• Issue

    Angewandte Chemie International Edition: Volume 61, Issue 13

    March 21, 2022

Cover Pictures

Free Access

Cover Picture: Solvent-Influenced Fragmentations in Free-Standing Three-Dimensional Covalent Organic Framework Membranes for Hydrophobicity Switching (Angew. Chem. Int. Ed. 13/2022)

  • First Published: 01 March 2022
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Can we tune the physicochemical properties of free-standing organic membranes without changing the building blocks or post-synthetic modifications? The Research Article (e202200905) by Dinesh Shetty et al. demonstrates a novel pre-synthetically controlled framework growth strategy to tune the hydrophobicity of 3D-Covalent Organic Framework (3D-COF) membranes. The hydrophobic 3D-COF membrane shows potential use for the demulsification of an oil–water mixture, a significant environmental and water reuse issue.

Free Access

Inside Cover: Real-time Observation of Structural Dynamics Triggering Excimer Formation in a Perylene Bisimide Folda-dimer by Ultrafast Time-Domain Raman Spectroscopy (Angew. Chem. Int. Ed. 13/2022)

  • First Published: 03 March 2022
Description unavailable

The excimer (a contraction of the excited-state dimer) is the most classical photoproduct which has been generally regarded as a trap site. In their Research Article (202114474), Hyungjun Kim, Frank Würthner, Dongho Kim and co-workers have captured the vibrational snapshots triggering the excimer formation and relaxation processes of the perylene bisimide folda-dimer using the ultrafast time-domain Raman spectroscopy. Understanding the mechanism of the excimer provides important criteria for designing the π-conjugated organic molecules.

Free Access

Inside Back Cover: Highly Enhanced Aromatics Selectivity by Coupling of Chloromethane and Carbon Monoxide over H-ZSM-5 (Angew. Chem. Int. Ed. 13/2022)

  • First Published: 01 March 2022
Description unavailable

The coupling of CH3Cl with CO over H-zeolites is an efficient reaction strategy for the transformation of methane into aromatics, which ensures the sustainable development of natural gas in an environmental pathway. In their Research Article (e202114953), Hongchao Liu, Wenliang Zhu, Zhongmin Liu, and co-workers report that high aromatics and BTX (benzene, toluene, and xylene) selectivity can be achieved with complete conversion of CH3Cl over HZSM-5, following a new aromatization mechanism.

Free Access

Back Cover: Halogen Bonding: A New Platform for Achieving Multi-Stimuli-Responsive Persistent Phosphorescence (Angew. Chem. Int. Ed. 13/2022)

  • First Published: 03 March 2022
Description unavailable

Halogen bonding is an effective tool in solid-state supramolecular chemistry to stabilize crystal structures. In their Research Article (e202200236), Zhengxu Cai and co-workers introduced intermolecular halogen bonding (CN⋅⋅⋅Br) into a host—guest room-temperature phosphorescence (RTP) system, achieving fluorescence—phosphorescence dual emission. The weak intermolecular interactions of the halogen bond are sensitive to external stimuli (heat, mechanical force and X-rays), realizing colorimetric multi-stimuli response behavior.

Frontispiece

Free Access

Frontispiece: Palladium-Catalyzed Tail-to-Tail Reductive Dimerization of Terminal Alkynes to 2,3-Dibranched Butadienes

  • First Published: 14 March 2022
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Homogeneous Catalysis The palladium-catalyzed tail-to-tail reductive dimerization of terminal alkynes to 2,3-dibranched butadienes is reported by Yang Li, Ming Bao et al. in their Communication (e202116870).

Graphical Abstract

Free Access

Graphical Abstract: Angew. Chem. Int. Ed. 13/2022

  • First Published: 14 March 2022

Introducing …

Free Access

Shuang Li

  • First Published: 18 January 2022
Description unavailable

The most important factor in the choice of my current research topic was catalysis, which is a real magic show that happens every day and everywhere in our life … I chose chemistry as a career because I can feel the real freedom in building things under different scales: nanometer scale, molecular scale, and even atomic scale …” Find out more about Shuang Li in her Introducing … Profile.

Free Access

Dinesh Shetty

  • First Published: 11 February 2022
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My favorite place on earth is my hometown (Koodlu, Karnataka) in India, a beautiful countryside village with loads of human values … I chose my current career path because it surprises me daily by tossing new challenges and excitements …” Find out more about Dinesh Shetty in his Introducing … Profile.

Highlights

Nanocomposites

Layered Biomimetic Composites from MXenes with Sequential Bridging

  • First Published: 19 January 2022
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Layered nanocomposites fabricated by techniques other than layer-by-layer assembly (e.g. vacuum-assisted filtration and blade coating) contain voids in their structure, which reduces their performance. Cheng and co-workers have now found that the problem of voids in Ti3C2Tx MXene composites can be solved by sequential bridging of MXEne platelets with sodium carboxymethyl cellulose combined with covalent bridging by borate ions.

