• Issue

    Angewandte Chemie: Volume 137, Issue 9

    February 24, 2025

Cover

Free Access

Titelbild: Entschlüsselung der Polymer-Interaktionen in Biokonjugaten unterschiedlicher Architektur durch zeitaufgelöste limitierte Proteolyse mit massenspektrometrischer Analyse (Angew. Chem. 9/2025)

  • First Published: 10 February 2025

Titelbild: Entschlüsselung der Polymer-Interaktionen in Biokonjugaten unterschiedlicher Architektur durch zeitaufgelöste limitierte Proteolyse mit massenspektrometrischer Analyse (Angew. Chem. 9/2025) Volume 137 Issue 9, 2025

Limited proteolysis mass spectrometry allows for in deep molecular characterization of complex bioconjugates. In their Communication (e202415354), Lorenz Meinel, Tessa Lühmann et al. present a protocol for time-resolved proteolysis, deciphering interaction sites within protein–protein complexes and protein–polymer bioconjugates by 15N labeling. The cover image showcases the proteolysis of interferon-α2a and interferon-bioconjugates, resulting in peptide fragments that are analyzed using mass spectrometry.

Free Access

Innentitelbild: Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States (Angew. Chem. 9/2025)

  • First Published: 10 February 2025

Innentitelbild: Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States (Angew. Chem. 9/2025) Volume 137 Issue 9, 2025

The first wide-view image of multiple structural and phase transformations in MOFs is presented by Ming-Hua Zeng and co-workers in their Research Article (e202411150). The MOFs exhibit dynamic chemistry covering crystal-crystal and crystal-amorphous-liquid-glass-crystal evolution. The disordered hierarchical pores in amorphous and glassy MOFs enable efficient separation of C2H2/C2H4 and C3H6/C3H8 gases mixtures.

Free Access

Innenrücktitelbild: Scalable Atomic-Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low-Metal-Loading Dehydrogenation (Angew. Chem. 9/2025)

  • First Published: 10 February 2025

Innenrücktitelbild: Scalable Atomic-Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low-Metal-Loading Dehydrogenation (Angew. Chem. 9/2025) Volume 137 Issue 9, 2025

A novel approach to H2 extraction from liquid organic hydrocarbon carriers (LOHCs) using ultralow loading of Pt nanoparticles on a modified alumina structure with an ALD-titanium oxide shell is shown by Yongmin Kim et al. in their Research Article (e202417598). This unique catalyst design efficiently releases hydrogen from LOHCs, outperforming equivalent Pt and commercial catalysts. The ALD-TiO2 shell enhances the catalytic activity while minimizing Pt usage.

Free Access

Rücktitelbild: Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions (Angew. Chem. 9/2025)

  • First Published: 10 February 2025

Rücktitelbild: Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions (Angew. Chem. 9/2025) Volume 137 Issue 9, 2025

Non-stoichiometric cocrystals of hydrogen-bonded organic framework were constructed from two tetracarboxylic acids, possessing naphthalene and benzothiadiazole cores. The single crystals showed versatile fluorescence, including not only homogeneous color such as purple, blue, green and white, but also heterogeneous bicolor such as blue-green and green-yellow depending on the component ratios and distributions. In their Research Article (e202419992), Ichiro Hisaki, Abderrazzak Douhal and co-workers revealed the relationship between crystal structures and fluorescent properties of single crystals.

Frontispiz

Free Access

Frontispiz: CO2 Reduction at a Borane-Modified Iron Complex: A Secondary Coordination Sphere Strategy

  • First Published: 24 February 2025
Frontispiz: CO2 Reduction at a Borane-Modified Iron Complex: A Secondary Coordination Sphere Strategy Volume 137 Issue 9, 2025

Bifunctional complex design can enable selective activation of the strong C=O bonds in CO2. Much like a fiddler crab, the {Fe-H/Cp*-BCy2} complex employed by Marcus W. Drover and co-workers in their Research Article (e202421599), features two distinct "claws". This study highlights that cooperativity between the iron hydride and pendant Lewis acidic borane is integral to facilitate the reduction of CO2 to a C1 product.

Free Access

Frontispiz: Rapid N2O Formation from N2 on Water Droplet Surfaces

  • First Published: 24 February 2025
Frontispiz: Rapid N2O Formation from N2 on Water Droplet Surfaces Volume 137 Issue 9, 2025

N2 has long been considered as a stable reservoir in the atmosphere. However, in their Communication (e202421002), Deming Xia, Jingwen Chen, Joseph S. Francisco et al. proposed a novel reduction-then-oxidation pathway, through which N2 can be rapidly converted to N2O by O2 and O3 on water droplet surfaces.

Introducing …

Free Access

Anna Wuttig

  • First Published: 05 February 2025

Anna Wuttig

“I am most proud of my group when we follow the molecules, wherever they may take us, and, at the same time, maximize the impact of our findings… My favorite job in the lab is when seemingly disparate sets of data start to make sense in light of new thinking…” Find out more about Anna Wuttig in her Introducing… Profile.

Free Access

Marcus W. Drover

  • First Published: 05 February 2025

Marcus W. Drover

“The most rewarding aspect of being a scientist is pursuing fundamental curiosity-driven research simply because you wonder ‘what if…?’ followed by the thrill of figuring out what you've made!… I get my best ideas when I'm running on a treadmill…” Find out more about Marcus Drover in his Introducing… Profile.

Kurzaufsatz

Photochemistry

Open Access

Photoacids and Photobases: Applications in Functional Dynamic Systems

  • First Published: 31 January 2025
Photoacids and Photobases: Applications in Functional Dynamic Systems

Brønsted Photoacids and Photobases represent a unique class capable of donating or accepting a proton only after excitation. Here, we review the utilization of such molecules to light-trigger the direction and amplitude of functional dynamic systems. We discuss the guidelines of how to use such molecules in various systems and give a futuristic outlook on the current technology gap for further utilization.

Aufsatz

Photoactivatable Metallodrugs

Open Access

Advances in the Design of Photoactivatable Metallodrugs: Excited State Metallomics

  • First Published: 13 January 2025
Advances in the Design of Photoactivatable Metallodrugs: Excited State Metallomics

Fasten your seat belt! Choose lightning-speed, photoactivated journeys for complexes by selecting the metal, its oxidation state, ligands and geometry. Track complexes through excited singlet (S) states, intersystem crossing (ISC) to triplet (T) states, energy/charge-transfer, luminescence, ligand substitutions and redox reactions. Pathways to novel drugs with new mechanisms of action. Unravelling excited metallomics on the way is challenging.

Photocatalysis

Photoinduced Late-Stage Radical Decarboxylative and Deoxygenative Coupling of Complex Carboxylic Acids and Their Derivatives

  • First Published: 15 January 2025
Photoinduced Late-Stage Radical Decarboxylative and Deoxygenative Coupling of Complex Carboxylic Acids and Their Derivatives

Carboxylic acids serve as versatile building blocks in organic synthesis. This review highlights recent developments and trends in the late-stage functionalization of complex carboxylic acids and their derivatives enabled by visible light photocatalysis. It discusses a variety of radical decarboxylative and deoxygenative coupling reactions, with particular emphasis on the reaction mechanisms involved, as well as potential future directions for the field.

Forschungsartikel

Metal–Ligand Cooperativity | Hot Paper

CO2 Reduction at a Borane-Modified Iron Complex: A Secondary Coordination Sphere Strategy

  • First Published: 07 January 2025

CO2 Reduction at a Borane-Modified Iron Complex: A Secondary Coordination Sphere Strategy

Using a bifunctional {Fe-H/Cp*-BCy2} (Cp* = C5Me5) complex, which includes both iron-hydride and Lewis acid (borane) components, we demonstrate controlled CO2 reactivity to yield a formoxy borane-bound ferra(II)lactone [(η5-C5Me5-CH2-CO2(BCy2O2CH))FeII(diphosphine)] that incorporates two equivalents of reduced CO2. With excess HBCy2, we additionally establish catalytic dihydroboration of CO2 to produce the bis-acetal, Cy2BOCH2OBCy2 at room temperature (TON = 220 h−1).

