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Communication
Glycosylation
Harnessing Free Sulfate Groups in Glycosylation Reactions
- Version of Record online: 06 December 2024
Research Article
Solid-State NMR Spectroscopy | Very Important Paper
Surface Coordination Chemistry of Graphitic Carbon Nitride from Ag Molecular Probes
- Version of Record online: 05 December 2024
Graphitic carbon nitride (g-C3N4) is functionalized with organosilver probe molecules through a Surface OrganoMetallic Chemistry (SOMC) approach. In-depth characterization using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray absorption (XAS), and solid-state NMR (ssNMR) spectroscopy reveal the dynamic processes during metal grafting to generate three distinct surface sites: bis-NHC-Ag+, dispersed Ag+ sites, and physisorbed molecular precursor.
Machine Learning for Batteries
Machine Learning Assisted Prediction of Donor Numbers: Guiding Rational Fabrication of Polymer Electrolytes for Lithium-Ion Batteries
- Version of Record online: 05 December 2024
A prediction model for donor number (DN) was developed using machine-learning techniques, while the electron-donating ability of polymer segments to regulate the Li+ solvation structure was revealed and verified. Furthermore, a high-DN zwitterionic polymer electrolyte was designed to facilitate rapid Li+ transportation and ensure stable long-term high-voltage cyclability in lithium-ion batteries.
Carbohydrates | Hot Paper
Versatile Strategy for the Chemoenzymatic Synthesis of Branched Human Milk Oligosaccharides Containing the Lacto-N-Biose Motif
- Version of Record online: 05 December 2024
A universal core saccharide was prepared on a hundred-milligram scale by glycosyltransferases and amino protecting group (APG) conversions. This core saccharide was further extended into branched precursors with specific APGs, enabling controlled glycosylations, which allowed the facile synthesis of diversified branched human milk oligosaccharides (HMOs). Glycan microarray analysis showed that these HMOs, featuring a type 1 glycan, specifically bound to certain lectins.
Enzyme Catalysis | Very Important Paper
Functional Characterization and Molecular Basis of a Multi-Site Halogenase in Naphthacemycin Biosynthesis
- Version of Record online: 05 December 2024
FasV-catalyzed multiple halogenations in naphthacemycin biosynthesis were elucidated, which led to the discovery of previously unrecognized amino acid residues critical for controlling regioselectivity and substrate specificity. These findings suggest a novel dual-activation mechanism and demonstrate its biocatalytic potential for a broader range of phenolic hydroxy-containing substrates with diverse structural frameworks.
Rare Earth Metal Complexes
Stabilization of the Compressed Planar Benzene Dianion in Inverse-Sandwich Rare Earth Metal Complexes
- Version of Record online: 05 December 2024
The first inverse sandwich complexes [{(Me3Si)2NC(NiPr)2}2RE]2(μ-η6 : η6-C6H6) with RE = trivalent yttrium, dysprosium, and erbium, are presented, which exhibit a completely planar antiaromatic benzene bridging dianion ligand. The remarkable planarity of the bridging parent benzene dianion is otherwise unknown with any s-, p-, d-, or 4f- metal, and rationalized by the match of the metals d-manifold with the π*-molecular orbital of the bridging benzene unit and strong electrostatically compression through coordination with the two cationic REIII sites.
Highlight
Biosynthesis
Giant Polyketide Synthases Biosynthesize a Marine Polyether Biotoxin
- Version of Record online: 05 December 2024
Fallon, Shende, Moore, and co-workers have identified for the first time genes encoding giant type I polyketide synthases (PKZILLA-1 & 2) in the “golden alga” Prymnesium parvum for the biosynthesis of the polyether toxin prymnesin-1, corroborating long-held biosynthetic postulates. The authors’ approach may serve as a blueprint for the future discovery of the biosynthetic machineries underlying other polyether toxins.
Research Article
Homogeneous Catalysis
Copper-Catalyzed Regioselective and Enantioselective Hydropyridylation of Dienes for the Synthesis of Chiral Diaryl Compounds via Concerted Nucleophilic Aromatic Substitution
- Version of Record online: 05 December 2024
A copper-catalyzed enantioselective and 1,4-selective hydropyridylation has been developed. Using 2-fluoropyridine as the electrophile and a copper catalyst in conjunction with (R)-Tol-BINAP, the desired chiral 1,1-diaryl product was synthesized via a concerted nucleophilic aromatic substitution mechanism.
Communication
Photochemistry
Oxenoid Reactivity Enabled by Targeted Photoactivation of Periodate
- Version of Record online: 05 December 2024
The targeted photoactivation of periodate provides a novel and operationally straightforward method for accessing oxenoid-type reactivity. Computational studies have revealed a geometric transition in periodate geometry which, when irradiated, allows for the facile extrusion of molecular oxygen. This new reaction pathway allows for the epoxidation of a broad range of olefin substrates using an organic-soluble source of periodate and violet light irradiation.
Research Article
Redox Flow Batteries
Manipulating Aggregate Electrochemistry for High-Performance Organic Redox Flow Batteries
- Version of Record online: 05 December 2024
Aggregation of electroactive organic molecules in solution yields a linear relationship between the potential shift and the aggregation number, yielding a substantial voltage loss at a high concentration in an organic redox flow battery. Molecular anti-aggregation strategy is applied and the sensitivity between the voltage and the concentration is lowered.
Organocatalysis | Very Important Paper
Catalytic Asymmetric Synthesis of Inherently Chiral Eight-Membered O-Heterocycles through Cross-[4+4] Cycloaddition of Quinone Methides
- Version of Record online: 05 December 2024
Cross-[4+4] cycloaddition reactions of vinylidene ortho-quinone methides (VQMs) with either ortho- or para-quinone methides yielded inherently chiral eight-membered O-heterocycles in high yields with high to excellent stereoselectivity. These products display a unique combination of inherent, axial, and central chirality.
