been developed. The rapid fluorine-editing of drugs demonstrates the synthetic versatility and utility of this protocol, showing the perspective in modern drug discovery.
Research Article
Room-Temperature Phosphorescence
Modulating Room-Temperature Phosphorescence of Phenothiazine Dioxide via External Heavy Atoms
- Version of Record online: 27 November 2024
External halogen-π interactions have been demonstrated to be a key feature for the development of ultralong phosphorescent material. A phenothiazine dioxide (DOPTZ) featuring a chloride atom linked through a flexible alkyl chain (DOPTZ-C3Cl) exhibits an ultralong phosphorescence lifetime of 1351 ms and a phosphorescence quantum yield of 10.1 %, the highest values among phenothiazine-based phosphorescent substances.
Asymmetric Catalysis
Enantioselective Synthesis of Axially Chiral Tetrasubstituted Alkenes by Copper-Catalyzed C(sp2)–H Functionalization of Arenes with Vinyl Cations
- Version of Record online: 27 November 2024
A copper-catalyzed enantioselective C(sp2)-H functionalization of arenes with vinyl cations has been realized, enabling the atom-economical preparation of axially chiral acyclic tetrasubstituted alkenes. This transformation is the first example of the assembly of atropisomeric alkenes via vinyl cations. Notably, the constructed axially chiral skeletons were shown to be applicable to asymmetric catalysis.
Glycopeptides
Diastereoselective Anomeric C(sp3)−H Cyclization Towards the Design of New Cyclophane-Braced Glycopeptides
- Version of Record online: 27 November 2024
An efficient Pd-catalyzed C(sp3)−H anomeric activation approach has been developed for the synthesis of cyclophane-braced glycopeptides. This technique is versatile and can be applied to glycopeptides of various cyclic sizes. In addition, biological evaluations of some glycophanes revealed that this series exhibits promising antiproliferative activity against various cancer cell lines.
Covalent Organic Frameworks
Highly Efficient Chiral Separation Based on Alkali-proof Protein Immobilization by Covalent Organic Frameworks
- Version of Record online: 27 November 2024
Basophilic alcalase is creatively developed to fabricate ultrastable protein-based chiral stationary phases that can efficiently work under alkaline conditions. Upon incorporating CSPs into chiral separation columns, we enable high-precision chiral chromatographic separation with exceptional stability.
Dimetallocenes | Hot Paper
Heavy Pentaisopropylcyclopentadienyltriylenes and their Heterobimetallic Complexes
- Version of Record online: 27 November 2024
Molecular Crystals
Precise Photochemical Post-Processing of Molecular Crystals
- Version of Record online: 27 November 2024
We report a method to fabricate molecular crystals of desired size and aspect ratio that capitalizes on their photochemical reactivity. The resulting crystals retain their physical properties and can be used to transduce light, among other applications requiring aspect ratios that are currently unavailable by crystallization approaches.
Biomaterials
Printing Cell Embedded Sacrificial Strategy for Microvasculature using Degradable DNA Biolubricant
- Version of Record online: 27 November 2024
We developed a general PRINting Cell Embedded Sacrificial Strategy (PRINCESS) and successfully fabricated microvasculatures using degradable DNA biolubricant. This is the first demonstration of direct cell printing to fabricate microvasculature. Utilizing the DNA hydrogel as biolubricant, we can print a 70 μm endothelialized microvasculature and cell-laden tissue constructs with branched microvasculatures.
Communication
Stereoselective Synthesis
Stereoselective Synthesis of 1,n-Dicarbonyl Compounds Through Palladium-Catalyzed Ring Opening/Isomerization of Densely Substituted Cyclopropanols
- Version of Record online: 27 November 2024
We report the stereoselective synthesis of highly substituted cyclopropanols and their palladium-catalyzed stereospecific transformation into 1,4- and 1,5-dicarbonyls. The developed ring opening/chain walking sequence enables access to dialdehydes and ketoaldehydes bearing vicinal tertiary and quaternary stereocenters as single diastereomers in moderate to high yields.
