• Issue

    Angewandte Chemie International Edition: Volume 63, Issue 17

    April 22, 2024

Covers

Free Access

Cover Picture: Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics (Angew. Chem. Int. Ed. 17/2024)

  • First Published: 28 March 2024
Description unavailable

An erbium triple-decker complex featuring a 9,10-diborataanthracene middle deck and two substituted cyclooctatetraene outer decks is depicted on the cover. The magnetic interaction between the two erbium ions is highlighted, since the title compound allows the evaluation of the 9,10-diborataanthracene ligand for possible exchange interactions. In addition, the two ligands that compose the triple-decker complexes are displayed. The title compound represents the first triple-decker complexes of lanthanides with a six-membered ring, as illustrated by Eufemio Moreno-Pineda, Peter W. Roesky et al. in their Research Article (e202401372).

Free Access

Back Cover: PAM-Engineered Toehold Switches as Input-Responsive Activators of CRISPR-Cas12a for Sensing Applications (Angew. Chem. Int. Ed. 17/2024)

  • First Published: 15 April 2024
Description unavailable

The RNA-programmed CRISPR-Cas12a activity requires two factors: complementarity between the guide RNA and the dsDNA, and a short Palindromic Adjacent Motif (PAM) flanking the target. In their Research Article (e202319677), Alessandro Porchetta et al. rationally designed PAM-engineered DNA hairpins as input-responsive activators of Cas12a. By utilizing the trans-cleavage activity of Cas12a as a signal transduction method, the authors demonstrated the rapid, one-pot detection of IgG antibodies and small molecules.

Graphical Abstract

Free Access

Graphical Abstract: Angew. Chem. Int. Ed. 17/2024

  • First Published: 15 April 2024

Corrigenda

Introducing …

Free Access

Ujjal Das

  • First Published: 20 March 2024
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“The most exciting thing about my research is that it is very different from textbook organic and organometallic chemistry, thus providing opportunities to create new knowledge about chemical structure, bonding and reactivity… The most important thing I have learned from my students is their enthusiasm for chemistry.” Find out more about Ujjal Das in his Introducing… Profile.

Minireviews

Analytical Chemistry

Emerging Data Processing Methods for Single-Entity Electrochemistry

  • First Published: 27 February 2024
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This Minireview summarizes the latest advances in data processing techniques for single-entity electrochemistry towards achieving automation, real-time monitoring, increased sensitivity, as well as improved temporal and current resolution.

Zn-ion Batteries

Open Access

Zinc ion Batteries: Bridging the Gap from Academia to Industry for Grid-Scale Energy Storage

  • First Published: 22 February 2024
Description unavailable

Zinc ion batteries (ZIBs) hold great promise for grid-scale energy storage. However, the practical capability of ZIBs is ambiguous due to technical gaps between small scale laboratory coin cells and large commercial energy storage systems. This Minireview explores limiting factors for ZIBs practicality, using formulations to estimate practical energy density and predict battery lifespan in lab research activities.

Redox Chemistry

Open Access

Spontaneous Oxidation in Aqueous Microdroplets: Water Radical Cation as Primary Oxidizing Agent

  • First Published: 01 February 2024
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Spontaneous oxidation in aqueous microdroplets has led to controversy as to the identity of the oxidants. This minireview summarizes unique features of microdroplets, proposing water radical cation-driven reactions that reconcile different interpretations of the experimental results.

Reviews

Solar Cells

Crystallization Kinetics of Hybrid Perovskite Solar Cells

  • First Published: 17 January 2024
Description unavailable

Metal halide perovskites (MHPs) are outstanding photovoltaic materials. Nonetheless, despite significant progress, perovskite solar cells (PSCs) still face challenges. It is crucial to adjust the crystallization process during solution crystallization and film formation to overcome this challenge. We primarily discuss the relevant aspects of MHP crystallization kinetics, systematically summarize theoretical methods, and outline modulation techniques for MHP crystallization, including solution engineering, additive engineering, and component engineering.

Metabolic Labeling

Development and Applications of D-Amino Acid Derivatives-based Metabolic Labeling of Bacterial Peptidoglycan

  • First Published: 29 January 2024
Description unavailable

The promiscuity of the PG synthesis machinery allows for D-amino acid derivatives to selectively label PG within bacterial cell surface, while sparing host mammalian cells. This metabolic labeling strategy is selective, biocompatible, and broadly applicable, which has been utilized in various fields. In this review, we introduce the labeling approaches for PG using D-amino acid derivatives and the applications of this metabolic labeling strategy.

Research Articles

CO2 Electroreduction | Very Important Paper

(111) Facet-oriented Cu2Mg Intermetallic Compound with Cu3-Mg Sites for CO2 Electroreduction to Ethanol with Industrial Current Density

  • First Published: 04 March 2024
Description unavailable

The (111) facet-oriented Cu2Mg intermetallic compound with high-density ordered Cu3-Mg sites can stabilize oxygen-containing ethanol intermediates (*CHCHOH) at adjacent Cu catalytic sites during CO2 electroreduction, thus promoting the ethanol production with high selectivity.

Solar Cells

Colloidal Zeta Potential Modulation as a Handle to Control the Crystallization Kinetics of Tin Halide Perovskites for Photovoltaic Applications

  • First Published: 29 February 2024
Description unavailable

We provided a new method for accurately controlling the nucleation kinetics of tin halide perovskite films through modulating zeta potential of tin halide perovskite colloids. A fast nucleation rate was achieved by adding 3-aminopyrrolidine dihydroiodate (APDI2) in the precursor solution to change the zeta potential of the FASnI3 colloids. The high-quality tin halide perovskite film with APDI2 yields a high photovoltaic efficiency of 15.13 %.