Nanosensitizers
Intratumoral Transforming Boron Nanosensitizers for Amplified Boron Neutron Capture Therapy
- Version of Record online: 05 December 2024
A novel smart boron nanosensitizer (BATBN) is comprised of ultrasmall boron quantum dots (BQDs) conjugated with cell-penetrating peptides, which facilitates its cellular uptake and deep tumor penetration. A self-condensation reaction of BATBN triggered by the tumor biomarker, leading to the formation of larger-sized nanoaggregates, presents a supramolecular strategy which enables precise and efficient boron neutron capture therapy (BCNT) for cancer treatment.
Organic Lasers | Hot Paper
Mechanochromic Organic Micro-Laser
- Version of Record online: 05 December 2024
An organic laser material has been shown to be capable of simultaneously exhibiting amplified spontaneous emission and mechanofluorochromic properties under a wide range of shear and normal force conditions. Applying a localized mechanical pressure as low as 0.1 MPa inhibits the micro-laser behavior at the given spot, while a hydrostatic pressure of 1 to 2 GPa leads to a narrow emission and a pressure-dependent shift in the emission wavelength.
Communication
Glycopolymers
Glycopolymer-Mediated Selective Separation of Middle Rare Earth Elements
- Version of Record online: 05 December 2024
Bio-inspired, stimuli-responsive glucuronate-functionalized polymers selectively separate middle rare earth elements (MREEs), such as Samarium, over Holmium and Cerium, through tailored charge density and polymer length. Acidification triggers glucuronate protonation, releasing the MREEs and resolubilizing the polymer. The material's efficiency in separating MREEs from complex mixtures is showcased, offering a reusable, size-selective strategy for addressing challenges in MREE recovery.
Research Article
Supramolecular Chemistry
Fuel-Driven π-Conjugated Superstructures to Form Transient Conductive Hydrogels
- Version of Record online: 05 December 2024
Electrocatalysis
H Induced Metal-Insulation Transition Boosts the Stability of High Temperature Polymer Electrolyte Membrane Fuel Cells
- Version of Record online: 05 December 2024
The frequent start-up and shut-down (SU/SD) caused fuel starvation operation condition seriously deteriorates the performance and lifetime of the fuel cell (HT-PEMFCs). We proposed the temperature-matched hydrogen-induced metal-insulator phase transition for controlling activity and fuel starvation tolerance in HT-PEMFCs.
Communication
Analytical Chemistry
Single-Cell Secretome Profiling Enabled by Selective Enrichment and NanoLC-MS/MS Analysis
- Version of Record online: 05 December 2024
A new strategy for comprehensive single-cell secretome profiling (SCSP) by integrating metabolic labeling of newly synthesized proteins, click chemistry-based enrichment in an alkyne micro-reactor, in situ digestion, and nanoLC-MS/MS analysis. SCSP enables an unprecedented depth of the secretome identification, providing a new avenue for studying secretion heterogeneity at the single-cell level.
Research Article
Organic Electronics
Full Conjugation in a Polymer with Non-conjugated Piperazine-2,5-dione Units via Energy-minimized Lactam-to-Lactim Tautomerization Enables Water-gated Transistor Fluoride Sensors
- Version of Record online: 05 December 2024
We discovered that the non-conjugated piperazine-2,5-dione unit fully tautomerizes into the conjugated 3,6-dihydropyrazine-2,5-diol unit via a long-range vinylogous effect, driven by energy minimization through π-electron delocalization along the polymer backbone. This fully conjugated backbone enhances charge transport, while lactim units strongly interact with fluoride ions, making this polymer effective in water-gated field-effect transistor fluoride sensors.
Microdroplets
The Effect of Electric Fields on Oxidization Processes at the Air-Water Interface
- Version of Record online: 05 December 2024
Some difficult chemical reactions occur spontaneously in water microdroplets, and electric fields at the air–water interface are thought to be the main cause. Using theoretical computations for two prototypical processes involving OH− we show that the magnitude of the electric fields required to make the processes favorable are much higher than those existing at the pristine air–water interface. We discuss the implications of the results.
Electrocatalytic Urea Oxidation | Very Important Paper
Electron Delocalized Ni Active Sites in Spinel Catalysts Enable Efficient Urea Oxidation
- Version of Record online: 05 December 2024
Hydrogen Oxidation Electrocatalysis
Hollow Pt-Encrusted RuCu Nanocages Optimizing OH Adsorption for Efficient Hydrogen Oxidation Electrocatalysis
- Version of Record online: 05 December 2024
Hollow nanocages with Pt epitaxy grown on RuCu have been successfully synthesized as efficient electrocatalysts via a galvanic replacement strategy, exploiting the distinct electrochemical potentials of Pt, Ru, and Cu. The optimized Pt8.7-RuCu NCs/C catalysts not only exhibite exceptional HOR performance, but achieve a significantly higher specific peak power density (15.9 W mgPt+Ru−1) under fuel cell conditions, making them a promising high-efficiency anode nanocatalyst for practical AEMFC applications.
Solar Cells | Hot Paper
Enhancing Mechanical Durability and Long-Term Stability in Organic Solar Cells via Flexible Linker-Sequential Block Copolymerized Donors
- Version of Record online: 05 December 2024
A series of novel multi-component copolymerized donors were successfully synthesized, and excellent efficiencies in both rigid binary (18.09 %) and ternary (19.05 %) as well as flexible binary (16.63 %) OSCs for flexible linker-sequential block MCD PM6-C10.8-b-D18-Cl0.2-BTD were achieved, along with excellent long term photovoltaic stability (T80=9,078 h) and photo-stability (T80=568 h) in invert OSCs as well as outstanding crack-onset strain (COS) value of 49.88 % and 31.29 % in both pristine and blend films, respectively.