MOF Glasses | Very Important Paper

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States

  • First Published: 13 August 2024

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States

The multiple structure transformation and phase evolution within MOF provide a vivid example showing the diverse MOF dynamic chemistry under both room and high temperature. The generated disordered hierarchical pores in amorphous and glassy MOFs different to the crystalline precursor, contributes to efficient separation of either C2H2/C2H4 or C3H6/C3H8 gases mixture for the first time in breakthrough experiments.

Low-Noble-Metal Catalysts

Scalable Atomic-Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low-Metal-Loading Dehydrogenation

  • First Published: 06 November 2024

Scalable Atomic-Layer Tailoring of Abundant Oxide Supports Unlocks Superior Interfaces for Low-Metal-Loading Dehydrogenation

TOC illustrates an approach to hydrogen release using low-load Pt on ALD-TiO2-modified γ-Al2O3 pellets for the dehydrogenation of liquid organic hydrogen carriers (LOHC), such as methylcyclohexane and hydrogenated biphenyl/diphenylmethane mixture. The cost-efficient catalytic reactor is crucial for LOHC import scenarios, enabling effective hydrogen storage, release and transport within existing infrastructure.

Organic Materials | Very Important Paper

Open Access

Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions

  • First Published: 25 November 2024

Single Crystalline, Non-Stoichiometric Hydrogen-Bonded Organic Frameworks Showing Versatile Fluorescence Depending on Composition Ratios and Distributions

Homogeneous and heterogeneous fluorescence with versatile colors were achieved on single crystals of non-stoichiometrically mixed bicomponent hydrogen-bonded organic frameworks with permanent porosity. Focused synchrotron X-ray diffraction analysis and microscopic fluorescence spectroscopy on single crystals reveal structure and property relationship.

Porous Materials | Very Important Paper

Anion-π Interactions on Functionalized Porous Aromatic Cages for Gold Recovery from Complex Aqueous with High Capacity

  • First Published: 18 January 2025
Anion-π Interactions on Functionalized Porous Aromatic Cages for Gold Recovery from Complex Aqueous with High Capacity

Preparation of a thiophene-modified aromatic porous organic cage (T-PAC) with high stability for efficient high-capacity gold recovery. It's also used to selectively recover gold from a variety of complex aqueous solutions in a stable and efficient manner. The theoretical calculations and dedicated experiments suggest that anion-π interactions between the [AuCl4] and TFP fractions on T-PAC cooperated with S/N boning and redox effects play the decisive role for the highly efficient gold-recovery performance.

Protein Switches

Open Access

Lanthanide-Controlled Protein Switches: Development and In Vitro and In Vivo Applications

  • First Published: 24 January 2025
Lanthanide-Controlled Protein Switches: Development and In Vitro and In Vivo Applications

Engineering artificial allosteric protein switches controlled by rare earth elements allows the development of assays, construction of bioelectronic devices, and REE-controlled microorganisms.

Nanoparticles | Very Important Paper

Open Access

Autocatalytic Nucleation and Self-Assembly of Inorganic Nanoparticles into Complex Biosimilar Networks

  • First Published: 12 December 2024
Autocatalytic Nucleation and Self-Assembly of Inorganic Nanoparticles into Complex Biosimilar Networks

Silver nanoparticles multiply via autocatalytic nucleation. They also subsequently self-assemble into percolating chains via spatially restricted attachment. Structural analysis using graph theory (GT) reveals biomimetic organizational patterns akin to those found in biofilms. GT descriptors suggest a fundamental similarity in the mechanisms driving the emergence of complexity in both biological and abiological systems.

Covalent Organic Frameworks | Hot Paper

Constructing Donor-Acceptor Covalent Organic Frameworks for Highly Efficient H2O2 Photosynthesis Coupled with Oxidative Organic Transformations

  • First Published: 19 September 2024
Constructing Donor-Acceptor Covalent Organic Frameworks for Highly Efficient H2O2 Photosynthesis Coupled with Oxidative Organic Transformations

We have developed a series of donor-acceptor covalent organic frameworks (COFs) that demonstrate exceptional efficiency in H2O2 photosynthesis, coupled with the selective oxidation of organic molecules. These COFs have set a new benchmark for H2O2 production, achieving one of the highest performances reported to date. Additionally, they exhibit remarkable selectivity and yield in the oxidation of various organic substrates. This work represents a significant breakthrough in the development of COF-based photocatalytic platforms for dual-function co-production systems.

Oxygen Evolution

Cation Migration-Induced Lattice Oxygen Oxidation in Spinel Oxide for Superior Oxygen Evolution Reaction

  • First Published: 10 November 2024
Cation Migration-Induced Lattice Oxygen Oxidation in Spinel Oxide for Superior Oxygen Evolution Reaction

Spinel oxide, Fe0.3Co0.9Cr1.8O4 with active lattice oxygen is developed by high-throughput methods. The lattice oxygen activation is facilitated by Cr oxidation (Cr3+→Cr6+), accompanied by cation migration from octahedral to tetrahedral sites. This geometric conversion generates oxygen non-bonding states essential for lattice oxygen oxidation. Oxidized oxygen species are stabilized through dimerization with CrO4 tetrahedra (d0 Cr6+). The oxide demonstrates high activity and stability at high current densities.

Perowskit-Photovoltaik

Aryl-Acetylen-Schichthybrid-Perowskite in der Photovoltaik

  • First Published: 11 January 2025
Aryl-Acetylen-Schichthybrid-Perowskite in der Photovoltaik

Wir demonstrieren die Fähigkeit, Zugang zu Ruddlesden-Popper- und Dion-Jacobson-2D-Perowskiten zu erhalten, die organische Spacer-Kationen auf Aryl-Acetylenbasis enthalten. Wir bewerten ihre einzigartigen opto(elektro)ionischen Eigenschaften durch eine Kombination von Techniken und verwenden sie in gemischtdimensionalen Perowskit-Solarzellen, die überlegene Leistungen und eine verbesserte Betriebsstabilität aufweisen und den Weg für Multifunktionalität in geschichteten Hybridmaterialien und deren Anwendung ebnen

Supramolecular Polymers | Hot Paper

Cu(I)-Induced G-Quartets: Robust Supramolecular Polymers Exhibiting Heating-Induced Aqueous Phase Transitions Into Gel or Precipitate

  • First Published: 20 January 2025

Cu(I)-Induced G-Quartets: Robust Supramolecular Polymers Exhibiting Heating-Induced Aqueous Phase Transitions Into Gel or Precipitate

Guided by Cu+, guanosine (G) forms robust, thermoset, and redox-responsive G-quadruplex (G4.Cu+) supramolecular polymers (SPs) through unique metallophilic interactions, π–π stacking, and hydrophobic forces. Interestingly, these SPs undergo aqueous phase transitions into a hydrogel via slow dehydration-driven crosslinking below the cloud temperature (Tcp) and fast, complete dehydration into a solid precipitate above Tcp, exhibiting LCST behavior.

NMR Spectroscopy

Open Access

Optimization of Structure-Guided Development of Chemical Probes for the Pseudoknot RNA of the Frameshift Element in SARS-CoV-2

  • First Published: 29 January 2025
Optimization of Structure-Guided Development of Chemical Probes for the Pseudoknot RNA of the Frameshift Element in SARS-CoV-2

The SARS-CoV-2 frameshift element pseudoknot plays a crucial role in viral replication. Using various techniques, especially NMR spectroscopy and in vitro frameshift assays, we have developed and optimized chemical probes that serve as fundamental structures for potential inhibitors targeting viral RNAs.

Analytical Chemistry

Dynamic, Single-cell Monitoring of RNA Modifications Response to Viral Infection Using a Genetically Encoded Live-cell RNA Methylation Sensor

  • First Published: 23 January 2025
Dynamic, Single-cell Monitoring of RNA Modifications Response to Viral Infection Using a Genetically Encoded Live-cell RNA Methylation Sensor

A genetically encoded live-cell RNA methylation sensor allowing for dynamically monitoring of RNA m6A modification at single-cell resolution is reported, and has been used to elucidate the interaction between host-cell RNA modifications and the infection of SARS-CoV-2 and its variants.