Leukemia Treatment

Discovery of Selective and Potent ATR Degrader for Exploration its Kinase-Independent Functions in Acute Myeloid Leukemia Cells

  • First Published: 03 March 2024
Description unavailable

In the present work, a selective and potent ATR degrader was identified which was used as probe for explore the kinase-independent function of ATR. The results showed that ATR kinase inhibitor induced cell cycle arrest and inhibited the growth of AML cells. The ATR degrader was inclined to trigger immediate apoptosis in AML cells. A plausible explanation for this phenomenon is that ATR deletion induced nuclear envelope rupture, leading to genome instability, irreparable DNA damage. It causes to upregulate the level of p53 and subsequently triggers p53-mediated cell apoptosis.

Caged Compounds

Direct Activation of Nucleobases with Small Molecules for the Conditional Control of Antisense Function

  • First Published: 27 February 2024
Description unavailable

The incorporation of azidomethylene (Azm)-caged nucleobases into morpholino oligonucleotides via solid phase synthesis, enabled by the unique compatibility of azides with P(V) chemistry, allowed for conditional control of antisense function. The developed Azm-caged MOs (azMOs) were readily activated by a small molecule phosphine trigger through a Staudinger reduction and exhibited robust knockdown of exogenous and endogenous genes in cells and aquatic embryos. Furthermore, orthogonal knockdown of two genes in zebrafish embryos were enabled through use of azMO in combination with a photoactivatable MO.

Fluorescent Nanoparticles

Organic Fluorophores with Large Stokes Shift for the Visualization of Rapid Protein and Nucleic Acid Assays

  • First Published: 05 March 2024
Description unavailable

By assembling organic modules like building blocks, we explored design strategies for large Stokes shift fluorophores. A series of wavelength-tunable fluorophores have been synthesized, which exhibit large Stokes shift and satisfactory brightness. Furthermore, these dyes were applied in lateral flow assay (LFA). Consequently, direct visualization of protein assays with 100-fold sensitivity improvement over colloidal gold based LFA was achieved.

Artificial Ion Channels | Hot Paper

Concentration-Driven Evolution of Adaptive Artificial Ion Channels or Nanopores with Specific Anticancer Activities

  • First Published: 28 February 2024
Description unavailable

We constructed a novel class of artificial channels, showing an intriguing adaptive ability to form chloride ion channels at low concentrations while transforming into nanopores at high concentrations. The triphenylphosphonium (TPP) groups endow the channel-forming units with mitochondria-targeting properties, enabling them to drill holes on the mitochondrial membrane which subsequently induce targeted apoptosis of cancer cells.

Photoredox Catalysis

Open Access

Asymmetric, Remote C(sp3)−H Arylation via Sulfinyl-Smiles Rearrangement

  • First Published: 20 March 2024
Description unavailable

The merger of hydrogen atom transfer and Sulfinyl-Smiles rearrangement enables the asymmetric arylation of C(sp3)−H bonds in remote position to the double bond under photoredox conditions. Various chiral α-arylated amides are obtained with up to >99 : 1 er where the sulfinamido groups dictates the stereochemical outcome.

Electrochemistry

Phase-Transfer Catalysis for Electrochemical Chlorination and Nitration of Arenes

  • First Published: 23 February 2024
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A unique biphasic electrochemical reaction, wherein tetrabutylammonium (TBA+) salts play a dual role as both electrolyte and phase transfer catalysts, was developed to furnish chlorination and nitration of aromatic compounds using cheap inorganic salts with up to 98 % yield, shorter reaction time and higher Faradaic efficiency.

DNA Nanotechnology | Hot Paper

Synthetic Genes For Dynamic Regulation Of DNA-Based Receptors

  • First Published: 08 March 2024
Description unavailable

We demonstrate a general strategy that uses synthetic genes encoding for RNA effector strands that, by binding to a synthetic DNA ligand-binding receptor can induce the release or the loading of a molecular ligand.

Oxygen Evolution

Reconstructing Hydrogen-Bond Network for Efficient Acidic Oxygen Evolution

  • First Published: 29 January 2024
Description unavailable

We proposed reconstructing connected hydrogen-bond networks on the spinel surface by coupling hydrophilic units to defuse the trade-off of free water migration and deprotonation. The designed Mn−Co3O4@CN as a non-precious OER catalyst demonstrated a low overpotential of 395 mV at 10 mA cm−2 in an acidic medium and even surpasses RuO2 activity at high current density (100 mA cm−2 @ ~538 mV).

Solid-State Lithium-Oxygen Batteries

Light Enables the Cathodic Interface Reaction Reversibility in Solid-State Lithium-Oxygen Batteries

  • First Published: 05 March 2024
Description unavailable

Granulate-like discharge products are randomly stacked on solid-state cathodes (SSCs), facilitating their accommodation and ensuring the effective triple-phase boundaries (TPBs) of SSLOBs, thereby improving the battery reversibility of light irradiation.

Heterogeneous Catalysis | Hot Paper

Open Access

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

  • First Published: 03 March 2024
Description unavailable

Efficient LDPE deconstruction into liquid alkanes is feasible at near-room temperature with anhydrous aluminum chloride and gallium chloride. Carbenium ion initiation and hydride transfer govern the rates, conversion, and selectivity of cracking and alkylation reactions. The polar environment created by Lewis acids stabilizes carbenium ions and catalyzes hydride transfer, facilitating C−C bond cleavage in LDPE during cracking and promoting C−C bond formation during alkylation.