Polymer Chemistry | Hot Paper
4D Printing of Liquid Crystal Emulsions for Smart Structures with Multiple Functionalities
- Version of Record online: 05 December 2024
We present a novel 4D printing approach using digital light processing (DLP) to fabricate complex, multifunctional 3D structures from liquid crystal (LC) emulsions. This method preserves LC ordering, imparting tunable shape memory, light responsiveness, and porosity. The addition of chiral nematic LCs enables adjustable reflective properties, offering potential for applications in adaptive optics, robotics, and photonics.
Solid-State Li-Air Batteries | Hot Paper
Coordination-Driven Crosslinking Electrolytes for Fast Lithium-Ion Conduction and Solid-State Battery Applications
- Version of Record online: 05 December 2024
A Li+-conducted coordination hypercrosslinked MOP (CHMOP-Li) polymer electrolyte was developed for high-energy solid-state Li batteries, which is based on a cellulose-based copolymer with metal-organic polyhedra (MOPs) as the crosslinking agent. Benefiting from the advantages of MOPs and cellulose-based copolymers, the CHMOP-Li electrolytes exhibit both high ionic conductivity of 1.02×10−3 S cm−1 and high Li+ transference number of 0.75 at 25 °C. The solid-state Li−O2 batteries fabricated with CHMOP electrolyte show good cycling performance (500 cycles) and high discharge capacity (15740 mAh g−1).
Communication
Artificial Synapses
Neuromorphic Nanofluidic Sense Digitalization
- Version of Record online: 05 December 2024
Neuromorphic nanofluidic sense digitalization is devised by a nanofluidic dopaminergic nerve to manage the robot. The dopamine recognition by aptamer and the corresponding ionic signaling are more analogous to the processes in biology. Dopaminergic modulation of synaptic transmission is uncovered by many neurologic functions, and control of the robotic arm is realized by digital representation of the dopamine-dependent plasticity.
Research Article
COFs
Covalent Organic Frameworks for Boosting H2O2 Photosynthesis via the Synergy of Multiple Charge Transfer Channels and Polarized Field
- Version of Record online: 05 December 2024
This work presents the first example of piezo-photocatalytic synthesis of hydrogen peroxide (H2O2) using covalent organic frameworks (COFs). Under the synergy of the intermolecular multiple-channel charge transfer and the piezoelectric polarization field, charge separation was greatly improved and ethenyl group-modified bicarbazole-based COFs (COF-DH-Eth) achieved a record-breaking H2O2 synthesis rate (9212 μmol g−1 h−1).
DNA Computing
Bead-Based DNA Synthesis and Sequencing for Integrated Data Storage Using Digital Microfluidics
- Version of Record online: 05 December 2024
An integrated DNA data storage pipeline is invented to streamline the whole process from DNA chemosynthesis to pyrosequencing on the surface of magnetic beads in droplets manipulated by a homemade digital microfluidic cartridge. Overall, it takes 6.5 hours to writing and reading 8 bytes of data (49 min/byte) with up to 100 % text accuracy by plural voting and RS coding.
Electrocyclic Reactions
Electrochemical CO2 Fixation and Release Cycle Featuring a Trinuclear Zinc Complex for Direct Air Capture
- Version of Record online: 05 December 2024
Cyclic fixation-release of dilute CO2 was carried out continuously in a system consisting of a zinc complex and an electrolytic cell with bipolar membrane. CO2 fixation is promoted by the formation of carbonate-coordinated complex, and CO2 release is induced by decomposition of the complex structure accompanied by protonation of the ligand. Reconstruction of the complex structure by ligand deprotonation closes the cycle to enable CO2 refixation.
Batteries
Depth-of-Discharge Dependent Capacity Decay Induced by the Accumulation of Oxidized Lattice Oxygen in Li-Rich Layered Oxide Cathode
- Version of Record online: 05 December 2024
The rapid capacity decay mechanism of LRLO during LDOD cycling is elucidated. The accumulation of activated On− and persistent vacancy-rich state intensified TM in-plane migration, leading to the vacancies transition from separated to aggregated states, facilitating detrimental out-of-plane TM migration. Furthermore, increased anionic redox reactions resulted in cathode-to-anode shuttle of On− and by-products, leading to lithium loss.
Flexible Crystals | Hot Paper
In Situ Generation of Microwire Heterojunctions with Flexible Optical Waveguide and Hydration-Mediated Photochromism
- Version of Record online: 04 December 2024
A hydration-mediated molecular engineering strategy has been used for the in situ generation of flexible heterojunctions that display ultralow-loss optical waveguides, high flexibility and controllable emission sequences. This integration of the benefits of flexibility and heterojunctions approach offers the possibility for developing photonic information encryption systems.
Communication
Molecular Motors
A Chemically Powered Rotary Molecular Motor Based on Reversible Oxazepine Formation
- Version of Record online: 04 December 2024
Here, we report an aniline-phenol-based rotary molecular motor that operates via an information ratchet mechanism. The 360° directional rotation about a single covalent bond can be chemically driven by reversible oxazepine formation. Both the oxazepine formation and hydrolysis steps are kinetically gated via dynamic kinetic resolution, arising from the kinetic bias of chiral catalysts for enantiomers.
Research Article
Asymmetric Ring-Opening
One-Pot Cobalt- or Copper-Catalyzed Asymmetric Ring-Opening Hydrosilylation/Hydroboration of Arylidenecyclopropanes
- Version of Record online: 04 December 2024
Operationally convenient one-pot one-step cobalt-catalyzed and enantioselective one-pot two-step copper-catalyzed sequential hydrosilylation/hydroboration of arylidenecylcopropanes are developed to prepare racemic and enantioenriched 1,4-borylsilylalkanes with high regio- and enantioselectivity, respectively. Mechanistic studies reveal that these reactions proceed by metal-hydride-catalyzed ring-opening regioselective hydrosilylation followed by hydroboration of homoallylsilane intermediates.