Solid-State Electrolytes | Hot Paper

Nanocrystals with Aggregate Anionic Structure Enable Ion Transport Decoupling of Chain Segment Movement in Poly(ethylene oxide) Electrolytes

  • First Published: 30 January 2025
Nanocrystals with Aggregate Anionic Structure Enable Ion Transport Decoupling of Chain Segment Movement in Poly(ethylene oxide) Electrolytes

Unlike classical poly(ethylene oxide) (PEO) electrolytes, single ion conductors, and crystalline polymers, this work discovered a novel ion transport mechanism mediated by PEO3: LiBF4 nanocrystals with aggregate anionic structure, which decouples the movement of PEO segments. The ultra-thin PEO/LiBF4 electrolyte exhibits balanced ion conductivity, Li+ transference number, and mechanical strength, extending the life of all-solid-state batteries.

Antibakterielle Nanogele

Open Access

pH-responsive Polyglycerol-Nanogele zur Behandlung von Parodontitis durch antibakterielle und pro-angiogenetische Wirkung

  • First Published: 19 January 2025
pH-responsive Polyglycerol-Nanogele zur Behandlung von Parodontitis durch antibakterielle und pro-angiogenetische Wirkung

Wir präsentieren hier einen bifunktionellen Nanogel-Komplex, der mit dem antimikrobiellen Wirkstoff Triclosan (TCS) und dem pro-angiogenetischen Wirkstoff Deferoxamin (DFO) ausgestattet ist, um mikrobielle Pathogene zu bekämpfen und die Geweberegeneration zu fördern. Durch den synergistischen Effekt von TCS und DFO zeigt der NG-TCS-DFO-Komplex eine signifikante Regeneration des Knochengewebes und eine beschleunigte Heilung der Parodontitis in vivo.

Hydroformilation | Hot Paper

Open Access

A Highly Dispersed Heterogeneous Cobalt Catalyst for Efficient Domino Hydroformylation Reductive Amination of Olefins

  • First Published: 29 January 2025
A Highly Dispersed Heterogeneous Cobalt Catalyst for Efficient Domino Hydroformylation Reductive Amination of Olefins

A highly dispersed Co−N/C catalyst has been developed for the efficient hydroaminomethylation of alkenes using CO and H2. This heterogeneous catalyst enables the synthesis of a broad range of secondary and tertiary amines, including pharmaceutically relevant molecules. The catalyst shows excellent activity, reusability, and scale-up potential, offering a green and cost-effective alternative to noble metal catalysts for amine synthesis.

Proton Exchange Membrane Fuel Cells

Converting Fe−N−C Single-atom Catalyst to a New FeNxSey Cluster Catalyst for Proton-exchange Membrane Fuel Cells

  • First Published: 21 January 2025
Converting Fe−N−C Single-atom Catalyst to a New FeNxSey Cluster Catalyst for Proton-exchange Membrane Fuel Cells

This work successfully converts Fe−N−C catalyst to an entirely new Fennessey cluster catalyst, which is highly active, selective, and strong H2O2-tolerance for proton-exchange membrane fuel cells.

Molecular Dynamics | Hot Paper

Harnessing Multi-Center-2-Electron Bonds for Carbene Metal-Hydride Nanocluster Catalysis

  • First Published: 16 January 2025
Harnessing Multi-Center-2-Electron Bonds for Carbene Metal-Hydride Nanocluster Catalysis

A bottom-up approach leveraging preexisting m-center-n-electron (mc-ne) bonds enables the synthesis of a highly stable cyclic(alkyl)amino carbene (CAAC) copper-hydride nanocluster, [(CAAC)6Cu14H12][OTf]2. With superior stability to Stryker's reagent, DFT calculations attribute this stability to hydride-to-ligand backbonding with π-accepting carbenes. This bench-stable cluster serves as an efficient and selective copper-hydride pre-catalyst in several catalytic applications.

Supramolecular Chemistry

Polymer Ligands with Multi-Nitrogen Heterocyclic Carbenes for Enhanced Stability and Reactivity in Nanoparticle Surface Functionalization

  • First Published: 26 January 2025
Polymer Ligands with Multi-Nitrogen Heterocyclic Carbenes for Enhanced Stability and Reactivity in Nanoparticle Surface Functionalization

This work presents a method for effective surface functionalization of nanoparticles (NPs) utilizing block copolymers containing nitrogen heterocyclic carbenes blocks and poly(reactive ester) block. This approach enhances NPs′ reactivity and stability, and is applicable to metal, metal oxide, and even rare-earth-doped upconversion NPs, thereby paving new pathways for the design and creation of nanoparticle-based functional materials.

Photodynamic Therapy

Open Access

Next-Generation Photosensitizers: Cyanine-Carborane Salts for Superior Photodynamic Therapy of Metastatic Cancer

  • First Published: 22 January 2025
Next-Generation Photosensitizers: Cyanine-Carborane Salts for Superior Photodynamic Therapy of Metastatic Cancer

We report a multifaceted assessment of novel cyanine-carborane salts as potent photosensitizers for photodynamic therapy (PDT). These compounds exhibit efficient tumor targeting through uptake by organic anion-transporting polypeptides (OATP). Upon near-infrared (NIR) light irradiation, cyanine-carborane salts generate reactive oxygen species (ROS), triggering apoptosis and significantly suppressing tumor cell proliferation and migration. In vivo studies demonstrate anti-tumor activity with minimal systemic toxicity, highlighting their potential as next-generation PDT therapeutics.

Photochemistry

Light-Driven Stepwise Reduction of Aliphatic Carboxylic Esters to Aldehydes and Alcohols

  • First Published: 21 January 2025
Light-Driven Stepwise Reduction of Aliphatic Carboxylic Esters to Aldehydes and Alcohols

The method described here unlocks the puzzle of the photochemical reduction of aliphatic carboxylic esters by sequential SET/HAT processes under the synergistic action of a phenolate-type photocatalyst and a thiol catalyst. The stepwise reduction of esters to aldehydes and alcohols under mild conditions provides a practical method for fundamental functional group transformation.

Prodrugs

Activatable Photosensitizer Prodrug for Self-Amplified Immune Therapy Via Pyroptosis

  • First Published: 17 January 2025
Activatable Photosensitizer Prodrug for Self-Amplified Immune Therapy Via Pyroptosis

The work proposes a self-amplified immune therapy strategy (SITS) for tumors and reports the first activatable photosensitizer immune-prodrug HDIM based on pyroptosis. Unlike existing combination therapies, HDIM demonstrates a significantly enhanced synergistic and cascading anti-tumor effect. Using HDIM, systemic immune activity is successfully remodeled to prevent tumor infiltration and metastasis.

Gold Nanoclusters

A Stable Open-Shelled Au26 Nanocluster with Remarkable Performance in Selective Oxidation of Benzyl Alcohol

  • First Published: 24 January 2025
A Stable Open-Shelled Au26 Nanocluster with Remarkable Performance in Selective Oxidation of Benzyl Alcohol

A stable open-shelled Au26 nanocluster with 15 valence electrons has been synthesized, and the presence of an unpaired electron is confirmed by magnetic measurements. This cluster shows high stability and excellent catalytic performance in selective oxidation of benzyl alcohol, achieving a record high TON of 100670 among atomically precise gold nanoclusters.

Synthetic Methods

Catalytic Asymmetric 1,4-Hydrocarbonation of 1,3-Enynes via Photoredox/Cobalt/Chromium Triple Catalysis

  • First Published: 10 January 2025
Catalytic Asymmetric 1,4-Hydrocarbonation of 1,3-Enynes via Photoredox/Cobalt/Chromium Triple Catalysis

A synergistic photoredox/cobalt/chromium triple catalysis system have been established, for selective 1,4-hydrocarbonation of readily available 1,3-enyne precursors, providing a modular synthetic platform for various trisubstituted axially chiral allenes bearing an extra central chirality. Furthermore, preliminary mechanistic studies are also conducted.