Polymer Chemistry

Functionalized Phenanthrene Imide-Based Polymers for n-Type Organic Thin-Film Transistors

  • First Published: 05 March 2024
Description unavailable

Two phenanthrene (PhA)-based electron-deficient moieties were developed and dual functionalization strategy was utilized to fine-tune the molecular lowest unoccupied molecular orbital (LUMO) energy levels. The synergetic effects from imide and carbonyl or cyano (CN) groups give these moieties suitable solubility and stabilized LUMOs. The CN-containing imide obtains a stronger electron-deficiency and its derivative polymer can achieve higher electron mobility under a lower voltage in transistors.

Analytical Chemistry

PAM-Engineered Toehold Switches as Input-Responsive Activators of CRISPR-Cas12a for Sensing Applications

  • First Published: 29 January 2024
Description unavailable

Toehold Switch DNA presenting a locked anti-PAM in the loop are designed to control Cas12a activity in response to different molecular inputs. The hairpin to duplex reconfiguration triggered by co-localization-based displacement reactions provides a means to control the accessibility of the PAM and Cas12a activity. We demonstrate the rapid, one-pot detection of antibodies and small molecules with high sensitivity and specificity.

Polymer Chemistry | Hot Paper

Open Access

Ring-Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium Catalysis

  • First Published: 29 February 2024
Description unavailable

Elemental sulfur, a waste product of the oil refinement process, cannot form a copolymer with industrially relevant propylene oxide unless a mechanistic trick is employed, wherein thiolate intermediates are formed in situ to combine the two incompatible monomers.

Bis(benzoselenadiazol)ethane: A π-Extended Acceptor-Dimeric Unit for Ambipolar Polymer Transistors with Hole and Electron Mobilities Exceeding 10 cm2 V−1 s−1

  • First Published: 05 March 2024
Description unavailable

A selenium-containing π-extended acceptor-dimeric unit, namely BBSeE, is designed and synthesized for constructing ambipolar polymer pN-BBSeE, featuring narrower band gap, high planarity, and low-lying LUMO. pN-BBSeE demonstrates ideally balanced ambipolar TFT performances with hole and electron mobility values up to 10.65 and 10.72 cm2 V−1 s−1, respectively, which is among the best ambipolar polymers reported so far.

Li-CO2 Batteries

Reversible Carbon Dioxide/Lithium Oxalate Regulation toward Advanced Aprotic Lithium Carbon Dioxide Battery

  • First Published: 26 February 2024
Description unavailable

The “trinity” strategy provides a new perspective for the development of Li−CO2 batteries. The addition of a soluble mediator, TEM RM, was used to modulate the three-phase interface and facilitate the conversion of CO2 to Li2C2O4. This strategy avoids a series of issues associated with the Li2CO3 product, contributing to excellent cycling performance for Li−CO2 battery.

Polymer Chemistry | Hot Paper

Sustainable Polymers with High Performance and Infinite Scalability

  • First Published: 29 February 2024
Description unavailable

We for the first time report the polyaddition of COS, diamines, and diacrylates, which is highly efficient, atom-economical, quantitatively yield, catalyst-free, and affords 46 polymers covering high-Tm crystalline plastics, thermoplastic elastomers, and amorphous plastics. The in-chain ester and thiourethane groups contribute to the enzyme-degradability and enhanced thermal/mechanical properties of the obtained polymers.

Solar Cells

Anti-Solvent-Free Preparation for Efficient and Photostable Pure-Iodide Wide-Bandgap Perovskite Solar Cells

  • First Published: 04 March 2024
Description unavailable

An anti-solvent-free (ASF) technique is devised to fabricate photostable pure-iodide wide-bandgap perovskite solar cells (PSCs). Compared with wide-bandgap PSCs made from anti-solvent process, the ASF method significantly improves the device performance and reproducibility. Furthermore, methylammonium chloride is applied to enhance the crystallinity. Consequently, the ASF-based PSCs deliver a highest PCE of 21.30 % with excellent photostability.

Li Metal Batteries | Hot Paper

Visualizing and Regulating Dynamic Evolution of Interfacial Electrolyte Configuration during De-solvation Process on Lithium-Metal Anode

  • First Published: 05 March 2024
Description unavailable

In situ FTIR and in situ MRI are employed to reveal the interfacial electrolyte configuration dynamic variation on Li-metal anode. During Li plating (de-solvation process), an anion-lean solvent-rich interface is revealed, which determines the SEI architecture.

Na-ion Batteries

MoS2 Hollow Multishelled Nanospheres Doped Fe Single Atoms Capable of Fast Phase Transformation for Fast-charging Na-ion Batteries

  • First Published: 05 March 2024
Description unavailable

An original Fe single atom doped MoS2 hollow multishelled structure (HoMS) is designed for the first time, which promotes the electron transfer and Na+ diffusion kinetic, thereby achieving excellent rate capability. Besides, the strong adsorption with Na+ and self-catalysis of Fe single atom facilitates the reversible conversion between 2H and 1T, and from NaxMoS2 to Mo and Na2S, combining buffering effect of HoMS to improve the cyclic stability.

Solid State Lithium Metal Batteries

Long-cycling and High-voltage Solid State Lithium Metal Batteries Enabled by Fluorinated and Crosslinked Polyether Electrolytes

  • First Published: 05 March 2024
Description unavailable

A fluorinated and crosslinked polyether electrolyte (FGPE) exhibiting excellent oxidation stability was developed, which enabled the polymer electrolyte-based Li||LiNi0.6Co0.2Mn0.2O2 batteries to achieve the longest cycling of 1000 cycles and high operating voltage of 4.7 V. Notably, solid-state industry-level 18650 cylindrical cells were first reported with an outstanding stability (500 cycles).