Research Article
Bioinorganic Chemistry
Imidazolate-Stabilized Cu(III): Dioxygen to Oxides at Type 3 Copper Sites
- Version of Record online: 27 November 2024
Type 3 (coupled binuclear) copper systems reduce dioxygen for transport, substrate oxygenation, and electron transfer across aerobic life. Using synthetic models with protic histidine environments, we find that the histidine-stabilized copper centers become not just one-electron but also two-electron shuttles—they isomerize to copper(III) when deprotonated by a base.
Host-Guest Systems
Temperature-Dependent Left- and Right-Twisted Conformational Changes in 1 : 1 Host-Guest Systems: Theoretical Modeling and Chiroptical Simulations
- Version of Record online: 27 November 2024
Novel equations based on the mass-balance model were applied to analyze 1 : 1 host-guest systems for achiral and chiral host molecules with left- and right-twisted conformations (HM and HP) and chiral and achiral guest molecules (GX). Theoretical analysis for the variable temperature circular dichroism (VT−CD) experiments resulted in the successful determination of the thermodynamic parameters, equilibrium constants (K), and molar CD values.
Gas Separation
A Microporous Hydrogen-Bonded Organic Framework with Open Pyrene Sites Isolated by Hydrogen-Bonded Helical Chains for Efficient Separation of Xenon and Krypton
- Version of Record online: 26 November 2024
Metal-Organic Frameworks
Regulated Charge Transfer in Donor-Acceptor Metal–Organic Frameworks for Highly-Sensitive Photodetectors
- Version of Record online: 26 November 2024
A layer-by-layer approach is used to grow naphthalenediimide-based donor-acceptor MOF thin films for efficient free charge generation in response to light. Interestingly, we find that the optimum photocurrent response is obtained at a low optimal doping concentration of acceptor, which outperforms traditional donor-MOF thin films by a factor of forty.
Photoisomerization
A Detailed View on the (Re)isomerization Dynamics in Microbial Rhodopsins Using Complementary Near-UV and IR Readouts
- Version of Record online: 26 November 2024
Communication
Heterogeneous Catalysis
Carbon Nanoparticle Oxidation by NO2 and O2: Chemical Kinetics and Reaction Pathways
- Version of Record online: 26 November 2024
Using a kinetic multilayer model and comprehensive experimental data, this study investigates the oxidation of carbon nanoparticles by NO2 and O2 under combustion exhaust conditions, going beyond traditional shrinking core modelling approaches. The study develops a molecular picture of the reaction system, including a reference chemical reaction mechanisms and energy profiles for three alternative reaction pathways.
Research Article
Polyoxometalates
Host-Guest Assemblies of Polyoxovanadate Clusters as Supramolecular Catalysts
- Version of Record online: 26 November 2024
An efficient strategy for embedding catalytically active polyoxovanadate (POV) into supramolecular assemblies was developed by utilizing host-guest interactions between pillararenes grafted on the cluster and ditopic linkers. The amphiphilic nature of the POV in the host-guest complex promoted responsive behavior of the assembly toward the solvent polarity. Lastly, the assembly showed enhanced catalytic properties compared to the parent POV.
Molecular Motors | Hot Paper
Coupling Rotary Motion to Helicene Inversion within a Molecular Motor
- Version of Record online: 26 November 2024
A light-powered molecular motor featuring a specifically engineered helicene moiety is presented. The inversion of the helicene fragment is mechanically coupled to the unidirectional rotation of the motor in a 6-step rotation cycle, which involves 8 isomers. This coupled motion results in the dynamic modulation of the handedness of the helicene by the motor via a central to helical to helical chiral transmission mechanism.
