• Issue

    Angewandte Chemie International Edition: Volume 62, Issue 8

    February 13, 2023

Cover Pictures

Free Access

Cover Picture: Electrochemical Cell-Free Biosensors for Antibody Detection (Angew. Chem. Int. Ed. 8/2023)

  • First Published: 03 January 2023
Cover Picture: Electrochemical Cell-Free Biosensors for Antibody Detection (Angew. Chem. Int. Ed. 8/2023) Volume 62 Issue 8, 2023

Programmable antigen-conjugated gene circuits, which, upon recognition of a target antibody, trigger the cell-free transcription of an RNA sequence that can be consequently detected with a disposable electrochemical sensor, were designed by Sara Bracaglia, Simona Ranallo, and Francesco Ricci in their Research Article (e202216512). The cell-free electrochemical biosensor allows the sensitive, specific, selective, and multiplexed detection of different antibodies in blood serum.

Free Access

Inside Cover: Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System (Angew. Chem. Int. Ed. 8/2023)

  • First Published: 23 January 2023
Inside Cover: Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System (Angew. Chem. Int. Ed. 8/2023) Volume 62 Issue 8, 2023

Redox-inactive substituents steer the activity of manganese oxide nanoparticles, Mn3O4:M, in the oxygen reduction reaction (ORR). In their Research Article (e202217186), Denis Kuznetsov, Christoph Müller, and co-workers describe how the ORR activity of Mn3O4:M correlates with the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M site. The work generalizes the role of redox-inactive elements in influencing the kinetics of electrocatalytic reactions and provides a perspective on the design of new catalyst compositions.

Free Access

Inside Back Cover: Reversible Handedness Inversion and Circularly Polarized Light Reflection Tuning in Self-Organized Helical Superstructures Using Visible-Light-Driven Macrocyclic Chiral Switches (Angew. Chem. Int. Ed. 8/2023)

  • First Published: 07 February 2023
Inside Back Cover: Reversible Handedness Inversion and Circularly Polarized Light Reflection Tuning in Self-Organized Helical Superstructures Using Visible-Light-Driven Macrocyclic Chiral Switches (Angew. Chem. Int. Ed. 8/2023) Volume 62 Issue 8, 2023

Reversible handedness inversion is achieved in self-organized helical superstructures using a visible-light-driven macrocyclic chiral switch, as reported by Quan Li and co-workers in their Research Article (e202216600). Green and blue light can drive the reversible switching between left- and right-handedness via the reversible cis/trans photoisomerization of azobenzene within the cyclic molecular switch.

Free Access

Back Cover: Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction (Angew. Chem. Int. Ed. 8/2023)

  • First Published: 07 February 2023
Back Cover: Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction (Angew. Chem. Int. Ed. 8/2023) Volume 62 Issue 8, 2023

Inspired by the active site of CO dehydrogenase, a metalloporphyrin-based mimic has been synthesized combining a multipoint hydrogen bond donor and a bimetallic active centre, as reported by Zakaria Halime, Ally Aukauloo, and co-workers in their Communication (e202214665). The cooperativity between the two metal centres of the catalyst was shown for both homo- and heterobimetallic analogues, leading to a significant enhancement of the catalytic performance in the heterogeneous CO2-to-CO electrocatalytic reduction.

Frontispiece

Free Access

Frontispiece: Anomalously Large Antiphase Signals from Hyperpolarized Orthohydrogen Using a MOF-Based SABRE Catalyst

  • First Published: 07 February 2023
Frontispiece: Anomalously Large Antiphase Signals from Hyperpolarized Orthohydrogen Using a MOF-Based SABRE Catalyst Volume 62 Issue 8, 2023

NMR Spectroscopy. In their Communication (e202213581), Boyd M. Goodson et al. report the addition of parahydrogen to particles comprised of an iridium-based catalyst on a metal–organic framework to produce orthohydrogen. A strongly hyperpolarized state is achieved.

Free Access

Frontispiece: Low-Valent MxAl3 Cluster Salts with Tetrahedral [SiAl3]+ and Trigonal-Bipyramidal [M2Al3]2+ Cores (M=Si/Ge)

  • First Published: 07 February 2023
Frontispiece: Low-Valent MxAl3 Cluster Salts with Tetrahedral [SiAl3]+ and Trigonal-Bipyramidal [M2Al3]2+ Cores (M=Si/Ge) Volume 62 Issue 8, 2023

Cluster Compounds. Low-valent MxAl3 and MxAl3 cluster salts with tetrahedral [SiAl3]+ and trigonal-bipyramidal [M2Al3]2+ cores (M=Si/Ge) are reported by Ingo Krossing et al. in their Research Article (e202215170).

Graphical Abstract

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Graphical Abstract: Angew. Chem. Int. Ed. 8/2023

  • First Published: 07 February 2023

Announcement

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Classifieds: Jobs and Awards, Products and Services

  • First Published: 07 February 2023
Classifieds: Jobs and Awards, Products and Services

Are you looking for a (new) job? Do you know someone who deserves an award? Are you trying to find a product or service to make your work more efficient? Our partners can help.

Introducing …

Free Access

Jifu Duan

  • First Published: 09 January 2023
Jifu Duan

“My biggest inspiration is critical thinking from reading papers … The most challenging part of my research is handling tiny protein crystals (about 0.2 mm long) under anaerobic conditions …” Find out more about Jifu Duan in his Introducing … Profile.

Free Access

Justina Jovaišaitė

  • First Published: 12 January 2023
Justina Jovaišaitė

“I chose my current career path because I couldn't do otherwise. It just happened naturally … The most challenging part of my job is a lot of freedom that results in a lot of responsibility …” Find out more about Justina Jovaišaitė in her Introducing … Profile.