Theranostics | Very Important Paper

Fused Azulenyl Squaraine Derivatives Improve Phototheranostics in the Second Near-Infrared Window by Concentrating Excited State Energy on Non-Radiative Decay Pathways

  • First Published: 06 March 2024
Description unavailable

The PS-1 nanoparticles based on fused azulenyl squaraine derivatives exhibit remarkable second near-infrared phototheranostic performance by allowing almost all excitation energy to dissipate through non-radiative decay pathways. Additionally, long-wavelength light harvesting capability also increases due to J aggregation. Finally, the potential of PS-1 nanoparticles for treating deep-seated cancer and root canal infection were demonstrated.

Solid Electrolytes | Hot Paper

Halide Superionic Conductors with Non-Close-Packed Anion Frameworks

  • First Published: 03 March 2024
Description unavailable

A novel design of non-close-packed anion frameworks for halide superionic conductors is reported to show great potential for achieving superionic conductivity due to the significantly more distorted site and larger diffusion channel compared to its close-packed counterparts.

Li Metal Batteries | Hot Paper

Bipolar Polymeric Protective Layer for Dendrite-Free and Corrosion-Resistant Lithium Metal Anode in Ethylene Carbonate Electrolyte

  • First Published: 25 February 2024
Description unavailable

Bipolar polymeric protective layer (BPPL) is developed using cyanoethyl (−CH2CH2C≡N) and hydroxyl (−OH) polar groups, aiming to prevent EC-induced corrosion and facilitating rapid, uniform Li+ ion transport, where the polar hydroxyl group provides hydrogen bonding interactions between bipolar polymer and carbonate solvent, which effectively facilitates the Li+ desolvation, and traps free solvent molecules to block side reactions. The polar cyanoethyl group anchors anions to polymer chains through ion-dipole interactions, improving Li+ migration and restraining Li dendrite growth.

Perovskite Solar Cells | Hot Paper

Regulating Charge Transport Dynamics at the Buried Interface and Bulk of Perovskites by Tailored-phase Two-dimensional Crystal Seed Layer

  • First Published: 04 March 2024
Description unavailable

Tailored-phase two-dimensional crystal seed layer has been developed to optimize the charge transport dynamics at the buried interface and crystallization kinetics of perovskite films. The corresponding solar cell delivers a power conversion efficiency of 24.58 %. The devices exhibit an improved photostability with 88.4 % of initial efficiency being retained after aging under continuous 0.8-sun illumination for 2000 h in air.

Bioimaging

Open Access

Polymer Dots with Delayed Fluorescence and Tunable Cellular Uptake for Photodynamic Therapy and Time-Gated Imaging

  • First Published: 05 March 2024
Description unavailable

Amphiphilic block copolymers capable of self-assembling into polymer dots (Pdots) with both delayed emission and singlet oxygen generation were prepared. The hydrophobic core shields an emitter with thermally activated delayed fluorescence (TADF) to allow for time-gated spectroscopy. Simultaneously, the hydrophilic corona exposes a photosensitizer to allow for photodynamic therapy (PDT) through a theranostic approach. In vitro studies with HeLa cells show that the nature of the hydrophilic corona can alter uptake while maintaining PDT efficiency.

Organic Synthesis

Catalytic and Base-free Suzuki-type α-Arylation of Cyclic 1,3-Dicarbonyls via a Cyclic Iodonium Ylide Strategy

  • First Published: 22 February 2024
Description unavailable

A general and catalytic α-arylation of cyclic 1,3-dicarbonyls have been developed, providing expedient access toward a wide range of high-value 2-aryl (hetero)cyclic 1,3-dicarbonyls. The key to success is through a cyclic iodonium ylide strategy. Our approach is base-free and exhibits broad substrate scope (>100 examples). Importantly, our approach allows late-stage modification and significantly simplifying previous synthesis.

Protein Sensing

A Universal and Programmable Platform based on Fluorescent Peptide-Conjugated Probes for Detection of Proteins in Organelles of Living Cells

  • First Published: 04 March 2024
Description unavailable

A universal detection platform based on the peptide-conjugated probes (PCPs, name as TP-TPE-TO) by integrating protein recognition units, signal units, and particularly introducing organelle targeting units. The universal detection platform can achieve six protein analysis in three different organelles through simple transformation of recognition units and targeting units.

Diradicaloids

Open Access

Breaking Global Diatropic Current to Tame Diradicaloid Character: Thiele's Hydrocarbon Under Macrocyclic Constraints

  • First Published: 26 February 2024
Description unavailable

Two p-phenylene units with dissimilar resonance character (benzene and quinone) are embedded in a macrocyclic system. Their mutual orientation, in terms of the dihedral angle between the carbocyclic units, can stabilize the diradicaloid character of the system. Detailed spectroscopic and theoretical analysis confirmed a presence of open-shell singlet state with a low ΔEST of −0.34 kcal/mol.

K-ion Batteries | Hot Paper

A P2/P3 Biphasic Layered Oxide Composite as a High-Energy and Long-Cycle-Life Cathode for Potassium-Ion Batteries

  • First Published: 05 March 2024
Description unavailable

A biphasic P2/P3-K0.7Mn0.67Ni0.33O2 composite is proposed for potassium-ion batteries with large energy density and long-term cycling stability and characterized by XRD refinement, HAADF and ABF-STEM, and Fourier transformation. This P2/P3 intergrown layered composite can manifest a high energy density of 321 Wh kg−1 and also exhibit excellent capacity preservation during 600 cycles of K+ uptake/release.