Viewpoint Article
Culture of Science
Cognitive Diversity for Creativity and Inclusive Growth
- Version of Record online: 26 November 2024
Cognitive diversity explores aspects beyond traditional lenses of culture, physical diversity, and merit and into variations in problem solving skills. Understanding aspects that need to be recognized in recruitment for various scientific enterprises will promote higher productivity, efficiency, diversity and heterogeneity in a team.
Research Article
Supramolecular Chemistry | Hot Paper
Transitioning Room-Temperature Phosphorescence from Solid States to Aqueous Phases via a Cyclic Peptide-Based Supramolecular Scaffold
- Version of Record online: 26 November 2024
A universally applicable supramolecular strategy to transition room-temperature phosphorescence (RTP) from solid states to aqueous phases is reported. By utilizing a cyclic peptide-based supramolecular scaffold, a series of aqueous RTP materials are constructed through the noncovalent dispersion of diverse organic phosphors within its rigid hydrophobic microdomain.
Photon Upconversion | Hot Paper
Anti-Stokes Emission Utilizing Reverse Intersystem Crossing
- Version of Record online: 26 November 2024
An alternative mechanism of photon-upconversion using a spin-flip process was proposed and demonstrated by combining a triplet sensitizer and a thermally activated delayed fluorescent (TADF) molecule. The triplet energy transfer from the green phosphorescent emitter (Ir(ppy)3) to the blue TADF emitter (CzBSe) results in anti-Stokes emission with an anti-Stokes energy of 0.18 eV.
Molecular Magnets
Exploiting High Order Magnetic Anisotropy for Advanced Magnetocaloric Refrigerants
- Version of Record online: 26 November 2024
Single-crystal experiments on the novel 3 d–4 f complex [DyDOTA][CrF2(py)4] (DOTA=tetraazacyclododecane-N,N′,N′′,N′′-tetraacetate, py=pyridine) have revealed a tetragonal easy-plane magnetic anisotropy. Temperature and magnetic-field dependent experiments to evaluate the rotating magnetocaloric effect demonstrated the potential of high-order anisotropies for developing more efficient magnetocaloric materials.
Communication
Total Synthesis
Total Synthesis and Configuration Assignment of (+)-Myxoquaterine-450
- Version of Record online: 26 November 2024
A concise, modular synthesis of the structurally novel natural product myxoquaterine-450 (1) has been accomplished. Four building blocks were assembled by cross-coupling reactions to establish the all-(E)-configured hexaene core. The C25,C26-diastereoisomer of 1 was prepared to clarify the absolute configuration of the yet unassigned stereogenic centers.
Research Article
Polymer Chemistry | Very Important Paper
Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts
- Version of Record online: 26 November 2024
Communication
Ring Expansion
Arene Ring Expansion by Ruthenium η6-Arene Complexes
- Version of Record online: 26 November 2024
The discovery of a new reactivity mode for π-arene metal complexes to promote carbon group insertion is reported. The reaction uses ruthenium η6-arene complexes supported by a tripodal ligand with enolates derived from α-halo- or α-(tosyloxy)esters to transform π-coordinated arenes to ring-expanded cycloheptatrienes in a single-step dearomatization process.
Research Article
Prebiotic Chemistry
Selective Nonenzymatic Formation of Biologically Common RNA Hairpins
- Version of Record online: 26 November 2024
Bioinspired Catalysis
Two-Phase Perchlorate Activation Enabled by a Dinuclear Fe-NHC (N-Heterocyclic Carbene) Complex
- Version of Record online: 26 November 2024
Inspired by the perchlorate activation process in microbes, a dinuclear Fe-NHC (NHC=N-heterocyclic carbene) complex was developed in this work to facilitate the two-phase activation of perchlorate through the cooperation of bimetallic centers. With the aid of photoirradiation, the oxidative potential of perchlorate could be released in a controllable manner to achieve the homocoupling of hydrocarbon substrates.