Highlights

Single-Atom Catalysts

Single Platinum Atom Catalysts with High Density

  • First Published: 07 December 2022
Single Platinum Atom Catalysts with High Density

Qiao and co-workers recently designed and interpreted the construction of high-density Pt single atoms in the Co3O4 host with inter-site interactions via the Hard-Soft Acid-Base principle and further revealed the dynamic structure evolution process of the single atom sites by a series of in situ/ex situ spectroscopic techniques and theoretical computation.

Correspondence

Water Harvesting

Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

  • First Published: 19 January 2023
Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

In this Correspondence, we show that the rapid and cyclable atmospheric water harvesting processes in a hydrogen-bonded organic framework (HOF) recently reported by Ben and co-workers involve massive structural rearrangement. Adsorption and desorption of water causes motion of the entire framework in a crystal-to-crystal manner.

Reply to the Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

  • First Published: 19 January 2023
Reply to the Correspondence on “Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System”

A rapid water adsorption/desorption process with low energy consumption was achieved in the nano-confined channels of CPOS-6. The confined water can be regarded as a molecular superfluid.

Minireviews

Perovskites

Open Access

Halide Chemistry in Tin Perovskite Optoelectronics: Bottlenecks and Opportunities

  • First Published: 11 November 2022
Halide Chemistry in Tin Perovskite Optoelectronics: Bottlenecks and Opportunities

Efforts to boost tin halide perovskite optoelectronics have focused heavily on the instability of SnII, while other inconspicuous chemical processes have remained unexplored. This Minireview highlights the key role of native halide chemistry in the stability, device performance, ecological impact and prospects for visible light emission in this class of materials. Halide management routes towards viable optoelectronics are also proposed.

Water Desalination

Open Access

Emerging Materials for Interfacial Solar-Driven Water Purification

  • First Published: 24 November 2022
Emerging Materials for Interfacial Solar-Driven Water Purification

Research on solar-driven water purification has grown rapidly over the past years and emerging materials such as polymers, MOFs and COFs have been employed in this field recently. This minireview gives an overview of the basic concepts and principles for solar evaporation systems and on the development of novel photothermal materials.

Reviews

Photocatalysis

Mechanisms and Synthetic Strategies in Visible Light-Driven [2+2]-Heterocycloadditions

  • First Published: 28 December 2022
Mechanisms and Synthetic Strategies in Visible Light-Driven [2+2]-Heterocycloadditions

The [2+2]-heterocycloaddition between alkenes and carbonyls is a formidable strategy for the synthesis of complex strained 3D architectures. This Review provides an overview on the recent development of [2+2]-heterocycloadditions driven by visible light. The diverse synthetic approaches are presented with special emphasis on the involved reaction mechanisms along with possible future directions of the field.

Supramolecular Chemistry

Caught in Action: Visualizing Dynamic Nanostructures Within Supramolecular Systems Chemistry

  • First Published: 05 December 2022
Caught in Action: Visualizing Dynamic Nanostructures Within Supramolecular Systems Chemistry

As supramolecular chemistry begins to develop dynamic nanostructures that change over time, it becomes imperative to visualize self-assembly processes in solution in real-time. Our Review demonstrates how solution-based visualization techniques, namely optical super-resolution microscopy, atomic force and electron microscopy in liquid, and molecular dynamics simulations, have enriched our understanding of nanomaterials to obtain novel functions.

Communications

Orthohydrogen

Anomalously Large Antiphase Signals from Hyperpolarized Orthohydrogen Using a MOF-Based SABRE Catalyst

  • First Published: 16 December 2022
Anomalously Large Antiphase Signals from Hyperpolarized Orthohydrogen Using a MOF-Based SABRE Catalyst

Addition of parahydrogen to particles comprised of an iridium-based catalyst supported on a metal–organic framework produces dissolved orthohydrogen, but with a twist: a strongly hyperpolarized state is achieved that is enriched in the T0 sublevel, giving rise to a surprising anti-phase signal with enhancement up to ≈500-fold and significantly increased hyperpolarization lifetime.

CO2 Reduction | Very Important Paper

Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction

  • First Published: 11 December 2022
Bio-Inspired Bimetallic Cooperativity Through a Hydrogen Bonding Spacer in CO2 Reduction

Inspired by the active site of CO dehydrogenase (CODH), a novel metalloporphyrin-based mimic has been synthesized combining a multipoint hydrogen bond donor and a bimetallic active centre. The cooperativity between the two metal centres of the catalyst was evidenced for both homo- and heterobimetallic analogues leading to a significant enhancement of the catalytic performances of the heterogeneous CO2-to-CO electrocatalytic reduction in water.

Membranes

Open Access

A Homochiral Poly(2-oxazoline)-based Membrane for Efficient Enantioselective Separation

  • First Published: 28 December 2022
A Homochiral Poly(2-oxazoline)-based Membrane for Efficient Enantioselective Separation

S-Poly(2,4-dimethyl-2-oxazoline)-based membranes (S-PdMeOx/GO) are prepared via a simple solution-based method on porous substrates for chiral separation. The S-PdMeOx-based network within the graphene oxide scaffold induced homochirality in the membrane. The resulting S-PdMeOx-based membrane displays excellent enantioselectivity in separating racemic limonene mixtures.

Hydrogen Isotope Exchange

Cesium Amide-Catalyzed Selective Deuteration of Benzylic C-H Bonds with D2 and Application for Tritiation of Pharmaceuticals

  • First Published: 26 October 2022
Cesium Amide-Catalyzed Selective Deuteration of Benzylic C-H Bonds with D2 and Application for Tritiation of Pharmaceuticals

Cesium amide catalyst establishes a new bridge between benzylic C−H bonds and D2/T2, facilitating deuteration and tritiation of pharmaceutical compounds.