Communication
Natural Products Synthesis
Research Article
Luminescence
Upconversion Luminescence with Bis-pyclen Yb(III) Chelates: Crown vs. Linear Polyether Linkers in Discrete Heteropolynuclear Architectures
- Version of Record online: 04 December 2024
This work presents the design and synthesis of pre-organized ligands combining two lateral bis-pyridyl-phosphonated-pyclen macrocycles bridged by either a flexible linear pegylated linker (L2) or a bulkier K22 crown-ether (L3), and the regioselective formation of their dinuclear Yb complexes. Upconversion (UC) sensitization of Tb upon excitation into the Yb NIR absorption band was evaluated in D2O, showing the heteropolynuclear complexes of L2 to be two times more intense for UC emission compared to those of L3.
Natural Products
Batrachopolyenes: Volatile Norsteroids from Femoral Scent Glands of Frogs
- Version of Record online: 04 December 2024
A new family of volatile steroidal natural products, the batrachopolyenes, have been isolated and identified from torrent frogs. A total synthesis established their structure. These norsteroids contain a unique contracted A-ring and unusual functionalization across the structural core, which were installed along a divergent total synthetic sequence.
Sodium-Sulfur Batteries
Unraveling the Multifunctional Mechanism of Fluoroethylene Carbonate in Enhancing High-Performance Room-Temperature Sodium-Sulfur Batteries
- Version of Record online: 04 December 2024
In this work, we comprehensively reveal the two-step “chocolate-cookie” shaped CEI formation mechanism in RT Na-S batteries driven by FEC. The solid-solid conversion of sulfur and impressive performance are achieved in this simplified system (456 mAh g−1 after 1000 cycles at 0.5 C), which has the potential for further improvement.
NMR Spectroscopy
High-Efficiency Trifluoromethyl-Methionine Incorporation into Cyclophilin A by Cell-Free Synthesis for 19F NMR Studies
- Version of Record online: 04 December 2024
Near-complete incorporation of trifluoromethyl methionine (tfmM) into Cyclophilin A (CypA) was achieved by cell-free synthesis, preserving its substrate binding affinity and enzymatic activity. Availability of the highly responsive and sensitive tfmM probe paves the way for studying protein-protein/ligand interactions and protein dynamics by 19F NMR spectroscopy.
Gas Separation | Very Important Paper
Self-adaptive Coordination Evolution Mediated Pore-Space-Partition in Metal–Organic Frameworks for Boosting SF6/N2 Separation
- Version of Record online: 04 December 2024
Pore space partition (PSP) has been successfully achieved in two isomorphic metal–organic frameworks (MOFs) mediated by an unprecedented self-adaptive coordination evolution (SACE) on low-symmetric M4 clusters, which provides new perspectives for MOF structural regulation and designing more advanced porous adsorbents.
Luminescent Materials | Very Important Paper
Pseudohalide Anions Driven Structural Modulation in Distorted Tetrahedral Manganese(II) Hybrids Toward Tunable Green-Red Emissions
- Version of Record online: 04 December 2024
Communication
Batteries
Engineering Stable Decomposition Products on Cathode Surfaces to Enable High Voltage All-Solid-State Batteries
- Version of Record online: 04 December 2024
Rational design of a cost-effective coating on high-voltage NCM85 cathode for all-solid-state batteries—utilizing the stable decomposition products of LiPO2F2—successfully suppresses the electrochemical decomposition of the argyrodite Li6PS5Cl solid electrolyte. Cells using the LiPOF-coated NCM85 demonstrated significantly improved capacity retention over 200 cycles, outperforming cells using uncoated NCM85.
Research Article
Organic Materials
Synthesis and Characterizations of Dibenzo-Fused Perioctacene
- Version of Record online: 04 December 2024
Dibenzoperioctacene (DBPO) with extended zigzag edges was synthesized and characterized. While the bond length analysis indicated a possible open-shell nature of DBPO, variable-temperature NMR analysis indicated its closed-shell character. The theoretical investigations revealed the DBPO has nearly degenerate closed-shell and open-shell singlet states with a large singlet-triplet energy gap.
Review
Nanographene Electrocatalysts
Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction
- Version of Record online: 04 December 2024
Nanographenes including 3D graphene, graphene quantum dots and graphene nanoribbons are among the fastest-growing materials used for the oxygen reduction reaction (ORR). The enhanced ORR activity of the nanographenes are original from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect, which can efficiently modify the charge distribution, optimize intermediate adsorption and accelerate electron transfer steps.
Communication
Photocatalysis
Modular Synthesis of Dehydroprolines by an Energy-Transfer Enabled Cloke-Wilson Rearrangement
- Version of Record online: 04 December 2024
A photocatalytic Cloke-Wilson rearrangement of crude aminocyclopropane carboxylate (ACPC) imines is reported. This leverages an energy-transfer mechanism transforming the core of ACPC to value added dehydroprolines—a useful synthetic intermediate en route to the synthesis of substituted unnatural proline derivatives. Both the 1,5-dehydroproline, as well as the uncommon 1,2-isomer are obtained from the same starting material under slightly modified conditions.
Research Article
Hydrogenation of Halogenated Nitroarenes | Hot Paper
Precisely Tailoring the Second Coordination Sphere of a Cobalt Single-Atom Catalyst for Selective Hydrogenation of Halogenated Nitroarenes
- Version of Record online: 04 December 2024
Co single-atom catalyst with an unsymmetric Co-N4P1 coordination configuration is developed by tailoring second coordination sphere. Due to the greatly improved H2 dissociation and product desorption, the catalyst exhibits superior activity, selectivity and stability for hydrogenation of halogenated nitroarenes to corresponding amines (20 examples, >99 % yields) at 80 °C under 0.5 MPa H2 pressure.