Polymer Chemistry | Hot Paper

Mechanically Adaptive Polymers Constructed from Dynamic Coordination Equilibria

  • First Published: 07 March 2024
Description unavailable

This work proposes a novel strategy with reversible coordination equilibria for fabricating rate- and temperature-responsive mechanically adaptive materials. Based on dynamic coordination interactions, the developed polymers demonstrate excellent energy dissipation, damping, self-healing and 3D printing properties, providing potential applications in durable and customizable impact protection fields.

Chiral Nanoclusters

Modulation by Co (II) Ion of Optical Activities of L/D-glutathione (GSH)-modified Chiral Copper Nanoclusters for Sensitive Adenosine Triphosphate Detection

  • First Published: 04 March 2024
Description unavailable

In this study, the regulation ability of Co2+ toward the chiral and fluorescent optical activities of chiral Cu NCs is discovered, which produces strong chiral optical activity (the asymmetry factor of chirality is enhanced by a factor of 223), and its distribution is modulated from the UV region to the visible region. More importantly, the chirality effect on the detection sensitivity of chiral biological targets is well illustrated, providing helpful guidance for constructing chiral nanoprobes with better detection performances for chiral biotargets.

Solar Cells

Achieving High Fill Factor in Organic Photovoltaic Cells by Tuning Molecular Electrostatic Potential Fluctuation

  • First Published: 07 March 2024
Description unavailable

We designed and synthesized an outstanding acceptor material, namely ITOC6-4F, characterized by a considerably low amplitude of electrostatic potential fluctuation (0.8 kcal/mol). The ITOC6-4F-based cell exhibits an extremely low bimolecular recombination rate constant of 0.66×10−14 cm3 s−1. Consequently, this has led to the attainment of a new record fill factor of 0.816 in binary organic photovoltaic cells.

Bioconjugation

Peptide-Directed Attachment of Hydroxylamines to Specific Lysines of IgG Antibodies for Bioconjugations with Acylboronates

  • First Published: 29 February 2024
Description unavailable

A cyclic peptide directs the covalent attachment of a hydroxylamine to specific lysine residues of the fragment crystallizable region of antibodies, and is cleaved upon potassium acyltrifluoroborate (KAT) ligation under physiological conditions in a traceless fashion. This convenient approach to the direct conjugation of commercial IgG antibodies is suitable for the formation of antibody–drug, antibody–protein, and antibody–DNA conjugates.

Supramolecular Chiral Assembly

Precise Modulation of Circularly Polarized Luminescence via Polymer Chiral Co-assembly and Contactless Dynamic Chiral Communication

  • First Published: 08 March 2024
Description unavailable

Precise modulation of circularly polarized luminescence (CPL) including formulated color coordinates and handedness is realized by quantitative supramolecular co-assembly of three similar fluorene-based polymers with distinct fluorescence, directed by the addition principle. Furthermore, a contactless chiral communication with azobenzene-containing polymer (PAzo), which is a reverse subtraction principle, is used to achieve dynamic switch of CPL.

Machine Learning | Hot Paper

Open Access

Predicting Lewis Acidity: Machine Learning the Fluoride Ion Affinity of p-Block-Atom-Based Molecules

  • First Published: 07 March 2024
Description unavailable

The fluoride ion affinity (FIA) is among the most prominent descriptors for Lewis acidity. This paper presents FIA-GNN, a machine learning model that predicts FIA values in gas and solution (CH2Cl2) phase within a fraction of a second on a standard personal laptop. This is several orders of magnitude faster compared to the conventional quantum chemical approach. FIA-GNN is applied in four different case studies including catalysis research.

Single-Molecule Magnets

Open Access

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics

  • First Published: 23 February 2024
Description unavailable

The first rare-earth complexes featuring diborataanthracene ligands are showcased. These are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first lanthanide triple-decker featuring a heterocycle in the coordination sphere.

Main-Group Chemistry

Open Access

The Fundamental Disorder Unit in (Si, P)−(O, N) Networks

  • First Published: 10 February 2024
Description unavailable

In this study, the new compound class of oxonitridosilicate phosphates is presented with the three representatives Sr3SiP3O2N7, Sr5Si2P4ON12, and Sr16Si9P9O7N33. All compounds feature a vierer single chain of disordered (Si,P)(O,N)4 tetrahedra, which is named the fundamental disorder unit. Investigations of luminescence on Eu2+-doped compounds showed a quenching behavior that makes them interesting model systems for theoretical calculations.

Chirality

Open Access

Conformer-Selective Photoelectron Circular Dichroism

  • First Published: 05 March 2024
Description unavailable

Conformer selective Photoelectron Circular Dichroism of chiral 1-indanol is obtained via a resonance-enhanced two-photon ionization Scheme, thanks to the selectivity due to the S1←S0 transition. The equatorial and axial conformers of 1-indanol display PECD that dramatically differ in both amplitude and sign.

H2O2 Cleavage | Very Important Paper

Efficient Homolytic Cleavage of H2O2 on Hydroxyl-Enriched Spinel CuFe2O4 with Dual Lewis Acid Sites

  • First Published: 29 February 2024
Description unavailable

Macroscopic electron transfer (MET) is indispensable during the traditional H2O2 cleavage process. We demonstrate a non-redox hydroxyl-enriched spinel CuFe2O4 with dual Lewis acid sites to realize the homolytic cleavage of H2O2 without MET, which truly promotes H2O2 utilization and the catalyst stability, thereby expanding the applicability of heterogeneous catalysts in environmental remediation and organic synthesis.