Micelles | Hot Paper

Open Access

Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly

  • First Published: 21 December 2022
Unimer Exchange Is not Necessary for Morphological Transitions in Polymerization-Induced Self-Assembly

We demonstrate that morphological transitions during radical RAFT-mediated PISA in water do not require unimer exchanges. The monomer present in the polymerization medium enables morphological transitions although it unexpectedly slows down unimer exchange.

Aqueous Zn-Ion Batteries | Hot Paper

Step by Step Induced Growth of Zinc-Metal Interface on Graphdiyne for Aqueous Zinc-Ion Batteries

  • First Published: 02 January 2023
Step by Step Induced Growth of Zinc-Metal Interface on Graphdiyne for Aqueous Zinc-Ion Batteries

Gradually inducing an increase in size from atoms to nanoflat surfaces shows the great power of the conjugated, multi-pore structure of graphdiyne (GDY). An electrode for aqueous zinc-ion batteries obtained by anchoring Zn atoms on graphdiyne shows excellent electroplating/stripping reversibility and lifespan without any Zn dendrites and side reactions, even at high current densities.

NMR Spectroscopy

SASSY NMR: Simultaneous Solid and Solution Spectroscopy

  • First Published: 01 January 2023
SASSY NMR: Simultaneous Solid and Solution Spectroscopy

SASSY NMR is a novel 2-in-1 technique capable of observing solid and solution phases simultaneously. Gel-like material appears in both fractions with a distribution proportional to the rigidity of the C−H dipoles. SASSY is advantageous when monitoring processes involving multiphase changes, as traditional sequential solid and solution NMR can miss rapid fluctuations. SASSY is easy to use, time efficient and can be applied universally.

Polymerization

Open Access

The Highly Controlled and Efficient Polymerization of Ethylene

  • First Published: 21 December 2022
The Highly Controlled and Efficient Polymerization of Ethylene

Coordinative chain transfer polymerization permits the controlled and efficient polymerization of ethylene, currently the most important monomer for plastic production. The key to the combination of control, very high activity, and an excellent catalyst economy seems to be a Group 4 metal complex stabilized by only one bulky and strongly bound monoanionic ligand. NH+B=N,N’-dimethylanilinium tetrakis (pentafluorophenyl)borate.

Asymmetric Catalysis

Copper-Catalyzed Enantioselective C1,N-Dipolar (3+2) Cycloadditions of 2-Aminoallyl Cations with Indoles

  • First Published: 23 December 2022
Copper-Catalyzed Enantioselective C1,N-Dipolar (3+2) Cycloadditions of 2-Aminoallyl Cations with Indoles

A binuclear copper-catalyzed (3+2) cycloaddition of 2-aminoallyl cations with indoles was achieved. This transformation featured a unique C1,N-dipolar cycloaddition reactivity for 2-aminoallyl cations. Enantioenriched pyrroloindoline derivatives were prepared by this cycloaddition in high yields with good enantio- and diastereoselectivities.

Organocatalysis

Diethylzinc-Mediated Cross-Coupling Reactions between Dibromoketones and Monobromo Carbonyl Compounds

  • First Published: 30 December 2022
Diethylzinc-Mediated Cross-Coupling Reactions between Dibromoketones and Monobromo Carbonyl Compounds

Chiral 1,4-dicarbonyl compounds can be obtained via the enantioselective bromination of aldehydes and subsequent cross-coupling reactions between the resulting chiral α-bromoaldehydes and α,α-dibromoketones. This cross-coupling reaction is enabled by the chemoselective formation of zinc enolates from α,α-dibromoketones in the presence of α-bromocarbonyl compounds.

Organic Phosphorescence | Hot Paper

Host–Guest Doping in Flexible Organic Crystals for Room-Temperature Phosphorescence

  • First Published: 30 December 2022
Host–Guest Doping in Flexible Organic Crystals for Room-Temperature Phosphorescence

The integration of flexibility and room-temperature phosphorescence in an organic single crystal is achieved by the host–guest doping strategy. The centimeter-scale crystals can be repeatedly bent and emit deep-red afterglow. This phenomenon occurs because the guest molecules, as trace impurities, greatly affect the emission properties of the materials, whereas the effect on the molecular packing of the host molecules is negligible.

Aromaticity

Open Access

Copper-Catalyzed C(sp3)-Amination of Ketone-Derived Dihydroquinazolinones by Aromatization-Driven C−C Bond Scission

  • First Published: 28 December 2022
Copper-Catalyzed C(sp3)-Amination of Ketone-Derived Dihydroquinazolinones by Aromatization-Driven C−C Bond Scission

Herein, we describe the development of a copper-catalyzed C(sp3)-amination of proaromatic dihydroquinazolinones derived from ketone building blocks. The reaction is enabled by the intermediacy of open-shell species arising from homolytic C−C bond-cleavage driven by aromatization. The protocol is characterized by its operational simplicity and generality, including chemical diversification of advanced intermediates.

Nanographenes | Hot Paper

A Triply Negatively Charged Nanographene Bilayer with Spin Frustration

  • First Published: 28 December 2022
A Triply Negatively Charged Nanographene Bilayer with Spin Frustration

A triply negatively charged radical species based on a bilayer of a C96 nanographene was synthesized and characterized. It is stabilized as an open-shell doublet ground state with an excited quartet state. It is the largest well-defined open-shell graphenic bilayer and also the first example of a triply negatively charged radical π-dimer. Spin frustration is observed in this species.