Solid State Lithium Metal Batteries
Self-Assembled Monolayer in Hybrid Quasi-Solid Electrolyte Enables Boosted Interface Stability and Ion Conduction
- Version of Record online: 04 December 2024
A self-assembled monolayer (SAM) on the surface of LLZTO powders is constructed to inhibit the Li+/H+ exchange reaction and provide extra Lewis acid-base site, which achieving the establishment of a long-term local conducive microenvironment of Li+ conduction on the surface of LLZTO. This work emphasizes the importance of modulating solvation structure for the hybrid quasi-solid electrolyte.
Analytical Chemistry
Cell-Sensing Analogue Nanopore for Rapid Detection of Protein-Related Targets
- Version of Record online: 04 December 2024
Cell-sensing analogue nanopore (CeSa-nanopore) captures SARS-CoV-2 by specific receptor proteins ACE2 and changes the charge on the outer surface of the nanopore to enable the detection of SARS-CoV-2. This method eliminates the need for sample pre-treatment, enables rapid target detection, and allows for the detection of different targets by changing the cell membrane.
Piezoelectric Covalent Triazine-based Nanotubes | Very Important Paper
Bottom-up Synthesis of Piezoelectric Covalent Triazine-based Nanotube for Hydrogen Peroxide Production from Water and Air
- Version of Record online: 04 December 2024
A novel fully conjugated covalent triazine-based hollow nanotube (CTN-1) with rich active sites and high surface areas has been prepared for piezocatalytic H2O2 evolution. Benefiting from piezoelectric response and fully conjugated framework, CTN-1 facilitated piezoelectric carrier separation, leading to highly efficient H2O2 production with a rate of 4115 μmol g−1 h−1, which is superior to other piezoelectric materials.
Hydrogen Isotope Exchange | Hot Paper
Hexafluorophosphate-Triggered Hydrogen Isotope Exchange (HIE) in Fluorinated Environments: A Platform for the Deuteration of Aromatic Compounds via Strong Bond Activation
- Version of Record online: 04 December 2024
A new synthetic route for hydrogen isotope exchange (HIE) in arenes has been developed using catalytic PF6− in deuterated hexafluoroisopropanol and D2O under mild conditions. This method achieves high yields and excellent deuterium incorporation in phenols, anisoles, anilines, and heteroaromatic substrates. An extended H-bonding network is responsible for activating the inert P−F bond in PF6−, allowing for HIE and the creation of deuterated compounds.
Spin Crossover Materials
Thermal Bistability of Magnetic Susceptibility, Light Absorption, Second Harmonic Generation, and Dielectric Properties in a Polar Spin-Crossover Iron–Rhenium Chain Material
- Version of Record online: 04 December 2024
Self-assembly of iron(II) centers with phenyl isonicotinate and octacyanidorhenate(V) leads to a polar molecule-based material incorporating heterometallic Fe(II)−Re(V) cyanido-bridged chains. It exhibits a thermally induced cooperative spin crossover (high-spin-to-low-spin) transition on Fe(II) sites which results in remarkable thermal bistability of magnetic, visible-light absorption, second-harmonic generation, and dielectric properties.
Molecular Electronics | Very Important Paper
A Molecular Engineering Approach to Conformationally Regulated Conductance Dualism in a Molecular Junction
- Version of Record online: 04 December 2024
A new and simple methodology to mechanically addressable molecular conductance switches with large conductance variations (~103) between high- and low-G states is presented. By chemical design, rotational flexibility in these molecules and variable anchor group distances are translated into distinct conductance pathways for the different conformers of the same single molecule.
Zinc-Air Batteries
O−O Radical Coupling in Ultrathin Reconstructed Co6.8Se8 Nanosheets for Effective Oxygen Evolution and Zinc-Air Batteries
- Version of Record online: 04 December 2024
The structure-dependent electrochemical performance and the underlying catalytic mechanisms are still not clearly distinguished toward oxygen evolution reaction (OER). Herein, we synthesized ultrathin Co6.8Se8 nanosheets with subnanometer thickness by incorporating catalytically inactive selenium into ultrathin Co(OH)2, thereby switching the OER reaction pathway from adsorbate evolution mechanism (AEM) to oxide path mechanism (OPM).
Supramolecular Chemistry
Chiroptical Response of Carbon Nanocages Enhanced by Achiral Guests
- Version of Record online: 04 December 2024
The geometrical reinforcement of chiral carbon cages by supramolecular technique led to enhancement of sensitivity against circularly polarized red light with an improved dissymmetry factor where the achiral guests such as Ar, CO2, and CH3CN are engaged in inhibition of undesired arrangement of transition dipole moments.
Oxygen Evolution | Very Important Paper
Ru0.1Mn0.9Ox Electrocatalyst for Durable Oxygen Evolution in Acid Seawater
- Version of Record online: 04 December 2024
We report a Cl−-assisted active site transfer strategy on Ru0.1Mn0.9Ox, achieving high OER selectivity and long-term stability in acidic seawater. Typically, *Cl occupies the Ru site, shifting the OER center to CER-insensitive Mn, preventing metal site dissolution. Additionally, the active Mn sites create an environment that favors OER over CER, offering a selective and durable solution for acidic seawater electrolysis.
Communication
RNA Modification | Very Important Paper
Visualization and Quantification of Single-Base m6A Methylation
- Version of Record online: 04 December 2024
We design a TadA8.20-assisted N6-methyladenosine RNA imaging at single-base resolution (TARS) method for in situ visualization of both A and m6A forms at specific RNA sites within single cells. This method enables the quantification of m6A modification fractions, providing precise and detailed insights into m6A modifications at the single-base level.