Hydrogen Production | Very Important Paper

Heteroatom-Doped Ag25 Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production

  • First Published: 26 February 2024
Description unavailable

Encapsulation of MAg24 (M=Ag, Pd, Pt, and Au) NCs into a metal-organic framework, UiO-66-NH2, affords MAg24@UiO-66-NH2 composites. The AuAg24@UiO-66-NH2 exhibits the best activity, surpassing all other counterparts, and demonstrates excellent recyclability in photocatalytic hydrogen production. The formation of Z-Scheme heterojunction promotes charge separation, in conjunction with optimized Ag electronic state, which are responsible for the enhanced photocatalysis.

Electrocatalysis

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis

  • First Published: 16 February 2024
Description unavailable

A novel strategy is applied to activate pyrite-type RuS2 for alkaline hydrogen oxidation reaction by introducing sulfur vacancies. The introduction of S vacancies can regulate the p orbital of S atoms, leading to enhanced binding strength between the S site of RuS2−x and H. The S−H bond is also observed through the in situ Raman, directly proving the S atom as the HOR catalytic active site.

Solid-state Na Metal Batteries

A High-Rate and Long-Life Sodium Metal Battery Based on a NaB3H8 ⋅ xNH3@NaB3H8 Composite Solid-State Electrolyte

  • First Published: 13 February 2024
Description unavailable

A novel NaB3H8 ⋅ xNH3@NaB3H8 composite electrolyte, composed of the disordered NaB3H8 ⋅ xNH3 and the ordered NaB3H8, was rapidly synthesized from the sticky NaB3H8 ⋅ NH3 after the partial removal of NH3 at room temperature and successfully used at rates above 1 C in a solid-state sodium metal battery. This work opens a new group of solid electrolytes with high ionic conductivity and excellent interfacial stability for high-rate sodium metal batteries.

Two-Dimensional Materials

Bio-inspired Two-dimensional Nanofluidic Ionic Transistor for Neuromorphic Signal Processing

  • First Published: 28 February 2024
Description unavailable

Inspired by voltage-gated ion channels in neurons, a two-dimensional nanofluidic ionic transistor was fabricated, which operates based on the response to transmembrane potential. The device demonstrates a high on/off ratio of ~2000 and can transition from ambipolar to unipolar behavior with a low subthreshold swing of 560 mV/decade. The successful implementation of ionic logic gate circuits, including “NOT”, “NAND”, and “NOR” gates, paves a promising pathway towards ion-based brain-like computing.

Batteries | Very Important Paper

Converting Commercial Zn Foils into Single (002)-Textured Zn with Millimeter-Sized Grains for Highly Reversible Aqueous Zinc Batteries

  • First Published: 26 February 2024
Description unavailable

A simple and fast melting-solidification approach was developed to effectively convert commercial Zn foils into single (002)-textured Zinc with millimeter-sized (eye-visible) grains. The single (002) texture and huge grain features ensure large-scale epitaxial Zn deposition and significantly minimize the intergranular reactions, resulting in impressive reversibility of Zn metal anode in both Zn||Zn symmetric cells and full cells.

Polyoxometalates

Water-Tolerant Superbase Polyoxometalate [H2(Nb6O19)]6− for Homogeneous Catalysis

  • First Published: 22 February 2024
Description unavailable

We developed a lowly-protonated hexaniobate cluster with Lindqvist structure by a microwave-assisted hydrothermal synthesis. The proton abstraction from substrates with pKa>26 and from a base indicator with pKa=26.5 revealed the superbase property of [H2(Nb6O19)]6−. The catalytic activity for Knoevenagel and crossed aldol condensation reactions maintained even in the presence of water. We reported for the first time TBA6[H2(Nb6O19)] as a water-tolerant superbase catalyst among the basic metal oxide catalysts.

Composite Materials

Highly Thermally Conductive Aramid Nanofiber Composite Films with Synchronous Visible/Infrared Camouflages and Information Encryption

  • First Published: 09 February 2024
Description unavailable

BAB composite film has maximum λ of 10.36 W/(m⋅K), excellent electrical insulation (breakdown strength and volume resistivity of 41.5 kV/mm and 1.21×1015 Ω⋅cm, respectively) and mechanical properties (tensile strength of 170.9 MPa), also boasts adaptive visible light/infrared dual camouflage properties, as well as the function of fast encryption of QR code information within 24 seconds.

Immunochemistry | Hot Paper

Open Access

Deciphering the Chemical Language of the Immunomodulatory Properties of Veillonella parvula Lipopolysaccharide

  • First Published: 23 February 2024
Description unavailable

The chemistry of lipopolysaccharides (LPS) from gut microbes might tip the delicate balance towards tolerance or inflammation. By analyzing the chemistry of LPS from two strains of the pathobiont Veillonella parvula, key and unprecedented structural differences were uncovered, which were reflected in diverse immunoactivities. Attempts were made to identify the molecular determinants governing this phenomenon.

Heterogeneous Catalysis | Hot Paper

Discriminating the Active Ru Species Towards the Selective Generation of Singlet Oxygen from Peroxymonosulfate: Nanoparticles Surpass Single-Atom Catalysts

  • First Published: 25 February 2024
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Compared to the single-atom structure, ruthenium nanoparticles with adjacent surface sites exhibit enhanced activation of O−O bonds in peroxymonosulfate. This promoted activation facilitates the selective production of singlet oxygen, resulting in a high degradation efficiency for electron-rich pollutants.

Synthetic Methods

Deoxygenative Transformation of Alcohols via Phosphoranyl Radical from Exogenous Radical Addition

  • First Published: 15 February 2024
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A general approach to the direct deoxygenative transformation of primary, secondary, and tertiary alcohols has been developed. It proceeds through phosphoranyl radical intermediates generated by the addition of exogenous iodine radical to trivalent alkoxylphosphanes. Since these alkoxylphosphanes are readily in situ obtained from alcohols and commercially available, inexpensive chlorodiphenylphosphine, a diverse range of alcohols with various functional groups can be utilized to undergo deoxygenative cross-couplings with alkenes or aryl iodides. The selective transformation of polyhydroxy substrates and the rapid synthesis of complex organic molecules are also demonstrated with this method.