Iminosugars

Open Access

Influence of Side Chain Conformation on the Activity of Glycosidase Inhibitors

  • First Published: 27 December 2022
Influence of Side Chain Conformation on the Activity of Glycosidase Inhibitors

The first experimental demonstration that preorganization of inhibitor side chain conformation can favorably impact glycosidase inhibition is reported. By strategic installation of a methyl group at C6, a manno-configured iminosugar with the gauche,gauche side chain conformation was found to be a 27-fold better inhibitor than 1-deoxymannojirimycin.

Ion Channels | Hot Paper

Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

  • First Published: 30 December 2022
Synthetic K+ Channels Constructed by Rebuilding the Core Modules of Natural K+ Channels in an Artificial System

Rebuilding the core modules of natural K+ channels in an artificial system has led to a biomimetic K+ channel. This channel possesses similar structural features as the natural version, which enables it to replicate the transport behavior and biological function of natural K+ channels.

Membrane Proteins

High-Precision Mapping of Membrane Proteins on Synaptic Vesicles using Spectrally Encoded Super-Resolution Imaging

  • First Published: 29 December 2022
High-Precision Mapping of Membrane Proteins on Synaptic Vesicles using Spectrally Encoded Super-Resolution Imaging

We used the intensity ratio of the first and second vibronic peaks of semiconducting polymer dots (Pdots) to correlate photoswitching events. Multi-fold localization precision enhancement was achieved by averaging over switching events from the same Pdot. This method was used to count and map two membrane proteins on synaptic vesicles.

Organic Electronics

π-Extended Pyrrole-Fused Heteropine: Synthesis, Properties, and Application in Organic Field-Effect Transistors

  • First Published: 27 December 2022
π-Extended Pyrrole-Fused Heteropine: Synthesis, Properties, and Application in Organic Field-Effect Transistors

Here we report an efficient method for the synthesis of π-extended pyrrole-fused heteropine compounds and investigated their optical and electronic properties. A π-extended pyrrole-fused thiepine exhibited a “pitched π-stacking” structure in the crystal, and exhibited a high charge carrier mobility of up to 1.0 cm2 V−1 s−1 in single-crystal field-effect transistors.

Dihydroxylation

Open Access

Olefin Dihydroxylation Using Nitroarenes as Photoresponsive Oxidants

  • First Published: 12 December 2022
Olefin Dihydroxylation Using Nitroarenes as Photoresponsive Oxidants

Photoexcited nitroarenes ca be used, in conjunction with Pd-mediated hydrogenation, as osmium surrogates for olefin dihydroxylation.

Research Articles

Main-Group Clusters

Open Access

Low-Valent MxAl3 Cluster Salts with Tetrahedral [SiAl3]+ and Trigonal-Bipyramidal [M2Al3]2+ Cores (M=Si/Ge)

  • First Published: 07 December 2022
Low-Valent MxAl3 Cluster Salts with Tetrahedral [SiAl3]+ and Trigonal-Bipyramidal [M2Al3]2+ Cores (M=Si/Ge)

The elusive tetrahedral [Cp*Si(AlCp*)3]+ cation is prepared as its aluminate salts starting from Jutzi's [SiCp*]+ cation and Schnöckel's [(AlCp*)4]. Owing to its good accessibility, [SiAl3]+ can act as starting point towards the synthesis of low-valent silicon-doped aluminium-cluster cores as shown by the preparation of the larger [Si2(AlCp*)5]2+ cluster cation.

Imaging Agents

Highly Bright Near-Infrared Chemiluminescent Probes for Cancer Imaging and Laparotomy

  • First Published: 29 December 2022
Highly Bright Near-Infrared Chemiluminescent Probes for Cancer Imaging and Laparotomy

Near-infrared chemiluminophores with high chemiluminescence quantum yields were synthesized and developed into an activatable chemiluminescence probe for real-time turn-on detection of deeply buried tumor tissues in living mice.

Electrochemical Hydrogenation | Hot Paper

Open Access

Selective Electrochemical Hydrogenation of Phenol with Earth-abundant Ni−MoO2 Heterostructured Catalysts: Effect of Oxygen Vacancy on Product Selectivity

  • First Published: 23 December 2022
Selective Electrochemical Hydrogenation of Phenol with Earth-abundant Ni−MoO2 Heterostructured Catalysts: Effect of Oxygen Vacancy on Product Selectivity

Incorporation of MoO2 enhances the catalytic efficiency of Ni in selective electrochemical hydrogenation of phenol in aqueous 0.1 M H2SO4 solutions. The origin of the superior performance is revealed by in situ diffuse reflectance infrared spectroscopy and density functional theory calculations.

Gas Separation

Open Access

Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

  • First Published: 13 December 2022
Dibenzomethanopentacene-Based Polymers of Intrinsic Microporosity for Use in Gas-Separation Membranes

A series of dibenzomethanopentacene (DBMP) containing polymers of intrinsic microporosity (PIMs) were synthesised showing both high performance for pure and mixed gas permeability/selectivity and reduced ageing. The data for DBMP-rich PIMs are close to the latest Robeson upper bounds for several important gas pairs indicating their potential for making gas separation membranes.

Al-Ion Batteries | Very Important Paper

Self-Adaptive Re-Organization Enables Polythiophene as an Extraordinary Cathode Material for Aluminum-Ion Batteries with a Cycle Life of 100 000 Cycles

  • First Published: 14 December 2022
Self-Adaptive Re-Organization Enables Polythiophene as an Extraordinary Cathode Material for Aluminum-Ion Batteries with a Cycle Life of 100 000 Cycles

A polythiophene (PT) with the ability of self-adaptive re-organization is used for the cathode of aluminum ion battery. The polymerization mode can change from Cα−Cα (α-PT) to Cβ−Cβ (β-PT) which makes the PT obtain fast kinetics and small steric hindrance. PT cathode achieves a high capacity and super long cycle life of 100 000 cycles.