Nitridophosphates

Open Access

Adamantane-Type Nitridophosphate Phosphors AExLi10−2xP4N10 : Eu2+ via Medium-Pressure Ion-Exchange Reactions

  • First Published: 19 November 2024
Adamantane-Type Nitridophosphate Phosphors AExLi10−2xP4N10 : Eu2+ via Medium-Pressure Ion-Exchange Reactions

A facile method for the synthesis of nitridophosphate-based phosphors using hot isostatic pressing is presented. Ion exchange reactions starting from the Li-ion conductor Li10P4N10 enables the preparation of single crystals and bulk samples of compounds with the general formula AExLi10−2xP4N10. Upon doping with Eu2+, these compounds exhibit remarkable luminescent properties across the green to red spectral range.

Peptide Self-Assembly | Very Important Paper

The Intrinsic Fluorescence of Peptide Self-Assemblies Across pH Levels

  • First Published: 13 December 2024
The Intrinsic Fluorescence of Peptide Self-Assemblies Across pH Levels

This investigation deciphers the pivotal role of main-chain hydrogen bonding in peptide self-assembly as the primary source of intrinsic fluorescence. It demonstrates how pH-induced morphological diversity in peptides maintains fixed fluorescence peaks through the integrity of these bonding networks, while fluorescence intensity is modulated by structural variations. The study preliminarily unveils the fluorescence properties and regulatory mechanisms of self-assembled peptides.

Porphyrinoids

Open Access

Coordinative Self-assembly of π-Electron Magnetic Porphyrins

  • First Published: 06 December 2024
Coordinative Self-assembly of π-Electron Magnetic Porphyrins

Gold-coordinated polymers of π-extended porphyrins were fabricated by on-surface synthesis and coordination chemistry methods. Each porphyrinoid monomer features antiferromagnetic coupling and no interaction between nearest neighbors within the polymer backbone, behaving as a single magnetic entity.

Supramolecular Chemistry

Open Access

Dendritic Molecular Baskets for Selective Binding of Toxic Methotrexate

  • First Published: 11 November 2024
Dendritic Molecular Baskets for Selective Binding of Toxic Methotrexate

Dendritic molecular baskets are biocompatible cavitands capable of including toxic methotrexate (MTX) in their aromatic cavity. The binding is chemoselective with the complex forming in competitive cell media. With the unique mode of recognition and modular structure, dendritic baskets are leading candidates for developing effective antidotes against MTX poisoning.

Solar Cells

Deciphering the Impact of Aromatic Linkers in Self-Assembled Monolayers on the Performance of Monolithic Perovskite/Si Tandem Photovoltaic

  • First Published: 11 December 2024
Deciphering the Impact of Aromatic Linkers in Self-Assembled Monolayers on the Performance of Monolithic Perovskite/Si Tandem Photovoltaic

PTZ-SAMs with various aromatic linkers and linking orientations were designed and synthesized as the hole-selective layer (HSL) in inverted wide-band gap perovskite solar cells (PSCs). β-NapPAPT could form dense and highly ordered HSLs, enhancing interfacial interactions and favoring optimal energy level alignment with the perovskite films.

Photocatalysis | Hot Paper

Buffered Hydroxyl Radical for Photocatalytic Non-Oxidative Methane Coupling

  • First Published: 12 January 2025
Buffered Hydroxyl Radical for Photocatalytic Non-Oxidative Methane Coupling

A light-driven chemical cycle to generate ⋅OH buffer, in which SO42− moderates ⋅OH concentration by balancing ⋅OH generation from excited-state [FeIII(SO4)(H2O)5]+ and the back reaction between ⋅OH and Fe2+.

Oxygen Evolution | Very Important Paper

Ru0.1Mn0.9Ox Electrocatalyst for Durable Oxygen Evolution in Acid Seawater

  • First Published: 24 November 2024
Ru0.1Mn0.9Ox Electrocatalyst for Durable Oxygen Evolution in Acid Seawater

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.

Water Harvesting

Low Evaporation Enthalpy Ionic Covalent Organic Frameworks for Efficient Atmospheric Water Harvesting at Low Humidity

  • First Published: 16 December 2024
Low Evaporation Enthalpy Ionic Covalent Organic Frameworks for Efficient Atmospheric Water Harvesting at Low Humidity

Ionic COFs with numerous hydrophilic sites and high water stability were developed, achieving efficient water vapor adsorption and low enthalpy of evaporation at low humidity, offering cost-effective solutions for fresh water collection in desert regions.

CO2 Hydrogenation | Hot Paper

Low-temperature CO2 Hydrogenation to Olefins on Anorthic NaCoFe Alloy Carbides

  • First Published: 19 November 2024
Low-temperature CO2 Hydrogenation to Olefins on Anorthic NaCoFe Alloy Carbides

A highly active (FexCoy)5C2 structure is developed through the synergistic effect of electronic (sodium) and structural (cobalt) promoters. This strategy facilitates the hydrogenation of carbon dioxide into olefins at a low temperature of 240 °C, achieving the highest STY of olefins at low temperatures, even better than a significant proportion under high-temperature operating conditions. Additionally, it retains the capability to synthesize olefins at 180 °C.

Photosensitizers

Electron Transfer Mediator Modulates Type II Porphyrin-Based Metal–Organic Framework Photosensitizers for Type I Photodynamic Therapy

  • First Published: 19 November 2024
Electron Transfer Mediator Modulates Type II Porphyrin-Based Metal–Organic Framework Photosensitizers for Type I Photodynamic Therapy

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.

Recyclable Thermosets | Very Important Paper

Tailoring the Reprocessability of Thiol-Ene Networks through Ring Size Effects

  • First Published: 26 December 2024
Tailoring the Reprocessability of Thiol-Ene Networks through Ring Size Effects

Reprocessing of thiol-ene networks was accomplished by carefully tuning the relative distance between two thioether functionalities and elevating the neighboring group participation concept. As a result we achieved a fast bond exchange at high temperatures. This allowed extrusion processing of cross-linked materials, while maintaining structural integrity below 70 °C.

Energy Transfer

Efficient Energy Transfer from Quantum Dots to Closely-Bound Dye Molecules without Spectral Overlap

  • First Published: 29 October 2024
Efficient Energy Transfer from Quantum Dots to Closely-Bound Dye Molecules without Spectral Overlap

This work designs a perovskite quantum dot (QD)-dye system for efficient energy transfer (ET) from QDs to dyes occurring via the Dexter exchange-type interaction, at minimal donor-acceptor spectral overlap. Dyes containing a dimethyl iminium binding group as part of their conjugated system are chosen for high binding affinity to QD surface, crucial for donor-acceptor spatial wavefunction overlap for efficient ET.

CO2 Reduction

Enhancing CO2 Electroreduction to Multicarbon Products by Modulating the Surface Microenvironment of Electrode with Polyethylene Glycol

  • First Published: 08 January 2025
Enhancing CO2 Electroreduction to Multicarbon Products by Modulating the Surface Microenvironment of Electrode with Polyethylene Glycol

PEG was incorporated into the Cu electrode, achieving an FEC2+ of 90.3 % at 500 mA cm−2. This modification relaxes Nafion, increasing active site availability and enhancing *CO and *OH adsorption, promoting C−C coupling. Simultaneously, the restructured hydrogen bond network reduces active hydrogen species, suppressing the hydrogen evolution reaction.

Asymmetric Catalysis

Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization

  • First Published: 13 January 2025
Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization

A practical synthesis of strained dehydro-[2,2]-paracyclophane, a benzyne analogue of [2.2]paracyclophane was realized and it could be utilized in various strain-release nucleophilic or cycloaddition reactions to synthesize diverse functionalized [2.2]paracyclophanes. A copper-catalyzed enantioconvergent alkynylation of this intermediate generated valuable planar chiral PCP building blocks and heterocycles in good yields with excellent enantioselectivity. This method provides a new general platform for challenging planar chirality construction.