Research Article
Natural Products Synthesis | Hot Paper
Chemoenzymatic Synthesis of the Cyclopiane Family of Diterpenoid Natural Products
- Version of Record online: 04 December 2024
Chemoenzymatic synthesis of cyclopiane and related diterpenes has been achieved in a three-stage manner. Ten cyclopiane diterpenes were obtained by skeleton construction with an engineered heterologous host, followed by late-stage functionalization of rings A, B and D by direct redox operations, directed C−H activation and enzymatic oxidation. Varied cyclopiane-related skeletons were further obtained by chemical transformation and genome mining.
Methanol-Water Electrolysis | Hot Paper
Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro-Reforming Coupled with Hydrogen Production
- Version of Record online: 04 December 2024
Stable CeF3@Ni3N heterostructure with abundant interfaces is fabricated, which exhibits high electrocatalytic activity and stability under industrial current density for methanol upgrading coupled with hydrogen production. CeF3@Ni3N heterostructure can adjust electron distribution and modulate surface adsorption kinetics/capability of methanol and OH−, which is conducive to enhanced methanol oxidation reaction activity and selectivity.
SO2 Adsorption
Counterions Determine if Metal-Organic Cages Convert SO2 to Sulfate or Reversibly Adsorb It
- Version of Record online: 04 December 2024
Different counterions modulate the solid-state SO2 adsorption behavior in M6L8 Metal-Organic Cages (M=Pd(II), Co(II), Cu(II), Zn(II)). Certain anions induce reversible SO2-adsorption, while nitrate promotes its transformation to sulfate at room temperature. Among these cages, Pd6L8 exhibits the highest cavity-mediated SO2 conversion, excellent stability, and is quantitatively regenerated.
Batteries | Hot Paper
Crystal Modulation of Mn-Based Layered Oxide toward Long-Enduring Anionic Redox with Fast Kinetics for Sodium-Ion Batteries
- Version of Record online: 04 December 2024
An innovative crystal modulation strategy was proposed and implemented on a Mn-based cathode Na0.72Li0.24Mn0.76O2 with highly exposed {010} active facets and reinforced Mn−O bond, facilitating enduring anionic redox activity with fast kinetics. The robust structural stability and zero-strain behavior with ultra-low volume variation (0.1 C: 1.75 %, 1 C: 0.31 %, 5 C: 0.04 %) are directly revealed via advanced nondestructive time-resolved operando 2D-XRD.
Clusters for Heterogeneous Catalysis
A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation
- Version of Record online: 04 December 2024
Two isostructural lanthanide-nickel clusters Ln132Ni78 (Ln=Gd, Eu) were synthesized by the co-hydrolysis of Ln3+ and Ni2+ in the presence of iminodiacetate. Both clusters feature a hollow truncated tetrahedral structure with trumpet-shaped passageways that connect the exterior and the interior of the cluster cage. The solution-stable cluster has been shown to catalyze size-selective Knoevenagel condensation and one-pot three-component synthesis of 4H-pyran derivatives.
Antibiotics | Hot Paper
Switching Residues: A Platform for the Synthesis of Fidaxomicin Antibiotics
- Version of Record online: 04 December 2024
Switching residues: Adding new substituents to natural products increases their molecular weight and often their lipophilicity. We developed a Pd-catalysed protocol to directly replace the rhamnoside-arene fragment of the antibiotic fidaxomicin with simple amines in 1 step from the unprotected natural product. This enabled direct access to Fdx derivatives of reduced complexity with activity against RNA polymerase and various bacteria.
Organometallic Chemistry
Sb-to-P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound
- Version of Record online: 04 December 2024
The structurally constrained, cationic PIII compound with the OCO dianionic pincer-type ligand [LP][SbCl4] was prepared in a single step via the Sb-to-P metathesis reaction of the LSb-Cl with PCl3. The preliminary reactivity of [LP][SbCl4] with water, ammonia, and amines showed that the [SbCl4]− is not innocent in these reactions. Changing the [SbCl4]− to [Cb]− anion, rerouted the reactivity of the resulting [LP][Cb] with water, alcohols, ammonia, and amines to the [LP]+ cation only. In the case of PhOH and PhNH2 activation, the reactions were found to be thermoneutral.
Communication
Photocatalysis | Hot Paper
Redox-Neutral Carboxylation of Benzylic Tertiary C−H Bonds with Carbon Dioxide
- Version of Record online: 04 December 2024
A novel photocatalysis combined with cascade hydrogen atom transfer cycles for the carboxylation of benzylic tertiary C−H bond with CO2 is reported. The power of this strategy is demonstrated for the late-stage carboxylation of broad bioactive molecule derivatives to obtain benzylic all-carbon quaternary carboxylic acids.
Research Article
CO2 Photoreduction
Structurally Asymmetric Ni−O−Mn Node in Metal–Organic Layers on Carbon Nitride Support for CO2 Photoreduction
- Version of Record online: 04 December 2024
Biosynthesis | Very Important Paper
The Kinetics of Carbon-Carbon Bond Formation in Metazoan Fatty Acid Synthase and Its Impact on Product Fidelity
- Version of Record online: 04 December 2024
The β-ketoacyl synthase (KS) domain of metazoan fatty acid synthase catalyzes the condensation reaction of an acyl and malonyl substrate with two cooperatively working subunits. The KS ensures the fidelity of the fatty acid biosynthesis i) by increasing the speed with substrate length and ii) by discriminating against the intermediates of the fatty acid cycle.
Energy Generation and Conversion | Hot Paper
Mineralizing Biofilm towards Sustainable Conversion of Plastic Wastes to Hydrogen
- Version of Record online: 04 December 2024
Biogenetical CdS nanoparticles were integrated with Shewanella oneidensis biofilm to be capable of sustainable plastic-to-hydrogen production under the air. The upper section of the Figure illustrates the process of mineralized biofilm formation, and the lower section depicts the hydrogen production procedure from the mineralized biofilm through plastic degradation.