Organic Light-Emitting Diodes | Hot Paper

Open Access

A Deep-Blue-Emitting Heteroatom-Doped MR-TADF Nonacene for High-Performance Organic Light-Emitting Diodes

  • First Published: 08 December 2022
A Deep-Blue-Emitting Heteroatom-Doped MR-TADF Nonacene for High-Performance Organic Light-Emitting Diodes**

A deep blue boron-, nitrogen- and oxygen-doped nonacene emitter that shows multi-resonant thermally activated delayed fluorescence (MR-TADF) is described. The emitter shows bright, deep-blue narrowband emission in an organic light emitting diode (OLED) device.

Aqueous Zn Metal Batteries

Comprehensive H2O Molecules Regulation via Deep Eutectic Solvents for Ultra-Stable Zinc Metal Anode

  • First Published: 19 December 2022
Comprehensive H2O Molecules Regulation via Deep Eutectic Solvents for Ultra-Stable Zinc Metal Anode

The Zn(TFSI)2-sulfolane-water hybrid electrolytes based on the deep eutectic solvents present an efficient strategy for hydrogen bond network reconstruction and multifunctional interfaces optimization, realizing highly reversible Zn plating/stripping and excellent electrochemical performance.

Organic Synthesis

I2-Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives

  • First Published: 26 December 2022
I2-Catalyzed Cycloisomerization of Ynamides: Chemoselective and Divergent Access to Indole Derivatives

An I2-catalyzed unprecedented cycloisomerization of ynamides is developed, allowing various bis(indole) derivatives in good to excellent yields with wide substrate scope, which not only represents the first molecular iodine-catalyzed tandem complex alkyne cycloisomerizations but also constitutes the first chemoselective cycloisomerization of tryptamine-ynamides involving distinctively different C−C (alkyl) bond cleavage and rearrangement.

Zn-Ion Batteries | Hot Paper

Engineering p-Band Center of Oxygen Boosting H+ Intercalation in δ-MnO2 for Aqueous Zinc Ion Batteries

  • First Published: 24 December 2022
Engineering p-Band Center of Oxygen Boosting H+ Intercalation in δ-MnO2 for Aqueous Zinc Ion Batteries

Tuning the ϵp of O in δ-MnO2 cathode can effectively increase H+ intercalation contribution with excellent rate capability for aqueous zinc ion batteries. The ϵp could be a significant descriptor for H+ intercalation contribution that describes a volcano curve as a function of ϵp, and the best cathode is optimized to be the Cu−MnO2 among Cu−, Ni−, Co−, Zn−MnO2.

Perovskites | Hot Paper

Uncovering Aging Chemistry of Perovskite Precursor Solutions and Anti-aging Mechanism of Additives

  • First Published: 27 December 2022
Uncovering Aging Chemistry of Perovskite Precursor Solutions and Anti-aging Mechanism of Additives

In situ liquid time-of-flight secondary ion mass spectrometry (ToF-SIMS) is established as a molecular probe to unveil the aging chemistry of perovskite precursor solutions. In addition to uncovering the molecular mechanism of chemical aging reactions, it is demonstrated that the structure and stability difference of precursor-additive interactions determines the anti-aging effects of additives.

Bioluminescence

Visualizing the Intermittent Gating of Na+/H+ Antiporters in Single Native Bioluminescent Bacteria

  • First Published: 23 December 2022
Visualizing the Intermittent Gating of Na+/H+ Antiporters in Single Native Bioluminescent Bacteria**

We report the observation of the intermittent BL blinking of a single bioluminescent bacterium. This study not only demonstrated, for the first time, the intermittent gating dynamics of NhaA antiporters in single native bacteria without any genetic engineering or chemical labeling, but also opened the door for P. phosphoreum to serve as model bacteria for reporting the physiological and metabolic status with spontaneous BL emission.

Self-Assembly

Ultrasound-Directed Symmetry Breaking and Spin Filtering of Supramolecular Assemblies from only Achiral Building Blocks

  • First Published: 15 December 2022
Ultrasound-Directed Symmetry Breaking and Spin Filtering of Supramolecular Assemblies from only Achiral Building Blocks

Helical nanofibers have been prepared from exclusively achiral building blocks upon ultrasonication-induced morphology transformation. The as-made helical nanofibers show a more robust and repeatable control of the helical handedness compared with those generated using common chiral solvents. It was further verified that the helical nanofibers can act as a spin filter with a comparable spin polarization (45 %) at room temperature.

Cycloaddition Reactions | Hot Paper

Open Access

Chemodivergent, Regio- and Enantioselective Cycloaddition Reactions between 1,3-Dienes and Alkynes

  • First Published: 15 December 2022
Chemodivergent, Regio- and Enantioselective Cycloaddition Reactions between 1,3-Dienes and Alkynes

Reported herein are ligand controlled, chemodivergent [4+2] or [2+2] cycloaddition reactions between readily available 1,3-dienes and alkynes. These reactions, catalyzed by cationic CoI proceed with high regio- and enantioselectivies to give nearly enantiopure functionalized 1,4- cyclohexadienes or cyclobutenes from the same starting materials.