Photocatalysis

Visible-Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis of Highly Functionalized Xanthenes with Antitumor Activity

  • First Published: 23 December 2024
Visible-Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis of Highly Functionalized Xanthenes with Antitumor Activity

This study presents the first example of a photocatalyzed intramolecular skeletal rearrangement strategy for constructing the xanthene scaffold. This approach has been successfully applied to synthesize highly functionalized xanthenes and to revise the structures of myrtucomvalones E and F. Furthermore, biological studies reveal that a xanthene demonstrates significant antiosteosarcoma activity both in vitro and in vivo.

Trifluoromethylation

Open Access

The Role of Electron Transfer in Copper-Mediated C(sp2)−H Trifluoromethylation

  • First Published: 03 December 2024
The Role of Electron Transfer in Copper-Mediated C(sp2)−H Trifluoromethylation

Copper(II) and copper(III) trifluoromethyl complexes were used to elucidate the mechanism of Cu-mediated C(sp2)−H trifluoromethylation. For electron-rich substrates, a previously unidentified single electron transfer (SET) mechanism is followed, whereas electron-poor substrates follow CF3 radical release/electrophilic aromatic substitution (SEAr).

Carbon Electrodes

Open Access

Unlocking Mesoscopic Disorder in Graphitic Carbon with Spectroelectrochemistry

  • First Published: 30 December 2024

Unlocking Mesoscopic Disorder in Graphitic Carbon with Spectroelectrochemistry

We show that graphitic carbon electrodes exhibit electric-field dependent infrared activity that is sensitive to the bulk mesoscopic intrinsic disorder. Our combined experimental and theoretical work provides a roadmap for elucidating mesoscopic disorder in graphitic carbon electrode materials under potential bias.

Perovskite Solar Cells

Achieving over 20 % Efficiency in Laminated HTM-Free Carbon Electrode Perovskite Solar Cells through In Situ Interface Reconstruction

  • First Published: 26 December 2024
Achieving over 20 % Efficiency in Laminated HTM-Free Carbon Electrode Perovskite Solar Cells through In Situ Interface Reconstruction

We reported a chemical-mechanical in situ interface reconstruction strategy for the fabrication of HTM-free carbon electrode perovskite solar cells (c-PSCs) by laminating a free-standing carbon electrode onto perovskite film. Our new strategy overcomes the contact issues within the perovskite/carbon electrode interface and boosts the efficiency to 20.31 % with enhanced stability.

Sustainable Chemistry | Hot Paper

Solvent-Free Chemical Recycling of Polyesters and Polycarbonates by Magnesium-Based Lewis Acid Catalyst

  • First Published: 24 December 2024
Solvent-Free Chemical Recycling of Polyesters and Polycarbonates by Magnesium-Based Lewis Acid Catalyst

A MgCl2 catalyst system exhibits high selectivity and compatibility towards the depolymerization of the aliphatic (co)polyesters and polycarbonates under mild, solvent-free conditions (up to 98 % monomer yields). This approach provides a promising solution to the circular utilization of plastic materials.

Polymer Electrolytes

Regulating Crystalline Phase/Plane of Polymer Electrolyte for Rapid Lithium Ion Transfer

  • First Published: 16 December 2024
Regulating Crystalline Phase/Plane of Polymer Electrolyte for Rapid Lithium Ion Transfer

A new insight into the mechanism of crystal phase and plane exerts on the transfer of lithium ion in poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP) based polymer electrolytes is investigated in depth. β-phase-dominant segments are obtained by regulating dissolving process and the newly exposed (111/201)β crystal planes are conducive to provide more ion transport channels, which is beneficial to the rapid and smooth transfer of lithium ion.

Information Encryption | Very Important Paper

Evolution of Supramolecular Coordination Assemblies Visually Monitored by Time-Dependent Multicolor Fluorescence

  • First Published: 01 December 2024
Evolution of Supramolecular Coordination Assemblies Visually Monitored by Time-Dependent Multicolor Fluorescence

The metastable nanofiber structures triggered by the synergistic effect of π–π stacking and coordination between zinc ions and the organic ligands evolved into nanosheet assemblies over time in water, accompanied by fluorescence changes that enabled visual monitoring. This strategy could be extended to multiple ions and offers applications in temporal dynamic fluorescence encryption.

Polymerization

Acid-Enhanced Photoiniferter Polymerization under Visible Light

  • First Published: 25 December 2024
Acid-Enhanced Photoiniferter Polymerization under Visible Light

An acid-enhanced photoiniferter polymerization operating efficiently under visible light is reported. Addition of biocompatible citric acid, accelerates photolysis, eliminating induction periods by enhancing chain transfer agent consumption and reaction rates. This method yields well-defined polymers with near-quantitative conversions in just two hours and demonstrates versatility across various monomers, including the synthesis of high molecular weight polymers.

Porous Organic Frameworks | Very Important Paper

Targeted Synthesis of Interpenetration-Free Mesoporous Aromatic Frameworks by Manipulating Catalysts as Templates

  • First Published: 27 November 2024
Targeted Synthesis of Interpenetration-Free Mesoporous Aromatic Frameworks by Manipulating Catalysts as Templates

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.

Clusters for Heterogeneous Catalysis

A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation

  • First Published: 12 November 2024
A Hollowed-Out Heterometallic Cluster for Catalytic Knoevenagel Condensation

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.

Aqueous Zinc Batteries | Hot Paper

Manipulating Interphase Chemistry for Aqueous Zn Stabilization: The Role of Supersaturation

  • First Published: 27 December 2024
Manipulating Interphase Chemistry for Aqueous Zn Stabilization: The Role of Supersaturation

We highlight the role of local supersaturation in governing the fundamental crystallization chemistry of Zn4SO4(OH)6⋅xH2O (ZSH) and propose a subtle supersaturation-controlled morphology strategy to tailor the interphase chemistry of Zn anode. Attributed to the supersaturated environment created by caprolactam, ZSH selectively exposes high-energy (001) plane and initiates a pseudo-coincidence interface that significantly boosts the Zn lifespan.

Polyoxometalates

Host-Guest Assemblies of Polyoxovanadate Clusters as Supramolecular Catalysts

  • First Published: 13 November 2024
Host-Guest Assemblies of Polyoxovanadate Clusters as Supramolecular Catalysts

An efficient strategy for embedding catalytically active polyoxovanadate (POV) into supramolecular assemblies was developed by utilizing host-guest interactions between pillararenes grafted on the cluster and ditopic linkers. The amphiphilic nature of the POV in the host-guest complex promoted responsive behavior of the assembly toward the solvent polarity. Lastly, the assembly showed enhanced catalytic properties compared to the parent POV.

DNA Nanotechnology

Open Access

Photomodulated Transient Catalytic Constitutional Dynamic Networks and Reaction Circuits

  • First Published: 05 January 2025
Photomodulated Transient Catalytic Constitutional Dynamic Networks and Reaction Circuits

Photomodulation of dynamic DNA circuits/networks is demonstrated by photoprotection of an auxiliary caged unit yielding an oligonucleotide intervening with the temporally operating circuits. This is exemplified with photomodulation of DNAzyme or of dynamically operating DNA networks. The concept is applied to photomodulated network-guided inhibition of fibrinogenesis and controlling biocatalytic cascades.

Radicals

Isolated Neutral Organic Radical Unveiled Solvent-Radical Interaction in Highly Reducing Photocatalysis

  • First Published: 03 January 2025
Isolated Neutral Organic Radical Unveiled Solvent-Radical Interaction in Highly Reducing Photocatalysis

Isolated neutral helicene radical revealed the missing link in highly photoreducing consecutive photoelectron transfer (conPET) mechanism. Extensive mechanistic studies implied interaction of short-lived, non-emissive photoexcited radical and acetonitrile that generates reduced solvent. To that end, numerous extreme photoreduction have been showcased through useful functionalization of aryl halides using reduced solvent mediated conPET method.

Autophagy Imaging | Hot Paper

A FRET Autophagy Imaging Platform by Macrocyclic Amphiphile

  • First Published: 12 December 2024
A FRET Autophagy Imaging Platform by Macrocyclic Amphiphile

Leveraging the robust assembly and broad-spectrum encapsulation of macrocyclic amphiphiles, we developed a FRET-based autophagy imaging platform that demonstrates versatility and convenience as a powerful tool for imaging organelle autophagy.