Biomaterials | Hot Paper
Nanocarriers Made of Natural Fatty Acids: Modulation of Their Release Profiles through Photo-Crosslinking
- Version of Record online: 04 December 2024
Minireview
Perovskite Solar Cells
Stabilization Strategies of Buried Interface for Efficient SAM-Based Inverted Perovskite Solar Cells
- Version of Record online: 04 December 2024
This minireview focuses on the analysis of the buried interface instability mechanisms of self-assembled monolayers (SAMs) in inverted perovskite solar cells, and highlights representative work to improve their stability. It also proposes potential strategies in material design and processing methods for achieving excellent stability in highly efficient SAM-based inverted devices.
Research Article
Sustainable Chemistry | Hot Paper
One-Step Esterification of Phosphoric, Phosphonic and Phosphinic Acids with Organosilicates: Phosphorus Chemical Recycling of Sewage Waste
- Version of Record online: 04 December 2024
Chemical recycling of phosphoric acid (H3PO4) recovered from sewage sludge ash into valuable phosphate triesters has been achieved via a novel esterification method with tetraalkyl orthosilicate. The approach offers an innovative recycling pathway, producing key industrial phosphorus chemicals without the use of white phosphorus while addressing phosphorus resource limitations and environmental impact.
Homogeneous Catalysis | Very Important Paper
Methanolation of Olefins: Low-Pressure Synthesis of Alcohols by the Formal Addition of Methanol to Olefins
- Version of Record online: 04 December 2024
Annulenes
Dicyclopenta[4,3,2,1-cde:4′,3′,2′,1′-pqr]-peri-tetracene: Synthesis and an Example of Annulene-within-an-Annulene Aromaticity in Different Redox States
- Version of Record online: 04 December 2024
A stable dicyclopenta[4,3,2,1-cde:4′,3′,2′,1′-pqr]-peri-tetracene derivative was successfully synthesized that shows global anti-aromaticity with small diradical character. The dication exhibits an open-shell diradical character and a unique [14]annulene-within-[22]annulene global aromatic structure, while the dianion is a closed-shell singlet in the ground state and displays a diatropic ring current on the π-conjugated periphery.
Autocatalytic Reaction Networks
Autocatalytic Reaction Networks: A Pathway to Spatial Temporal Mastery in Dynamic Materials
- Version of Record online: 04 December 2024
An autocatalytic chemical reaction network (CRN) has been developed that enables efficient control over sol(I)-gel and gel-sol(II) transitions through autocatalytic fronts. This approach, supported by a reaction-diffusion model, provides a theoretical framework for system preprogramming and demonstrates the potential for reversible, repeatable sol-gel transitions, shaping new frontiers in material science and bioengineering.
Review
DNA Nanotechnology
Crystalline Assemblies of DNA Nanostructures and Their Functional Properties
- Version of Record online: 04 December 2024
This review summarizes recent advancements in DNA tile and DNA origami-based 2D and 3D crystal lattice assemblies. It covers innovations in monomer design, guest molecule incorporation, and inorganic coating techniques. Key focus areas include assembly strategies, functional properties, structural challenges, and insights for future applications in programmable materials.
Research Article
Cancer Therapy | Very Important Paper
Near-Infrared Chemiluminophore Switches Photodynamic Processes via Protein Complexation for Biomarker-Activatable Cancer Therapy
- Version of Record online: 04 December 2024
Porous Organic Frameworks | Very Important Paper
Targeted Synthesis of Interpenetration-Free Mesoporous Aromatic Frameworks by Manipulating Catalysts as Templates
- Version of Record online: 04 December 2024
By tuning the size of the catalyst ligand, a mesoporous aromatic framework, PAF-333, was obtained. It was found that the steric hindrance of larger-sized ligands avoided the framework interpenetration. Thanks to its large pore volume (3.4 cm3 g−1), it could adsorb 13.4 wt % of hydrogen at 77 K, 100 bar and 0.537 g g−1 of methane at 298 K, 98 bar, making it an ideal candidate for large-scale on-board methane storage.
Communication
Ion Transport | Hot Paper
Transmembrane Delivery of an Aryl Azopyrazole Photo-switchable Ion Transporter Relay
- Version of Record online: 04 December 2024
The delivery of anion relay transporters across lipid membranes using a synthetic flippase is reported. These second generation photo-responsive relays incorporate an aryl azopyrazole photo-switch enabling greatly improved reversible photo-switching of the ion transport activity in situ, in real time.
Research Article
Organic Photovoltaics | Very Important Paper
Benzothiadiazole-Fused Cyanoindone: A Superior Building Block for Designing Ultra-Narrow Bandgap Electron Acceptor with Long-Range Ordered Stacking
- Version of Record online: 04 December 2024
A novel benzothiadiazole-fused cyanoindone (BTC) unit with ultra-strong electron-withdrawing ability was designed to synthesize an ultra-narrow bandgap acceptor BTC-2. Benefiting from long-range ordered stacking induced by BTC, PM6 : BTC-2 based organic photovoltaic device delivered a 17.17 % efficiency with a photocurrent of 30.34 mA cm−2, and achieved a light utilization efficiency of 4.88 % in binary semi-transparent application.
Zinc-Ion Batteries | Hot Paper
Polyoxotungstate Featuring Zinc-Ion-Triggered Structural Transformation as An Efficient Electrolyte Additive for Aqueous Zinc-Ion Batteries
- Version of Record online: 04 December 2024
Here, we present a rare instance of a soluble high-nuclearity polyoxometalate exhibiting Zn2+-triggered structural transformation from 0D nanocluster to 2D layer in ZnSO4 solution. Further, we showcase that such a kind of polyoxometalate, possessing Zn2+-triggered structural transformation properties, represents a new-type and promising class of additives for aqueous zinc battery electrolytes with significant potential applications.