Oxoboranes | Very Important Paper
A Base-Free Two-Coordinate Oxoborane
- Version of Record online: 26 November 2024
A base-free, two coordinate oxoborane (R-BO) has been isolated as a Lewis adduct with AlCl3 and shown to react in a unique way with PhN3. In contrast to the parent oxoborane, the oxoborane→AlCl3 adduct is stable towards oligomerisation and C−H cleavage of the Mes* group as AlCl3 coordination provides thermodynamic stabilization while also reducing the basicity of the oxygen unit thus reducing the biphilic character of the BO unit.
Radical Chemistry
Stable Mono-Radical and Triplet Diradicals Based on Allylic Radical-Embedded All-Benzenoid Polycyclic Hydrocarbons
- Version of Record online: 26 November 2024
Spin Catalysis
Coordination Induced Spin State Transition Switches the Reactivity of Nickel (II) Porphyrin in Hydrogen Evolution Reaction
- Version of Record online: 26 November 2024
The study explores the impact of coordination-induced spin-state switching on hydrogen evolution reaction activity of nickel(II) porphyrin, revealing that low-spin Ni(II) porphyrin favors hydrogen evolution while high-spin counterpart facilitates β-hydrogenation of porphyrin periphery. Our finding highlights the pivotal role of spin transition in regulating the reactivity and selectivity of metal-catalyzed reactions.
Communication
Metal Nitrides | Hot Paper
Combination of Ambient and High-Temperature Beryllium Nitride Motifs in W2Be4N5 and W4Be8N9
- Version of Record online: 26 November 2024
The two first transition metal nitridoberyllates W2Be4N5 and W4Be8N9 were synthesized in a high-temperature high-pressure approach starting from Be3N2, W and NH4N3 or NaN3, respectively. The layered crystal structures, which unite ambient and high-temperature motifs of beryllium nitride, was elucidated in a combined approach of several analytic techniques. The structure elucidation from X-ray diffraction data alone was not unambiguous.
Research Article
Nitridophosphates
Adamantane-Type Nitridophosphate Phosphors AExLi10−2xP4N10 : Eu2+ via Medium-Pressure Ion-Exchange Reactions
- Version of Record online: 26 November 2024
A facile method for the synthesis of nitridophosphate-based phosphors using hot isostatic pressing is presented. Ion exchange reactions starting from the Li-ion conductor Li10P4N10 enables the preparation of single crystals and bulk samples of compounds with the general formula AExLi10−2xP4N10. Upon doping with Eu2+, these compounds exhibit remarkable luminescent properties across the green to red spectral range.
Polymer Chemistry
Inverse Vulcanization of Aziridines: Enhancing Polysulfides for Superior Mechanical Strength and Adhesive Performance
- Version of Record online: 26 November 2024
Ion-Selective Mobility Differential Amplifier: Enhancing Pressure-Induced Voltage Response in Hydrogels
- Version of Record online: 26 November 2024
Communication
Gas Separation | Very Important Paper
Flexible ZSM-5 Zeolite Membrane for High-Performance Helium Separation
- Version of Record online: 26 November 2024
Continuous and scalable ZSM-5 zeolite membranes have been successfully fabricated on polytetrafluoroethylene (PTFE) polymer supports. The prepared ZSM-5 membranes exhibit high flexibility that allows helium separation from natural gas under various circumstances. The helium separation performance exceeds those of the state-of-the-art membranes.
Research Article
Analytical Chemistry
Designable Electrochemiluminescence Patterning for Renewable and Enhanced Bioimaging
- Version of Record online: 26 November 2024
Designable electrochemiluminescence patterning is achieved by focusing a 730 nm laser beam on the electrode surface. Through an in situ photothermal effect generated by the laser, which removes oxides formed by anodization, this approach enables enhanced bioimaging, highly sensitive immunoassays, and reversible luminescence-based anti-counterfeiting and encryption.