NIR Dyes

Charge-Segregated Stacking Structure with Anisotropic Electric Conductivity in NIR-Absorbing and Emitting Positively Charged π-Electronic Systems

  • First Published: 27 December 2022
Charge-Segregated Stacking Structure with Anisotropic Electric Conductivity in NIR-Absorbing and Emitting Positively Charged π-Electronic Systems

Ordered arrangements and resulting anion-dependent photophysical properties were observed in the dispersed- and solid-state ion pairs of squarylium-based π-electronic cation with an augmented dipole. A completely charge-segregated assembly was formed in the ion pair with a π-electronic anion, exhibiting solid-state photophysical properties and anisotropic electric conductivity according to the stacking structure.

Fluorescent Probes | Hot Paper

Open Access

Fluorogenic Granzyme A Substrates Enable Real-Time Imaging of Adaptive Immune Cell Activity

  • First Published: 23 December 2022
Fluorogenic Granzyme A Substrates Enable Real-Time Imaging of Adaptive Immune Cell Activity

We describe NIR fluorogenic substrates for granzyme A with rapid responses and enzyme sensitivity at physiological levels. We demonstrate that these probes can be used for real-time imaging of CTLs and NK cells in co-cultures with cancer cells and in ex vivo tissues, opening new avenues to monitor the functions of the immune system in the tumor microenvironment.

Lithium Batteries | Hot Paper

Open Access

High-Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential

  • First Published: 02 January 2023
High-Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential

Two cosolvents, MFSI and TFF, were synthesized and investigated for lithium metal batteries. Among the four different electrolytes, the TFF-containing electrolyte exhibited the highest coulombic efficiency of 99.59 %, which is due to the low redox potential of TFF promoting the anion reduction, leading to an inorganic SEI formation.

Li-Ion Batteries | Hot Paper

Non-Flammable Electrolyte Enables High-Voltage and Wide-Temperature Lithium-Ion Batteries with Fast Charging

  • First Published: 25 December 2022
Non-Flammable Electrolyte Enables High-Voltage and Wide-Temperature Lithium-Ion Batteries with Fast Charging

A novel non-flammable electrolyte that endows Li-ion battery with high voltage, wide temperature, and fast charging is developed. Moreover, a new solvation chemistry-derived dynamic interfacial model, involving the kinetic and thermodynamic properties of electrolyte components on the cathode and anode simultaneously, was presented for the first time to interpret such excellent performance and guide the electrolyte design at a molecular scale.

Li–S batteries

Cooperative Catalysis of Polysulfides in Lithium-Sulfur Batteries through Adsorption Competition by Tuning Cationic Geometric Configuration of Dual-active Sites in Spinel Oxides

  • First Published: 22 December 2022
Cooperative Catalysis of Polysulfides in Lithium-Sulfur Batteries through Adsorption Competition by Tuning Cationic Geometric Configuration of Dual-active Sites in Spinel Oxides

The charge, spin, and orbital topological regulation behind attractive physicochemical properties functions as a universal descriptor for determining the geometrical-site-dependent catalysis. By tuning cationic geometric configuration in spinel oxides, the lithium polysulfides (LiPSs) adsorption competition on Mn3+Oh−O−Co3+Td backbones is well leveraged to spark the cooperative catalysis of LiPSs in lithium-sulfur batteries.

Synthetic Methods

Open Access

Transition-Metal-Free Difunctionalization of Sulfur Nucleophiles

  • First Published: 22 December 2022
Transition-Metal-Free Difunctionalization of Sulfur Nucleophiles**

A transition-metal-free difunctionalization of bench-stable sulfur salts gives facile access to iodo-substituted sulfides using either diaryliodonium or vinyliodonium salts. The methodology was extended to one-pot syntheses of electron-rich thioanilines and efficient late-stage transformations of medicinally important compounds.

Biosensors

Electrochemical Cell-Free Biosensors for Antibody Detection

  • First Published: 19 December 2022
Electrochemical Cell-Free Biosensors for Antibody Detection

We demonstrate the sensitive, specific, selective, and multiplexed detection of different antibodies in blood serum using electrochemical cell-free biosensors. The platform is based on programmable antigen-conjugated gene circuits that, upon recognition of a target antibody, trigger the transcription of an RNA sequence consequently detected with a disposable electrochemical sensor.

Macrocyclic Photoswitches | Hot Paper

Reversible Handedness Inversion and Circularly Polarized Light Reflection Tuning in Self-Organized Helical Superstructures Using Visible-Light-Driven Macrocyclic Chiral Switches

  • First Published: 12 December 2022
Reversible Handedness Inversion and Circularly Polarized Light Reflection Tuning in Self-Organized Helical Superstructures Using Visible-Light-Driven Macrocyclic Chiral Switches

The synthesized macrocyclic chiral photoswitches are capable of reversible photoisomerization driven by visible light. The photoswitches show enhanced helical twisting power (HTP) in liquid crystals and diverse HTP changes upon photoisomerization. The photoswitches with shorter substituents enable visible-light-driven handedness inversion of the self-assembled helical superstructures.

NMR Spectroscopy | Hot Paper

Open Access

Pure Isotropic Proton NMR Spectra in Solids using Deep Learning

  • First Published: 23 December 2022
Pure Isotropic Proton NMR Spectra in Solids using Deep Learning

Machine learning provides a powerful and robust approach to remove broadening due to dipolar interactions in proton NMR spectra of solids.

2D Materials

Two-Dimensional Polymer Networks Locking on Inorganic Nanoparticles

  • First Published: 19 December 2022
Two-Dimensional Polymer Networks Locking on Inorganic Nanoparticles

A high-curvature two-dimensional (2D) polymerization is proposed to form a single-layer 2D polymer network as a non-contacting ligand on the surface of nanoparticles for their stabilization and functionalization. The 2D polymer network coated on nanoparticle surfaces can be turned into a non-contact ligand showing excellent shape retention and high nanoparticle-surface accessibility.