Vanadium Flow Batteries | Very Important Paper

In-Situ Constructed Core-Shell Catalyst Enabling Subzero Capacity Unlocking of Cost-Effective and Long-Life Vanadium Flow Batteries

  • First Published: 17 December 2024
In-Situ Constructed Core-Shell Catalyst Enabling Subzero Capacity Unlocking of Cost-Effective and Long-Life Vanadium Flow Batteries

An in situ constructed Cu@Cu6Sn5 core-shell catalyst is shown to enhance redox kinetics of V2+/V3+ and selectively inhibit hydrogen evolution side reaction, achieving stable operation over 1200 cycles and enabling subzero capacity unlocking for cost-effective vanadium flow batteries.

NLO Materials | Hot Paper

Unconventional Heterobidentate Coordination of 4-Hydroxypyridine Leading to Remarkably Strong Second-Harmonic Generation in Zn(C5H4NO)2

  • First Published: 26 November 2024
Unconventional Heterobidentate Coordination of 4-Hydroxypyridine Leading to Remarkably Strong Second-Harmonic Generation in Zn(C5H4NO)2

Unusual heterobidentate coordination generates a novel compound Zn(C5H4NO)2, which shows a uniform alignment of microscopic polarization that generates the record-high bulk SHG among all UV-transparent Zn-containing metal-organic compounds.

Methanol Oxidation Reaction | Hot Paper

Adjacent-Ligand Tuning of Atomically Precise Cu−Pd Sites Enables Efficient Methanol Electrooxidation with a CO-Free Pathway

  • First Published: 23 December 2024
Adjacent-Ligand Tuning of Atomically Precise Cu−Pd Sites Enables Efficient Methanol Electrooxidation with a CO-Free Pathway

By introducing axial organic ligands to modify the atomically dispersed copper single atoms on the surface of Pd-metallene, we have constructed a catalyst with adjacent-ligand regulation effect to significantly enhance the catalytic performance of MOR.

Homogeneous Catalysis | Hot Paper

Diverse Synthesis of Arene-Fused [n.1.1]-Bridged Molecules via Catalytic Cycloaddition and Rearrangement Reactions

  • First Published: 23 December 2024
Diverse Synthesis of Arene-Fused [n.1.1]-Bridged Molecules via Catalytic Cycloaddition and Rearrangement Reactions

Boronyl radical-catalyzed cycloaddition of o-QMs or p-QMs with bicyclo[1.1.0]butanes in combination with selective Lewis acid-catalyzed rearrangements provides a collective approach for 6 types of medicinally attractive 2D/3D polycyclic compounds featuring bicyclo[n.1.1] bridged scaffolds.

Oxygen Evolution

Chloride Residues in RuO2 Catalysts Enhance Its Stability and Efficiency for Acidic Oxygen Evolution Reaction

  • First Published: 10 January 2025
Chloride Residues in RuO2 Catalysts Enhance Its Stability and Efficiency for Acidic Oxygen Evolution Reaction

Chlorine-containing RuO2 catalysts and pure RuO2 catalysts with comparable morphology and crystallinity were synthesized to clarify the effects of chlorine residues on the performance of RuO2. Notably, the RuO2-Cl catalyst exhibited superior activity and stability in acidic OER by lowering the limiting potential and suppressing the LOM pathway, maintaining high performance for over 1200 hours at high current densities.

Li−S Batteries

Alloying Strategy Regulating Size and Electronic Structure of Mo0.25Nb0.75Se2 to Achieve High-Performance Lithium−Sulfur Batteries

  • First Published: 02 December 2024
Alloying Strategy Regulating Size and Electronic Structure of Mo0.25Nb0.75Se2 to Achieve High-Performance Lithium−Sulfur Batteries

Guided by binary descriptors, 16 transition metal selenides are screened, and an alloying strategy is subsequently employed to controllably synthesize Mo0.25Nb0.75Se2/NG. This approach significantly reduces the surface energy while precisely tuning the band alignment and lattice matching between polysulfides and Mo0.25Nb0.75Se2/NG, thereby enhancing interfacial reaction kinetics and enabling the successful construction of high-performance lithium−-sulfur batteries.

Photocatalytic H2O2 Synthesis

Open Access

Non-Radical Mediated Photocatalytic H2O2 Synthesis in Conjugate-Enhanced Phenolic Resins with Ultrafast Charge Separation

  • First Published: 11 December 2024
Non-Radical Mediated Photocatalytic H2O2 Synthesis in Conjugate-Enhanced Phenolic Resins with Ultrafast Charge Separation

A sulfur-infused phenolic (RS) resin photocatalyst was meticulously designed at the molecular level to fine-tune its conjugation degree, thereby enhancing both its charge separation capability and hydrophilicity. This structural optimization enables the RS resin to achieve overall photocatalytic H2O2 synthesis via non-radical pathways, resulting in an outstanding solar-to-chemical conversion efficiency of 1.4 %.

Electrocatalytic Nitrate Reduction | Hot Paper

Selenium-Deficient FeSe2/Fe3O4 Electrocatalyst for Nitrate Reduction to Ammonia

  • First Published: 24 December 2024
Selenium-Deficient FeSe2/Fe3O4 Electrocatalyst for Nitrate Reduction to Ammonia

The slow kinetics of the proton-coupled electron transfer process results in the low conversion efficiency of NO3RR. Selenium-deficient FeSe2/Fe3O4 heterojunction is synthesized. The Se-deficient FeSe2 contributes to nitrate-deoxidation and hydrogenation, and Fe3O4 promotes water decomposition to provide H protons, which jointly promotes NO3RR.

Photocatalytic H2O Splitting | Hot Paper

Decoupling H2 and O2 Release in Particulate Photocatalytic Overall Water Splitting Using a Reversible O2 Binder

  • First Published: 15 December 2024
Decoupling H2 and O2 Release in Particulate Photocatalytic Overall Water Splitting Using a Reversible O2 Binder

Co(5 %)-HPCN/(rGO/Pt) consisting of photoresponsive chip (HPCN), H2 evolution cocatalyst (rGO/Pt), and cobalt complex capable of reversibly binding O2 ([Co(II)N4(H2O)2]2+) is constructed to achieve the decoupling of particulate photocatalytic overall water splitting under alternating UV and visible light irradiations. Under UV irradiation, the photogenerated holes oxidize [Co(II)N4(H2O)2]2+ into [Co(III)N4(O2)]2+ and H+, while the photogenerated electrons transfer to Pt through rGO for reduction of H+ to H2. Under visible irradiation, [Co(III)N4(O2)]2+ is photolyzed back to [Co(II)N4(H2O)2]2+ along with O2 evolution.

Homogeneous Catalysis

Copper-Catalyzed Regioselective and Enantioselective Hydropyridylation of Dienes for the Synthesis of Chiral Diaryl Compounds via Concerted Nucleophilic Aromatic Substitution

  • First Published: 26 November 2024
Copper-Catalyzed Regioselective and Enantioselective Hydropyridylation of Dienes for the Synthesis of Chiral Diaryl Compounds via Concerted Nucleophilic Aromatic Substitution

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.

G-quadruplex | Hot Paper

Locking up G-Quadruplexes with Light-Triggered Staples Leads to Increased Topological, Thermodynamic, and Metabolic Stability

  • First Published: 25 November 2024
Locking up G-Quadruplexes with Light-Triggered Staples Leads to Increased Topological, Thermodynamic, and Metabolic Stability

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.

Photovoltaic Electrolysis

A 17.73 % Solar-To-Hydrogen Efficiency with Durably Active Catalyst in Stable Photovoltaic-Electrolysis Seawater System

  • First Published: 23 December 2024
A 17.73 % Solar-To-Hydrogen Efficiency with Durably Active Catalyst in Stable Photovoltaic-Electrolysis Seawater System

This study provides a forward-looking direction for the economically scalable production of green hydrogen and showcases an innovative insight for the dynamic evolutionary mechanism of interfacial-water dissociation-oxidation. The photovoltaic-electrolysis system efficiently converts renewable energy sources into hydrogen, the integration of durable RuldsNiCr-LDH catalyst promises industrial application viability. And the newly defined PVTH parameter sets a new benchmark for photovoltaic-electrolysis systems.