Gas Separation Membranes
Restricting Linker Rotation in Nanocages of ZIF-8 Membranes using Crown Ether “Molecular Locks” for Enhanced Propylene/Propane Separation
- Version of Record online: 26 November 2024
Benzo-15-crown-5 (15C5) molecules were in situ encapsulated within the sodalite cage of the ZIF-8 membranes to restrict their flexible pore structure. The resulting 15C5@ZIF-8 membranes exhibited exceptional C3H6/C3H8 selectivity, reaching 220, significantly surpassing most other membranes. Remarkably, as pressure increased, the separation factor continued to rise, achieving a record-high C3H6/C3H8 separation factor of 331 at 7 bar.
Luminescence
Outstanding Circularly Polarized TADF in Chiral Cu(I) Emitters: From Design to Application in CP-TADF OLEDs
- Version of Record online: 26 November 2024
Chiral Cu(I) emitters exhibiting circularly polarized thermally activated delayed fluorescence (CP-TADF) with a record-high quantum yield (close to 100 %) and high dissymmetry factor (|glum|~1×10−2) have been developed. Based on these emitters, efficient CP-TADF OLEDs with high |gEL| factors of 1.5×10−2 were fabricated. It was also discovered that a magnetic field significantly suppresses the CP-TADF of chiral Cu(I) emitters.
Electrocatalysis
Strontium Doped IrOx Triggers Direct O−O Coupling to Boost Acid Water Oxidation Electrocatalysis
- Version of Record online: 26 November 2024
Adsorption and Machine Learning | Hot Paper
The Operando Nature of Isobutene Adsorbed in Zeolite H−SSZ−13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy
- Version of Record online: 25 November 2024
A transfer learning approach is proposed to perform enhanced sampling molecular dynamics simulations with arbitrary accuracy. We study the chemisorption of isobutene in the H−SSZ−13 zeolite with RI-RPA and show that carbenium ions are not present in significant concentrations at reaction temperatures.
Biomaterials
Antioxidative Therapy of Alcoholic Liver Injury by Amorphous Two-Dimensional Cobalt Hydroxide Nanocatalyst
- Version of Record online: 25 November 2024
A novel nanocatalytic antioxidation approach is proposed for alcoholic liver injury therapy by developing amorphous Co(OH)2 nanosheets with a desirable hepatic passive targeting ability, as well as a high catalytic antioxidative activity, resulting in an efficient and sustainable ROS-scavenging effect in the liver.
Photoredox Chemistry
Chalcogen Bonds Enable Efficient Photoreduction of Sulfur-Containing Heterocycles
- Version of Record online: 25 November 2024
Zn-Metal Batteries | Hot Paper
High-Entropy Electrolyte Driven by Multi-Solvation Structures for Long-Lifespan Aqueous Zinc Metal Pouch Cells
- Version of Record online: 25 November 2024
A high-entropy electrolyte (HEE) is prepared by mixing ternary ClO4−-based salts. Compared with conventional aqueous electrolyte (AqE) and high-concentration electrolyte (HCE), which have high water activity and big ion clusters, respectively, HEE exhibits reduced free water, small clusters, and multi-solvation structures. These provide HEE with anti-freezing properties and high ionic conductivity, enabling sustainable cycling in pouch cells.
Zinc-Manganese Batteries | Hot Paper
Effective Proton Conduction in Quasi-Solid Zinc-Manganese Batteries via Constructing Highly Connected Transfer Pathways
- Version of Record online: 25 November 2024
We proposed a novel electrolyte with proton transfer properties suitable for AZMBs. The Pr3+, propionic acid and montmorillonite construct connected proton transfer pathways synergistically, and the Pr3+ participates the interfacial electric double layer of manganese deposition and enhances its electrochemical activity. This water-poor quasi-solid hybrid electrolyte could maintain cycle stability while also stimulates high specific capacity.