Batteries | Very Important Paper
Thiosulfate-Mediated Polysulfide Redox for Energetic Aqueous Battery
- Version of Record online: 04 December 2024
The sluggish redox kinetics of polysulfides significantly impeded the performance of sulfur-based aqueous batteries (SABs). We proposed an effective redox regulation strategy via a thiosulfate-mediated ligand-chain interaction within the K2S2O3 electrolyte, which accelerates the polysulfide redox process (S0/S2−) and provides an additional capacity contribution through the thiosulfate redox pair (S2O32−/S4O62−). The thiosulfate-mediated SAB exhibits an unprecedented K+ storage capacity of 2470 mAh g−1 and a high energy density of 616 Wh kgS+Zn−1, surpassing both organic K–S batteries and conventional aqueous battery systems.
H2O2 Photosynthesis
Unsymmetric Protonation Driven Highly Efficient H2O2 Photosynthesis in Supramolecular Photocatalysts via One-Step Two-Electron Oxygen Reduction
- Version of Record online: 04 December 2024
An anthrazoline-based supramolecular photocatalyst (SA-SADF-H+) with an unsymmetric protonation structure significantly boosts H2O2 production from water and air. This design enhances charge separation and promotes dual active sites for Yeager-type O2 adsorption, enabling a selective one-step two-electron ORR pathway. SA-SADF-H+ shows an H2O2 rate of 4666.7 μmol L−1 h−1 and 100 % antibacterial efficiency against Staphylococcus aureus.
Ammonia Fuel Cells
Cooperative Active Sites on Ag2Pt3TiS6 for Enhanced Low-Temperature Ammonia Fuel Cell Electrocatalysis
- Version of Record online: 04 December 2024
We discovered a new multi-element catalyst (Ag2Pt3TiS6) with enhanced ammonia oxidation reaction and oxygen reduction reaction mass activities compared to Pt/C. Through density functional theory calculations, we identify that this arises from active site motifs consisting of Pt and Ti atoms that work cooperatively. The bifunctional capability of Ag2Pt3TiS6 is demonstrated as both the cathode and anode in a direct ammonia fuel cell.
Organic Materials
A Helical Tubular Dyad of [9]Cycloparaphenylene: Synthesis, Chiroptical Properties and Post-Functionalization
- Version of Record online: 04 December 2024
Employing the site-specific functionalization strategy, a radially conjugated, helical tubular molecule has been constructed by covalently connecting [9]cycloparaphenylenes with three sp-hybridized all-carbon linkers. This compound exhibits intriguing solid-state packing patterns, exceptional CPL characteristics, and facile post-functionalization.
Electrochemistry | Very Important Paper
Pioneering Built-In Interfacial Electric Field for Enhanced Anion Exchange Membrane Water Electrolysis
- Version of Record online: 04 December 2024
The Ni3N@W5N4 nano-heterostructure catalyst, with built-in interfacial electric field and ultra-thin W5N4 shells, significantly enhances alkaline hydrogen evolution reaction kinetics involved in anion exchange membrane water electrolysis by reducing energy barriers and demonstrating excellent performance and stability.
Covalent Organic Frameworks
Flux Synthesis of Robust Polyimide Covalent Organic Frameworks with High-Density Redox Sites for Efficient Proton Batteries
- Version of Record online: 04 December 2024
A new rich nitrogen triazole-based monomer was used to fabricate two highly crystalline, porous and robust polyimide COFs with high-density redox-active groups through a flux synthesis method for proton batteries. The COF electrodes delivered a high reversible capacity, superior rate performance, and outstanding long-term stability, and the full cell with the COF anode and the MnO2 cathode achieved both a high energy and power density.
Heterogeneous Catalysis
Engineered Polymeric Carbon Nitride for Photocatalytic Diverse Functionalization of Electronic-Rich Alkenes
- Version of Record online: 04 December 2024
Fluorescent Materials | Very Important Paper
Unraveling the Configuration Modulation in Spiro-Based Through-Space Charge Transfer Materials
- Version of Record online: 04 December 2024
Through-space charge transfer (TSCT) materials show potential for optoelectronic applications. This study unravels how spatial configuration impacts TSCT properties. Different photophysical properties were observed in a series of spiro-based TSCT materials. Their external quantum efficiencies range from 28.0 % to 3.6 %, highlighting the importance of spatial arrangement.
CO2 Reduction | Very Important Paper
Organic Molecule Functionalization Enables Selective Electrochemical Reduction of Dilute CO2 Feedstock
- Version of Record online: 04 December 2024
We report an organic molecule functionalization strategy to boost selectivity towards CO2R and suppress HER over a range of catalysts including Bi, Cu and Zn. With a functionalized Bi catalyst, we attained a formate Faradaic efficiency of 85.8 % with dilute feedstock (15 % CO2) at 100 mA cm−2. Using an electrolyzer with a porous solid electrolyte layer, we successfully showcase 30 h of continuous high-purity formic acid production from dilute CO2.
Nanoclusters for Electrocatalysis | Very Important Paper
How Carbene Ligands Transform AuAg Alloy Nanoclusters for Electrocatalytic Urea Synthesis
- Version of Record online: 04 December 2024
In this work, we prepare an AuAg alloy nanocluster ligated by carbene, [Au13Ag12(PPh3)8(BMIm)2I8]SbF6, which is the first of its kind to show higher thermostability and higher sensitivity to light. It is attributed to a unique delocalization of electrons within the frontier orbitals. The Au13Ag12 : BMIm anchored on NiFe-LDH exhibits remarkable electrocatalytic activity in the electrosynthesis of urea.
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.
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
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
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
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.
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.
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.