Biomass Conversion | Very Important Paper

Electrokinetic Analyses Uncover the Rate-Determining Step of Biomass-Derived Monosaccharide Electroreduction on Copper

  • First Published: 12 February 2024
Description unavailable

Electrochemical DHA conversion undergoes an initial dehydration and the subsequent hydrogenation to the acetol product. The electrokinetic analysis reveals that the rate-determining step follows an Eley–Rideal mechanism, that is, increasing the concentration of the adsorbed reactant alone will promote the activity. At alkaline (local) pH, DHA conversion is a homogeneous chemical reaction.

Solar Cells

Triisocyanate Derived Interlayer and High-Melting-Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells

  • First Published: 27 February 2024
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A robust shield emerges on perovskite, crafted through the dance of nucleophilic addition, coordination, and polymerization with triphenylmethane triisocyanate. A high-melting-point organic promoter for air-doping bars ion diffusion in the transport layer. This duet yields >25 % efficient n-i-p perovskite solar cells, basking in operational stability at 65 °C.

Communications

Drug Discovery

Tapcin, an In Vivo Active Dual Topoisomerase I/II Inhibitor Discovered by Synthetic Bioinformatic Natural Product (Syn-BNP)-Coupled Metagenomics

  • First Published: 17 January 2024
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By coupling sequence-tag-based metagenome mining, bioinformatic structure prediction algorithms, and total chemical synthesis we discovered the synthetic bioinformatic natural product tapcin. Tapcin is a mixed p-aminobenzoic acid-thiazole with a rare tri-thiazole substructure. It has topoisomerase I and II activity and exhibits potent in vitro and in vivo antiproliferative activity.

Supramolecular Chemistry

Open Access

A Terrylene Bisimide based Universal Host for Aromatic Guests to Derive Contact Surface-Dependent Dispersion Energies

  • First Published: 28 February 2024
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The large π-surface provided by terrylene bisimide affords a cyclophane that can accommodate a large variety of π-conjugated guests with binding constants up to 108 M−1. A linear relationship between the Gibbs binding energy and the surface area of the guest could be used to derive the interaction parameter of 0.31 kJ/molÅ2.

Epigenetics

Open Access

Evolved Readers of 5-Carboxylcytosine CpG Dyads Reveal a High Versatility of the Methyl-CpG-Binding Domain for Recognition of Noncanonical Epigenetic Marks

  • First Published: 29 January 2024
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Cytosine 5-modifications–occurring in different combinations in the two DNA strands of CpG dyads–are central to human chromatin regulation, but the customized recognition of such combinatorial marks is challenging. By re-evolving MBDs, the readers of canonical 5-methylated CpGs, we identify strong and selective readers of noncanonical 5-carboxylcytosine-containing CpGs that have fully abandoned the conserved recognition of methylated CpGs.

Organic Materials | Hot Paper

Ostwald ripening for designing time-dependent crystal hydrogels

  • First Published: 28 February 2024
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Metastable fibrous crystal networks form within hydrogels via a growing process involving polymer-induced mismatching nucleation, stiffening the hydrogels. These fibrous crystals would undergo Ostwald ripening and convert into stable bulk crystals. A remarkable reduction in material stiffness and interfacial adhesion is observed in this process, suggesting a time-dependent mechanism to program hydrogel properties.

Polymer Chemistry | Hot Paper

Open Access

Redesigned Nylon 6 Variants with Enhanced Recyclability, Ductility, and Transparency

  • First Published: 28 February 2024
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Geminal disubstitution on ϵ-caprolactam (nylon 6’s monomer) at different positions greatly modulates lactam monomer's reactivity and gem-nylon's performance properties, with dimethylation at the γ position yielding the most intriguing nylon that exhibits a combination of desired properties including enhanced chemical recyclability, mechanical ductility, and optical clarity, compared to commercial nylon 6.

Photoredox Catalysis | Hot Paper

Integrating Olefin Carboamination and Hofmann-Löffler-Freytag Reaction by Radical Deconstruction of Hydrazonyl N−N Bond

  • First Published: 21 February 2024
Description unavailable

A novel conversion mode for hydrazone by the division use of N2-moiety is developed by the photocatalytic redox neutral reaction of N-homoallyl-N-mesitylenesulfonyl (Mts)-hydrazones with ICF2CO2Et. The reaction merges olefin carboamination and Hofmann-Löffler-Freytag (HLF) reaction by radical addition/crucial distal N and H transfer sequences to yield ϵ-N-sulphonamide-α,α-difluoro-γ-amino acid esters under tandem C−C and dual C−N bonds forging.

Natural Products Synthesis

Total Synthesis of Principinol B

  • First Published: 22 February 2024
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The enantioselective total synthesis of principinol B was achieved by convergent and modular synthetic strategies. Two enantioenriched fragments were assembled by a diastereoselective intermolecular aldol reaction/carbonyl–olefin metathesis sequence. The oxabicyclo[3.2.1] core structure was introduced by the Williamson ether synthesis.