Magnetic Properties
Planar Pentacoordinate Halogens
- Version of Record online: 25 November 2024
Planar pentacoordinate halogens present a challenge in chemistry, especially due to the electronegativity and restricted delocalization associated with halogens. Through extensive computational analysis, we identify a starlike D5h-symmetry global minimum structure in Li5X6− (X=F, Cl, Br) clusters, where the halogen is centrally positioned in a Li5X5 crown. Stability arises from electrostatic interactions, complemented by weak covalent dative bonding.
Fluorescence Imaging | Hot Paper
Long-Term Single-Molecule Tracking in Living Cells using Weak-Affinity Protein Labeling
- Version of Record online: 25 November 2024
Hydrogenase
Mesoporous Electrodes Enhance the Electrocatalytic Performance of [FeFe]-Hydrogenase
- Version of Record online: 25 November 2024
The metalloenzyme [FeFe]-hydrogenase from Clostridium pasteurianum (“CpI”) can be utilized for electroenzymatic hydrogen production under ambient conditions and neutral pH. Mesoporous indium tin oxide (ITO) electrodes have a hierarchical morphology with cavities and well-defined nanoparticle agglomerates, enhancing the electroenzymatic performance CpI.
Lithium Sulfur Batteries | Very Important Paper
Highly Solvating Electrolytes with Core-Shell Solvation Structure for Lean-Electrolyte Lithium-Sulfur Batteries
- Version of Record online: 25 November 2024
The core–shell solvation structured electrolyte, with phosphoramide confined in the first solvation shell via hydrogen bonding, inhibits the contact reaction with Li metal, and stabilizes the [S3]⋅− radical thus promoting a rapid solution-mediated sulfur reaction pathway and achieving high sulfur utilization at lean electrolyte condition. The 2.71-Ah pouch cell achieves high specific energy of 307 W h kg−1 and shows stable cycling over 20 cycles.
Pollutant Degradation
Aeration-Free Photo-Fenton-Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants
- Version of Record online: 25 November 2024
Dual-vacancy VO−M−Co3O4@CNx S-Scheme heterostructure with optimized defect concentration was successfully constructed, displaying excellent PMS activation ability synergized with photoexcitation for degrading organic pollutants without aeration. Emphasizing the competitive interaction between O2 and PMS within the catalyst is pivotal for controlling the synergistic photoexcitation of PMS for the first time.
Communication
Photoswitchable Catalysis | Hot Paper
Light-Responsive Aldehyde-Reduction Catalysis Through Catalyst Encapsulation
- Version of Record online: 25 November 2024
Light is an optimal stimulus to control the functioning of chemical systems, as it is clean, traceless, and easily applied. In this work we demonstrate a new way to couple catalytic activity to light input by encapsulating an aldehyde-reduction catalyst within a cage that opens upon illumination. This concept may enable illumination to be geared with catalytic activity for other reactions, including industrially relevant ones.
Review
Ion Channels
Transmembrane Ion Channels: From Natural to Artificial Systems
- Version of Record online: 25 November 2024
Ion channels play a crucial role in various physiological and pathological processes. Their importance is multifaceted and spans multiple disciplines, including biology, medicine, and pharmacology. In this Review, we introduce natural channel proteins and their structural features, gating properties, and physiological functions. We also discuss bioinspired ion channels and their fabricating strategies, dynamic regulation, and therapeutic applications.
Communication
Supramolecular Chemistry
Bioinspired “Intermolecular Pocket” in Soft Molecular Crystal of Porous Organic Cage Exhibiting Reversible Guest Recognition
- Version of Record online: 25 November 2024
A porous organic cage (POC) with hydrophobic intermolecular ‘pockets’ (HIMPs), constructed upon the lock of hydrophobic groups and disulfide bonds, has been achieved by biomimicking hydrophobic proteins. Similar to the specific substrate recognition observed in biological systems, NKPOC-DS exhibits selective “breathing behaviour” towards C2H6 through the expansion of its HIMPs, which makes NKPOC-DS a promising candidate for the one-step purification of C2H4 from a C2H6/C2H4 mixture.