Fluorescence | Very Important Paper

Boosting One- and Two-Photon Excited Fluorescence of Interpenetrated Tetraphenylethene-Based Metal–Organic Frameworks (TPE-MOFs) by Linker Installation

  • First Published: 12 January 2025
Boosting One- and Two-Photon Excited Fluorescence of Interpenetrated Tetraphenylethene-Based Metal–Organic Frameworks (TPE-MOFs) by Linker Installation

The optimization of one/two-photon excited fluorescence through linker installation in an interpenetrated TPE-MOF. Both the crystal packing density and ligand conformations can be modulated by linker installation.

Glycerol Oxidation | Very Important Paper

Active Hydroxyl-Mediated Preferential Cleavage of Carbon-Carbon Bonds in Electrocatalytic Glycerol Oxidation

  • First Published: 07 January 2025
Active Hydroxyl-Mediated Preferential Cleavage of Carbon-Carbon Bonds in Electrocatalytic Glycerol Oxidation

An electrocatalyst of Ni0.1Co0.9 alloy embedded in nitrogen-doped carbon nanotubes decorated with Ni−Co dual-atoms is constructed for glycerol oxidation reaction (GOR). The active *OH makes the GOR follow a direct oxidation pathway occurring at lower potentials. The optimized electronic state of Co single-atom regulated by Ni single-atom and Ni0.1Co0.9 alloy promotes *OH-mediated preferential cleavage of C−C bonds, leading to a high formate yield.

Electrocatalysis

Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis

  • First Published: 23 December 2024
Charge Manipulation of Porous Coordination Cages Tunes the Efficiency and Selectivity in Electrochemical Synthesis

The charge species of the porous coordination cages are regulated by ligand strategy. The charge-tunable porous coordination cages exhibit performance tweaking ability in the electrocatalytic nitrate reduction coupled 5-hydroxymethylfurfural oxidation system, which can not only indirectly adjust the efficiency of nitrate electrosynthesis of ammonia, but also modulate the product selectivity of 5-hydroxymethylfurfural oxidation.

Polymer Chemistry | Very Important Paper

New Thermoplastic Elastomers based on Ethylene-Butadiene-Rubber (EBR) by Switching from Anionic to Coordinative Chain Transfer Polymerization

  • First Published: 17 December 2024
New Thermoplastic Elastomers based on Ethylene-Butadiene-Rubber (EBR) by Switching from Anionic to Coordinative Chain Transfer Polymerization

Thermoplastic elastomers: Olefin triblock copolymers based on glassy polystyrene, ethylene butadiene rubber and highly crystalline polyethylene segments are prepared using a switch strategy from anionic polymerization to coordinative chain transfer (co)polymerization. They display low-viscosity above the melting point of PE and high elastic performances upon crystallization of PE segments.

Lithium Metal Batteries

A Lithiophilic Donor–Acceptor Polymer Modified Separator for High-Performance Lithium Metal Batteries

  • First Published: 23 December 2024
A Lithiophilic Donor–Acceptor Polymer Modified Separator for High-Performance Lithium Metal Batteries

A donor–acceptor polymer (ArMT) consisting of benzene rings and triazine was obtained and modified onto polypropylene (ArMT@PP) as separators for lithium metal batteries (LMBs). Due to the lithiophilic triazine units, this ArMT@PP simplifies the solvation structure of Li+, facilitates the migration of Li+ and forms a stable solid electrolyte interface. The assembled LMBs achieved a capacity retention of 90.58 % after 1200 cycles at 1 C.

Polycyclic Hydrocarbons

Intramolecular Charge Transfer in Antiaromatic Donor/Acceptor-Fused s-Indacenes

  • First Published: 05 December 2024
Intramolecular Charge Transfer in Antiaromatic Donor/Acceptor-Fused s-Indacenes

Late-stage oxidation of unsymmetrical benzofuran/benzothiophene-fused s-indacene regioisomers to their corresponding sulfones affords rationally designed molecules with varying degrees of donor/acceptor characteristics and intramolecular charge transfer (ICT). Depending on the fusion orientation of the donors and acceptors, the two most antiaromatic, oxidized isomers exhibit strong evidence of ICT with 30–40 nm solvatochromic shifts.

Electrocatalysis | Very Important Paper

Promoting Alcohols Electrooxidation Coupled with Hydrogen Production via Asymmetric Pulse Potential Strategy

  • First Published: 08 December 2024
Promoting Alcohols Electrooxidation Coupled with Hydrogen Production via Asymmetric Pulse Potential Strategy

A universal asymmetric pulse potential strategy was developed to promote the regeneration of active oxygen species which contribute to satble catalysis by noble metal catalysts for various alcohol oxidation reactions. Distinguished from conventional potentiostatic strategy, the operation time of stable glycerol oxidation electrocatalyzed by Pd was extended from 6 h to more than 2800 h under universal asymmetric pulse potential strategy.

Zuschrift

Homogeneous Catalysis | Hot Paper

Rapid N2O Formation from N2 on Water Droplet Surfaces

  • First Published: 23 December 2024
Rapid N2O Formation from N2 on Water Droplet Surfaces

Nitrogen (N2) is regarded as a stable reservoir for the N element in the atmosphere. However, this study finds that the stable N2 can rapidly react with atmospheric oxygen and ozone on ubiquitous water droplet surfaces via a novel reduction-then-oxidation pathway, resulting in the formation of nitrous oxide – the third most impactful greenhouse gas.

Coordination Polymers

Selenium-Substitution Strategy for Enhanced Mobility, Tunable Bandgap, and Improved Electrochemical Energy Storage in Semiconducting Conjugated Coordination Polymers

  • First Published: 21 January 2025
Selenium-Substitution Strategy for Enhanced Mobility, Tunable Bandgap, and Improved Electrochemical Energy Storage in Semiconducting Conjugated Coordination Polymers

Using a selenium-substitution strategy, a new selenium-based ligand, tetraseleno-hydroxyquinone (TSHQ), was synthesized, leading to the construction of a semiconducting three-dimensional Ag−Se coordination polymer (Ag4TSHQ). Ag4TSHQ shares the same topological structure as its sulfur counterpart, Ag4TTHQ, but exhibits superior charge mobility of approximately 350 cm2/V⋅s, which is twice that of Ag4TTHQ. Additionally, it demonstrates enhanced electrochemical energy storage capabilities. This research underscores the advantages of selenium-ligand-based coordination polymers (c-CPs) in optoelectronic devices and energy storage technologies.

Nanopore | Very Important Paper

Identification of Oligosaccharide Isomers Using Electrostatically Asymmetric OmpF Nanopore

  • First Published: 24 January 2025
Identification of Oligosaccharide Isomers Using Electrostatically Asymmetric OmpF Nanopore

A novel single-molecule oligosaccharide sensor, the OmpF nanopore, was developed for detecting unlabeled neutral oligosaccharides at low concentrations.

Polymer Chemistry | Very Important Paper

A Regio- and Stereoselective Ring-Opening Polymerization Approach to Isotactic Alternating Poly(lactic-co-glycolic acid) with Stereocomplexation

  • First Published: 20 January 2025
A Regio- and Stereoselective Ring-Opening Polymerization Approach to Isotactic Alternating Poly(lactic-co-glycolic acid) with Stereocomplexation

A robust regio- and stereoselective ROP approach was developed for the synthesis of isoenriched alt-PLGA (Regioselectivity up to 97 %, Pm up to 0.91) from rac-MG by the exploit of our spiro-salen scandium complexes, which represents a versatile platform for the preparation of high-performance biodegradable PLGA materials with diverse material properties and biodegradability.