Dual-Atom Catalysis | Very Important Paper

Single-Atom or Dual-Atom in TiO2 Nanosheet: Which is the Better Choice for Electrocatalytic Urea Synthesis?

  • First Published: 30 November 2022
Single-Atom or Dual-Atom in TiO2 Nanosheet: Which is the Better Choice for Electrocatalytic Urea Synthesis?

Dual-atom Pd1Cu1 active center in Pd1Cu1−TiO2 is more favourable for producing urea, and experiences a C−N coupling pathway with a lower energy barrier as compared with single-atom Pd1 in Pd1−TiO2.

Cluster Catalysis | Very Important Paper

Reactivity and Recyclability of Ligand-Protected Metal Cluster Catalysts for CO2 Transformation

  • First Published: 22 December 2022
Reactivity and Recyclability of Ligand-Protected Metal Cluster Catalysts for CO2 Transformation

Ligand-protected metal clusters composed of silver, gold, and copper integrate the merits of homogeneous and heterogeneous catalysts and exhibit an excellent reactivity and recyclability for CO2 formylation with secondary amines. Fundamental insights are provided into the heterogeneously catalyzed reaction and design rules are presented for preparation of metal clusters with high stability and recyclability.

Platinum Drugs

Disruption of Zinc Homeostasis by a Novel Platinum(IV)-Terthiophene Complex for Antitumor Immunity

  • First Published: 22 December 2022
Disruption of Zinc Homeostasis by a Novel Platinum(IV)-Terthiophene Complex for Antitumor Immunity

We developed a novel cyclometalated PtIV-terthiophene complex as the first metal-based zinc homeostatic medicine that regulates zinc homeostasis to activate antitumor immunity.

Oxygen Reduction

Open Access

Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System

  • First Published: 20 December 2022
Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System**

Substituted manganese oxide nanoparticles, Mn3O4:M, were studied as a model system to generalize the electronic effect of redox-inactive substituents on the electrocatalytic activity of the oxides. The oxygen reduction activity of Mn3O4:M correlates with the enthalpy of formation of the binary MO oxide and the Lewis acidity of the M2+ site. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis.

Perovskite Solar Cells | Hot Paper

Rational Design of Ferroelectric 2D Perovskite for Improving the Efficiency of Flexible Perovskite Solar Cells Over 23 %

  • First Published: 29 December 2022
Rational Design of Ferroelectric 2D Perovskite for Improving the Efficiency of Flexible Perovskite Solar Cells Over 23 %

A ferroelectric two-dimensional (2D) perovskite has been designed based on a pyridine ring as the organic interlayer. Incorporation of the ferroelectric 2D material into 3D perovskite induces an increased built-in electric field and optimized perovskite crystallization, delivering an exceptional efficiency over 23 % for flexible perovskite solar cells.

Gas Separation | Hot Paper

Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions

  • First Published: 31 December 2022
Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions

Two highly robust microporous metal–organic frameworks with high ethane uptake and selectivity, ultrahigh water stability, high chemical stability, and low ethane/ethene adsorption enthalpy were designed and synthesized, which could realize one-step C2H4 purification from binary C2H6/C2H4 mixtures under both dry and humid conditions.

Photophysics

Thermodynamic Control of Intramolecular Singlet Fission and Exciton Transport in Linear Tetracene Oligomers

  • First Published: 28 December 2022
Thermodynamic Control of Intramolecular Singlet Fission and Exciton Transport in Linear Tetracene Oligomers

A series of newly synthesized homo- and hetero-tetracene (Tc) oligomers are presented. The molecular design strategy achieves efficient exciton transport in linear tetracene oligomers by promoting correlated triplet pair (TT) dissociation and controlling a sequential exciton trapping process by intramolecular singlet fission.

Bottlebrush Polymers

Circular Upcycling of Bottlebrush Thermosets

  • First Published: 30 December 2022
Circular Upcycling of Bottlebrush Thermosets

Built-in circularity can be achieved by integrating closed-loop recycling and upcycling in brush-like thermosets with dynamic crosslinks.

Dyes/Pigments

Helical β-isoindigo-Based Chromophores with B−O−B Bridge: Facile Synthesis and Tunable Near-Infrared Circularly Polarized Luminescence

  • First Published: 30 December 2022
Helical β-isoindigo-Based Chromophores with B−O−B Bridge: Facile Synthesis and Tunable Near-Infrared Circularly Polarized Luminescence

A study of a series of helical β-isoindigo-based B−O−B-bridged chromophores has shown that the bridge leads to distorted conformations. This results in the chromophores having excellent spectroscopic and chiroptical properties, such as tunable circularly polarized luminescence (CPL), with a high luminescence dissymmetry factor (glum) of 1.3×10−3 and a CPL brightness (BCPL) of 11.5 M−1 cm−1 in the near-infrared region observed for one of the compounds.

Boron Chemistry | Hot Paper

Site- and Stereoselective C(sp3)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

  • First Published: 29 December 2022
Site- and Stereoselective C(sp3)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

A combination of chiral bidentate boryl ligand (CBL) and iridium precursor was found effective in catalyzing carbamate-directed C(sp3)−H borylation of strained (hetero)cycloalkanols in a site- and stereoselective manner. This method features broad substrate scope (>50 examples), excellent site-selectivity, and high enantioselectivity (up to 95 % ee), providing a robust protocol for access to diverse, densely substituted (hetero)cycloalkanols.