Heteroatom-Doped Nanocarbons
A Carbazole-Centered Expanded Helicene Stabilized with Hexabenzocoronene (HBC) Units
- Version of Record online: 25 November 2024
Supramolecular Chemistry | Very Important Paper
Covalent Folding of Fluorinated Polyphenylene by Sulfur Fluorine Annulative Substitution
- Version of Record online: 25 November 2024
Monodisperse fluorinated polyphenylene undergoes folding-like sulfur fluorine annulative substitution (SFAS) to form a well-defined tubular helix H50. This is achieved with atomic precision in an exceptionally efficient manner, involving the simultaneous transformation of 98 C−F bonds with the yield per reaction site approaching 99.9 %. The desired product H50 features a fully fused dibenzothiophene skeleton of 5.8 helical turns in total and has an unambiguous single crystal X-ray structure. It can be resolved via chiral HPLC, displays distinct chiroptical properties, and forms strong through-cavity threading complex.
Research Article
Organic Polymer Photocatalysts
Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H2O2 Production and Organic Synthesis
- Version of Record online: 25 November 2024
Electron-donor backbone incorporating with pendant benzothiadiazole acceptor are elaborately designed to create directional charge-transfer channels in linear conjugated polymers (LCPs). This design efficiently directs electrons towards reduction centers, facilitating reactive oxygen species generation, while simultaneously guiding holes towards oxidation centers, thus significantly boosting photocatalytic H2O2 production and organic synthesis.
Review
Sensors
Aptamer and DNAzyme Based Colorimetric Biosensors for Pathogen Detection
- Version of Record online: 25 November 2024
Pathogen detection is crucial for preventing and managing health risks. This review consolidates the selection of functional nucleic acids (FNAs) for pathogen detection and the development of cost-effective, simple diagnostic applications. It focuses on integrating FNAs with gold nanoparticles, polydiacetylenes, protein enzymes, G-quadruplexes, and nanozymes in colorimetric biosensors.
Research Article
Phototheranostic Agents | Very Important Paper
Side Chain Phenyl Isomerization-Induced Spatial Conjugation for Achieving Efficient Near-Infrared II Phototheranostic Agents
- Version of Record online: 25 November 2024
Side chain phenyl positional isomerization induces strong intermolecular spatial conjugation, simultaneously improving the fluorescence brightness and photothermal properties of phototheranostic agents in the near-infrared II (NIR-II) window. The obtained o-ITNP NPs excels in high signal-to-noise NIR-II angiography, tumor localization, and NIR-II imaging-guided tumor photothermal therapy.
Communication
Cyclic Dinucleotides
A Phosphotriester-Masked Dideoxy-cGAMP Derivative as a Cell-Permeable STING Agonist
- Version of Record online: 25 November 2024
A dideoxy analog of cGAS/STING second messenger 2′,3′-cyclic GMP-AMP (cGAMP) was prepared using a new and concise synthetic combination of phosphoramidite and phosphotriester chemistry. By masking the negative charges of the phosphate backbones, the cellular uptake of cGAMP was highly increased from EC50=5 μM to 25 nM.
Research Article
Mechanochemistry
Using Near-Infrared Irradiation for Heating Mechanochemical Reactions in Organic-Dye-Doped Epoxy Milling Jars
- Version of Record online: 25 November 2024
Communication
Weakly-Coordinating Anions
Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications
- Version of Record online: 25 November 2024
Research Article
Probes
NIR-II Fluorescence/Photoacoustic Dual Ratiometric Probes with Unique Recognition Site for Quantitatively Visualizing H2S2 in Vivo
- Version of Record online: 25 November 2024
We have described a unique H2S2-mediated dithiole formation reaction under physiological conditions. Based on this reaction, we construct the first NIR-II fluorescence and photoacoustic dual-ratiometric probe (NIR-II-H2S2) for quantitatively and precisely visualizing H2S2 fluctuations in LPS/MET-induced liver injury.