Analytical Chemistry | Very Important Paper

Precise Identification of Native Peptides with Posttranslational Proline Hydroxylation by Nanopore

  • First Published: 25 January 2025
Precise Identification of Native Peptides with Posttranslational Proline Hydroxylation by Nanopore

A rationally engineered nanopore was constructed to directly discriminate posttranslational proline hydroxylation in native peptides. By modeling the specific binding structure, hydrophobic region was introduced into aerolysin to transduce the hydrophobicity difference induced by hydroxylation. Precise identification of proline hydroxylation in hypoxia-induced factor protein was achieved without interference from adjacent oxidation.

Molecular Photoelectrocatalysis | Hot Paper

Unlocking HFIP for Fluoroalkylation with Molecular Photoelectrocatalysis

  • First Published: 23 January 2025
Unlocking HFIP for Fluoroalkylation with Molecular Photoelectrocatalysis

Organofluorine compounds bearing the hexafluoroisopropyl group remain extremely scarce due to the lack of appropriate fluoroalkylation reagents. Herein we report a molecular photoelectrocatalysis method for the C−H hexafluoroisopropylation of indoles and tryptophan peptides, utilizing hexafluoro-2-propanol (HFIP) as the fluoroalkylation reagent.

Biocatalysis | Hot Paper

Enantioselective Trifluoromethylazidation of Styrenyl Olefins Catalyzed by an Engineered Nonheme Iron Enzyme

  • First Published: 23 January 2025
Enantioselective Trifluoromethylazidation of Styrenyl Olefins Catalyzed by an Engineered Nonheme Iron Enzyme

A new-to-nature enzymatic platform for the enantioselective trifluoromethylazidation of alkenes has been successfully established. Through 11 rounds of directed evolution, an engineered variant of nonheme iron enzyme, BsQueD-CF3, was developed, enabling the production of a wide range of enantioenriched CF3-containing molecules. This platform based on metalloenzymes would open a new avenue for biocatalytic trifluoromethylation chemistry.

Heterotriangulenes | Hot Paper

Open Access

A Trithia-Bridged N-Heterotriangulene: The Hitherto Missing Electron Donor

  • First Published: 16 December 2024
A Trithia-Bridged N-Heterotriangulene: The Hitherto Missing Electron Donor

An unprecedented triphenylamine with three sulfur ortho bridges has been developed as the very first representative of the hitherto elusive family of electron donors. The compound is readily oxidized to the corresponding radical cation with exceptional stability and forms crystalline donor-acceptor complexes with cyano-based acceptors.

Natural Products

Secupyritines A-C, Three Natural Propellane Securinega Alkaloids: Structure Elucidation and Total Synthesis Based on Biogenetic Building Blocks

  • First Published: 03 January 2025
Secupyritines A-C, Three Natural Propellane Securinega Alkaloids: Structure Elucidation and Total Synthesis Based on Biogenetic Building Blocks

Three novel polycyclic pyridine alkaloids (1-3) featuring a unique 2-oxa-6-aza[4.4.3]propellane skeleton were discovered from the twigs and leaves of Flueggea suffruticosa. Guided by a synthesis strategy based on the biogenetic building blocks, the first total synthesis of 1-3 was achieved through vinylogous Mannich-type reaction, Suzuki coupling reaction, and intramolecular aza-Michael addition reaction as key steps.

C-H functionalization

Late-Stage Pd(II)-Catalyzed C(sp3)−H Functionalization of Peptides Directed by a Removable, Backbone-Inserted Amidoxime Ether

  • First Published: 05 January 2025
Late-Stage Pd(II)-Catalyzed C(sp3)−H Functionalization of Peptides Directed by a Removable, Backbone-Inserted Amidoxime Ether

A Pd-catalyzed C(sp3)−H arylation of peptides has been developed, directed by an amidoxime ether, which can be incorporated into peptides at any amide bond. The backbone-installed directing group facilitates site- and stereoselective arylation of peptides, including at internal residues. Removal of the amidoxime ether generates the parent amide enabling a traceless C−H functionalization process.

Genetic Code Expansion

Design of Cell-Penetrating Domain Antibodies via a Genetically Encoded β-Lactam Amino Acid

  • First Published: 07 January 2025
Design of Cell-Penetrating Domain Antibodies via a Genetically Encoded β-Lactam Amino Acid

A genetically encoded β-lactam-lysine (BeLaK) enables a spontaneous inter-strand crosslinking with a proximal lysine in a supercharged monobody, affording a rigidified cell-penetrating variant with enhanced thermostability, greater cellular uptake, and potent inhibitory activity.

Supramolecular Chemistry | Very Important Paper

Kinetic Control of Self-Assembly Pathway in Dual Dynamic Covalent Polymeric Systems

  • First Published: 14 January 2025

Kinetic Control of Self-Assembly Pathway in Dual Dynamic Covalent Polymeric Systems

“One monomer for two materials”: Dual dynamic covalent chemistries diversify the pathway of molecular self-assembly and produce distinct polymeric materials as a function of evaporation rate.

Ferroelectric Perovskite | Hot Paper

Precise Tailoring of Unprecedent Layered Perovskite-Type Heterostructure Ferroelectric via Chemical Molecular Scissor

  • First Published: 20 January 2025
Precise Tailoring of Unprecedent Layered Perovskite-Type Heterostructure Ferroelectric via Chemical Molecular Scissor

This work reports the first ferroelectric of 2D perovskite heterostructures as single crystal by precisely tailoring inorganic sheets via a chemical molecular scissor. Combining its strong ferroelectricity and inherent anisotropy, crystal-based device exhibits an ultrahigh polarized-light sensitivity up to ~37 in self-powered mode. This work will facilitate the further development of ferroelectric materials for optoelectronic device applications.

Organometallic Chemistry

Open Access

The Interplay of Methylidyne and Carbido Species: Modeling a Fundamental Step in the Fischer–Tropsch Synthesis

  • First Published: 20 January 2025
The Interplay of Methylidyne and Carbido Species: Modeling a Fundamental Step in the Fischer–Tropsch Synthesis

The simplest organometallic reaction, the coupling of carbon and hydrogen atoms on a metal surface is demonstrated for the first time in a molecular system. Hydride migration to a μ2-carbido is shown to be favoured over alkyl migration.

Anion Channels

Open Access

Anion Transport by Bambusuril-Bile Acid Conjugates: Drastic Effect of the Cholesterol Content

  • First Published: 10 January 2025
Anion Transport by Bambusuril-Bile Acid Conjugates: Drastic Effect of the Cholesterol Content

Bambusuril macrocycles were functionalized with bile acids of different polarities and studied as anion transporters. The bambusuril with the most polar bile acids was demonstrated to form a unimolecular anion channel. Furthermore, increasing the cholesterol content in the membrane of liposomes drastically decreased the ion transport activity, likely squeezing the bile acid arms together to close the channel.

Li–O2 Batteries | Very Important Paper

Machine Learning-Guided Modulation of Li+ Solvation Structures towards Optimal Electrolyte Systems for High-Performance Li−O2 Battery

  • First Published: 26 January 2025
Machine Learning-Guided Modulation of Li+ Solvation Structures towards Optimal Electrolyte Systems for High-Performance Li−O2 Battery

A dual-solvent electrolyte has been successfully developed by aid of machine learning, which can show anion-induced ion-solvent-coordinated structures. As a result, a stable inorganic-rich SEI could be formed on anode, while large sized Li2O2 particles on cathode by regulating the growth pathway, enabling exceptional Li−O2 battery performance. These findings highlight the critical role of solvation structures and provide valuable theoretical guidance for rational design of next-generation electrolyte systems.

Electrocatalysis | Hot Paper

Electrochemical Cyclopropanation of Unactivated Alkenes with Methylene Compounds

  • First Published: 24 January 2025
Electrochemical Cyclopropanation of Unactivated Alkenes with Methylene Compounds

A general and efficient method for the organo-mediated electrooxidative cyclopropanation of unactivated alkenes with methylene compounds has been developed. The method shows excellent functional group tolerance and a broad substrate scope that can be extended to late-stage modification of biorelevant compounds.