Single-Atom Catalysis

Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

  • First Published: 27 December 2022
Tuning the CO2 Hydrogenation Selectivity of Rhodium Single-Atom Catalysts on Zirconium Dioxide with Alkali Ions

Doping alkali ions (e.g., Na) into Rh1/ZrO2 enables complete switching of the reaction product from CH4 to CO in CO2 hydrogenation over a broad temperature range. It was found that Na+ ions change the surface intermediate from HCOO* to COOH* and render the Rh1 atoms electron deficient with restrained H2 activation capability and weakened CO adsorption, thus cooperatively boosting CO formation.

CO2 Reduction

Mechanistic Elucidations of Highly Dispersed Metalloporphyrin Metal-Organic Framework Catalysts for CO2 Electroreduction

  • First Published: 30 December 2022
Mechanistic Elucidations of Highly Dispersed Metalloporphyrin Metal-Organic Framework Catalysts for CO2 Electroreduction

PCN-222(Fe), a metalloporphyrin-based metal–organic framework (MOF), was used for the CO2 electroreduction reaction. The proposed reaction mechanism necessitated catalyst weight loadings of 1 wt.% to mitigate obfuscations from mass transfer and in situ Raman spectroscopy confirmed the structural and reactive stability of the MOF under operating conditions.

Block Copolymers | Very Important Paper

An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

  • First Published: 28 December 2022
An Arbitrarily Regulated Monomer Sequence in Multi-Block Copolymer Synthesis by Frustrated Lewis Pairs

The combination of livingness, dual-initiation, and CSC feature of Lewis pair polymerization enabled the efficient synthesis of well-defined multi-block copolymers from monomer mixtures of methacrylate and acrylates in a one-pot process. Importantly, monomer sequence can be arbitrarily-regulated by changing the composition and adding order of the monomer mixtures.

Supramolecular Chemistry | Very Important Paper

Mechanical Training Enabled Reinforcement of Polyrotaxane-Containing Hydrogel

  • First Published: 30 December 2022
Mechanical Training Enabled Reinforcement of Polyrotaxane-Containing Hydrogel

A naphthotube-based polyrotaxane-containing hydrogel was constructed through one-pot photo-initiated copolymerization. Naphthotube can slide along the PEG chain upon repeated stretching. The slide motion further induces the zipping of adjacent polymer chains to form compact hydrogen bonded nanocrystalline domains through integrated hydrogen bonds, which enabled the hydrogel to achieve reinforcement.

Zn-Ion Batteries | Hot Paper

Constructing 2D Sandwich-like MOF/MXene Heterostructures for Durable and Fast Aqueous Zinc-Ion Batteries

  • First Published: 23 December 2022
Constructing 2D Sandwich-like MOF/MXene Heterostructures for Durable and Fast Aqueous Zinc-Ion Batteries

A MOF/MXene heterostructure, which exhibits a molecular-scale hybridized MOF (Cu-HHTP) and MX (V2CTx MXene) nanosheets, is successfully synthesized. The results show that the Zn2+ storage capability of such a 2D heterostructure is boosted by enhancing the structural stability, electrical conductivity, and the utilization of active sites.

Photocatalysis

Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy

  • First Published: 29 December 2022
Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy

The construction of CdS/pyrene-alt-difluorinated benzothiadiazole (PDB) inorganic/organic S-scheme heterojunction leads to efficient photocatalytic H2 production coupled with selective 1,2-diols oxidation. The interfacial S-scheme charge-transfer process was explored with transient absorption spectroscopy.

Post-translational Modification

Open Access

The Alarmone Diadenosine Tetraphosphate as a Cosubstrate for Protein AMPylation

  • First Published: 16 December 2022
The Alarmone Diadenosine Tetraphosphate as a Cosubstrate for Protein AMPylation

Ap4A was investigated for its potential applicability as a cosubstrate in AMPylation mediated by FICD, instead of the common cosubstrate ATP. Proficient AMPylation capability of Ap4A was observed, and new potential target proteins were found by chemical proteomics. Interestingly, AMPylation targets of FICD may differ depending on the cosubstrate.

Nitrate Reduction

Open Access

Single-entity Electrochemistry Unveils Dynamic Transformation during Tandem Catalysis of Cu2O and Co3O4 for Converting NO3 to NH3

  • First Published: 05 December 2022
Single-entity Electrochemistry Unveils Dynamic Transformation during Tandem Catalysis of Cu2O and Co3O4 for Converting NO3− to NH3

A rational catalyst design strategy is vital for a highly efficient conversion of NO3 to NH3. Cu2O+Co3O4 tandem catalyst exhibit a much higher NH3 yield rate than the single component alone. More importantly, we confirmed tandem catalysis by placing individual single Cu2O and Co3O4 on carbon nanoelectrode. Using single-entity electrochemistry and identical-location TEM we unveiled the dynamic transformation caused by tandem catalysis.

Photochemistry | Very Important Paper

Open Access

Blue-to-UVB Upconversion, Solvent Sensitization and Challenging Bond Activation Enabled by a Benzene-Based Annihilator

  • First Published: 18 November 2022
Blue-to-UVB Upconversion, Solvent Sensitization and Challenging Bond Activation Enabled by a Benzene-Based Annihilator

Blue-to-UVB photon upconversion (UC) enabled by a benzene-based annihilator is presented for the first time. The annihilator's unprecedented singlet-excited energy of 4.15 eV was successfully employed to activate inert carbonyls via a subsequent FRET energy transfer. This UC-FRET reaction scheme was directly monitored by laser techniques and exploited in lab-scale NMR experiments demonstrating its potential in light-to-chemical energy conversion.