Communication
C-H Activation
Meta-Dimethylation of Arenes via Catellani Reaction from Aryl Thianthrenium Salts
- Version of Record online: 25 November 2024
The combination of a site-selective thianthrenation with a Catellani reaction provides access to 3,5-dimethylated arenes. The developed reaction is complementary to the previously discovered reductive ipso-alkylation of aryl thianthrenium salts and extends the possibilities for late-stage methylation of arenes with a single aryl thianthrenium salt.
Boranes
Stabilization of Ethane-Like Dianionic Diborane(6) in Monometallic Titanium Complexes and its Subsequent B(sp3)−B(sp3) Bond Cleavage
- Version of Record online: 25 November 2024
Ethane-like classical dianionic diborane(6) species stabilized by mononuclear Cp*Ti have been isolated and structurally characterized. Treatment of these diborane(6) species with [M(CO)5 ⋅ THF] (M=Mo or W) led to the cleavage of electron-precise B(sp3)−B(sp3) bonds that yielded ĸ3-hydridoborato complexes (see picture).
DNA Sequencing | Hot Paper
Robust Bisulfite-Free Single-Molecule Real-Time Sequencing of Methyldeoxycytidine Based on a Novel hpTet3 Enzyme
- Version of Record online: 25 November 2024
Research Article
Battery Recycling | Very Important Paper
Direct Regeneration of Industrial LiFePO4 Black Mass Through A Glycerol-Enabled Granule Reconstruction Strategy
- Version of Record online: 25 November 2024
Nanozymes
Tailored Metal–Organic Framework-Based Nanozymes for Enhanced Enzyme-Like Catalysis
- Version of Record online: 25 November 2024
This work developed a novel metal–organic framework-based nanozyme that effectively blocks bacterial energy metabolism pathways through finely tuned catalytic center and substrate channel structures, demonstrating excellent antimicrobial properties and the potential to promote infected wound healing.
Communication
Asymmetric Catalysis | Hot Paper
Enantioselective Three-Component α-Allylic Alkylation of α-Amino Esters by Synergistic Photoinduced Pd/Carbonyl Catalysis
- Version of Record online: 25 November 2024
Introducing …
Linli Xu
- Version of Record online: 25 November 2024
“I chose chemistry as a career because it provides opportunities for research and innovation, allowing me to work across various industries and satisfying my desire for exploration in the realm of advanced materials… The most important thing I have learned from my students is the value of inclusiveness, patience, and love….” Find out more about Linli Xu in her Introducing… Profile.
Research Article
Small Molecule Modulators
Crafting Molecular Tools for 15-Lipoxygenase-1 in a Single Step
- Version of Record online: 22 November 2024
Small molecule modulators are essential for probing protein function, but their development is often limited by complex synthesis. We introduce a simple, one-step method to create multifunctional modulators. We developed a library for human 15-lipoxygenase-1, including probes, sensors, photocrosslinkers, and inhibitors. Our technology shows promise for complex biological applications, demonstrated by successful protein inhibition and labeling in vitro, in cellulo, and in vivo.
Zinc-Ion Capacitors | Hot Paper
Strong Replaces Weak: Hydrogen Bond-Anchored Electrolyte Enabling Ultra-Stable and Wide-Temperature Aqueous Zinc-Ion Capacitors
- Version of Record online: 22 November 2024
We report a hydrogen bond-anchored electrolyte by introducing sulfolane to reconstruct hydrogen-bond network, solvation structure and contribute to excellent temperature adaptability. The hydrogen bond network in free water is significantly weakened, while that between sulfolane and water is highly strengthened. The zinc-ion capacitor shows remarkable cycling stability over 55000 cycles and excellent temperature adaptability from −20 °C to 60 °C.