Zeolites

Open Access

CO Cofeeding Affects Product Distribution in CH3Cl Coupling over ZSM-5 Zeolite: Pressure Twists the Plot

  • First Published: 07 March 2024
Description unavailable

The use of oxygenate co-feeding presents intriguing prospects to manipulate reactivity patterns and catalyst stability in the conversion of methyl chloride to hydrocarbons over zeolite catalysts. CO-cofeeding induces a Koch carbonylation path as revealed through detection of the reactive intermediate ketene via operando PEPICO spectroscopy, boosting olefin selectivity at low pressure. Extrapolation to more easily activated CH3OH extends the catalyst lifetime under ambient pressure conditions.

Organic Synthesis | Hot Paper

Selective Ring-Opening Amination of Isochromans and Tetrahydroisoquinolines

  • First Published: 08 March 2024
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A novel selective ring-opening amination of isochromans and tetrahydroisoquinolines have been developed by employing molecular editing strategy. This chemistry offers a practical method to access various valuable compounds from easily available starting materials.

Luminescent Materials | Hot Paper

Open Access

Expanding Luminescence Horizons in Macropolyhedral Heteroboranes

  • First Published: 24 February 2024
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An investigation of the new 18- and 19-vertex macropolyhedral heteroborane clusters reported here containing sulphur and selenium cluster vertices and a subsequent reinvestigation of analogous known species has revealed that the property of luminescence in this wide range of structural types is much more extensive than previously recognised, where it has been restricted to those of the binary borane anti-B18H22 and its derivatives.

Photocatalysis | Hot Paper

Photoelectron Migration Boosted by Hollow Double-Shell Dyads Based on Covalent Organic Frameworks for Highly Efficient Photocatalytic Hydrogen Generation

  • First Published: 19 February 2024
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Hollow double-shell dyads have been constructed using covalent organic frameworks and transition metal sulfides, the double-shell architecture broadens light absorption, improves hydrogen evolution kinetics and reduces the photogenerated electron transfer resistance, resulting in high performance in photocatalytic hydrogen evolution reaction.

Aqueous Zn Batteries | Hot Paper

Unlocking Double Redox Reaction of Metal–Organic Framework for Aqueous Zinc-Ion Battery

  • First Published: 06 March 2024
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An innovative strategy of organic/inorganic double electroactive sites is proposed to obtain extra capacity and enhance the energy density in a manganese-based metal–organic framework (Mn-MOF-74). Simultaneously, a co-insertion/extraction of Zn2+ and H+ is demonstrated accompanying with manganese and oxygen double redox reactions in Mn-MOF-74 cathode. As a result, the Zn/Mn-MOF-74 batteries exhibit a high energy density and superior cycling stability in the electrolyte of 2 M ZnSO4.

Atropisomerism

Regio- and Atroposelective Ring-Opening of 1H-Benzo[4,5]oxazolopyridinones

  • First Published: 26 February 2024
Description unavailable

Regioselective and stereoselective C−O activation was achieved for atroposelective synthesis of N-arylisoquinoline-1,3(2H,4H)-diones. This method set up a new synthetic strategy for C−N atropisomer synthesis via an enantioselective ring-opening dynamic kinetic resolution process.

Macrolide Natural Products

Open Access

Total Synthesis of Lobatamides A and C

  • First Published: 08 March 2024
Description unavailable

Lobatamides are the most complex salicylate enamide natural products known and are expected to be a new class of antitumor agents through V-ATPase inhibition. The instability of the β-salicyloxy ester has prevented the late-stage installation of the enamide side chains, which play a crucial role in the biological activity. Now a common bislactone intermediate has been used for the total synthesis of lobatamides A and C.

Covalent Organic Frameworks | Hot Paper

Bimodal Oxidation Electrochemiluminescence Mechanism of Coreactant-Embedded Covalent Organic Frameworks via Postsynthetic Modification

  • First Published: 05 March 2024
Description unavailable

A coreactant-embedded nanoemitter (C–COF) is obtained by covalently linking a covalent organic framework (COF) with a coreactant via a postsynthetic modification strategy, resulting in a 1008-fold increase in electrochemiluminescence (ECL) intensity compared to the COF with an equivalent external coreactant. Notably, a bimodal oxidation ECL mechanism emerges from the oxidation of the coreactant in the framework and COF self-oxidation.

Photocatalysis | Hot Paper

Open Access

Photocatalytic O- to S-Rearrangement of Tertiary Cyclopropanols

  • First Published: 28 February 2024
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Inspired by the Newman-Kwart rearrangement, the development of a photocatalyzed O- to S-rearrangement of tertiary thiocarbonyl-activated cyclopropanol derivatives to access cyclopropanethiols is disclosed. Mechanistic findings enabled a preliminary extension toward other aliphatic alcohol classes. This work is anticipated to inspire new radical approaches to other valuable C(sp3)−S derivatives from abundant aliphatic feedstocks.

Electrocatalysis | Very Important Paper

Exfoliation of Metal–Organic Frameworks to Give 2D MOF Nanosheets for the Electrocatalytic Oxygen Evolution Reaction

  • First Published: 26 February 2024
Description unavailable

A strategy to synthesize ultrathin metal–organic framework (MOF) nanosheets is developed by selective thermal decomposition and liquid nitrogen exfoliation. This method advances the precise control of chemical bonds to give materials that are shown to be active electrocatalysts for the oxygen evolution reaction.

Metal-Organic Cages | Very Important Paper

Open Access

Fabrication of Self-Expanding Metal–Organic Cages Using a Ring-Openable Ligand

  • First Published: 07 March 2024
Description unavailable

The framework of a metal–organic cage can be expanded drastically with its topology retained (self-expansion). A rigid RhII6 cage with an oligomer-functionalized, stilbene-type dicarboxylic ligand transformed into a flexible cage upon cleavage of C=C double bond and simultaneous ring-opening. The dramatic increase in the cavity size enabled the effective trapping of multidentate N-donor guest molecules.