Minireviews

Cyclophanes

Open Access

Planar Chirality: A Mine for Catalysis and Structure Discovery

  • First Published: 30 October 2021
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Although the benefits of molecules exhibiting planar chirality have recently been recognized in different areas of chemistry, the shortage of available catalytic methods for generating planar chirality has precluded their use. This Minireview aims to highlight the infancy of the area and serve as a source of inspiration for the design of unconventional methods for the generation of three-dimensional complexity from accessible simple/linear molecules.

Multivalency

Open Access

Significance of Receptor Mobility in Multivalent Binding on Lipid Membranes

  • First Published: 04 January 2022
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Multivalent membrane processes result in numerous receptors being coupled on a diffusive surface. As such, these binding mechanisms depend heavily on the intrinsic mobility on the cell membrane. The Minireview discusses the importance of mobility in multivalent binding, demonstrating that it is crucial for the deeper understanding of receptor interactions, and to guide the design of new generations of multivalent ligands.

Reviews

Biosensors

Open Access

Advances in the Sensing and Treatment of Wound Biofilms

  • First Published: 21 November 2021
Description unavailable

Wound biofilms are a challenging problem for modern medicine. Advances in the areas of sensors and reporters that can accurately detect early biofilm formation in the wound, and new materials to treat wound biofilms, offer promise for better detection and treatment. This review focuses on novel approaches to biofilm eradication and detection and compares them to conventional methods.

Communications

Alkyne Dimerization | Hot Paper

Palladium-Catalyzed Tail-to-Tail Reductive Dimerization of Terminal Alkynes to 2,3-Dibranched Butadienes

  • First Published: 01 February 2022
Description unavailable

The use of a combination of pivalic acid and para-toluenesulfonic acid proved successful in favoring the selective highly chemo- and regioselective tail-to-tail reductive dimerization of terminal alkynes over the competitive head-to-tail dimerization pathway. The target reaction, proposed to proceed via a cationic alkenyl palladium intermediate, presents a facile and straightforward approach for accessing 2,3-dibranched butadienes.

Uranium Extraction

In Situ Synthesis of Uranyl-Imprinted Nanocage for Selective Uranium Recovery from Seawater

  • First Published: 16 February 2021
Description unavailable

An adsorbent was fabricated by the in situ construction of a uranyl-imprinted nanostructure in a MOF material. Impressively, the adsorbent shows highly selective uranium extraction ability in natural seawater, which was attributed to the fitting coordination structure for uranyl.

Non-Canonical Amino Acids

Open Access

Genetic Encoding of Cyanopyridylalanine for In-Cell Protein Macrocyclization by the Nitrile–Aminothiol Click Reaction

  • First Published: 31 January 2022
Description unavailable

Genetic encoded cyanopyridylalanines are presented as convenient and highly selective reactive groups for in vivo functionalization, cyclization and stapling of polypeptides. The non-toxic compounds can be genetically incorporated into proteins with high yields and their biocompatible reaction with amino-thiol moieties proceeds under physiological conditions to near completion without requiring a catalyst.

Relay Catalysis

Enantioselective Cascade Annulation of α-Amino-ynones and Enals Enabled by Gold and Oxidative NHC Relay Catalysis

  • First Published: 13 January 2022
Description unavailable

An unprecedented system of gold and oxidative NHC relay catalysis was developed, which enables highly enantioselective cascade annulation between readily available α-amino-ynones with enals to afford pyrrole-fused lactones in high yield and excellent level of enantioselectivity. The lactone products could be readily converted to diverse densely functionalized pyrroles and pyrrolin-4-ones in high yields and diastereoselectivity.

Lithium Batteries | Hot Paper

A Facile Potential Hold Method for Fostering an Inorganic Solid-Electrolyte Interphase for Anode-Free Lithium-Metal Batteries

  • First Published: 18 January 2022
Description unavailable

A facile potential hold process fosters the growth of a more inorganic solid-electrolyte interphase (SEI) for anode-free lithium-metal batteries. Owing to the various decomposition potentials of the Li-solvation structures, salt anion-derived SEI was preferentially established on the current collector while reducing the components from organic solvents.

Catalysis in Flow

Continuous-Flow Synthesis of (R)-Tamsulosin Utilizing Sequential Heterogeneous Catalysis

  • First Published: 23 January 2022
Description unavailable

In a multistep continuous-flow synthesis of (R)-tamsulosin, three C−N bond formation/cleavage reactions with hydrogen gas over heterogeneous catalysts enabled the efficient construction of the key skeleton. Two different polysilane-modified Pd catalysts were developed for these transformations, which were followed by a deprotection step under homogeneous catalysis to provide tamsulosin in 60 % overall yield in a flow stream.

Catalytic Asymmetric Dearomatization | Hot Paper

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium-Catalyzed Asymmetric Dearomatization of Indoles

  • First Published: 25 January 2022
Description unavailable

A palladium-catalyzed intermolecular asymmetric spiroannulation of 2,3-disubstituted indoles with internal alkynes was developed for the efficient construction of indoline structures with a C2-quaternary stereocenter. A stereospecific aza-semipinacol rearrangement was achieved to afford diverse indolenine products bearing a C3-quaternary stereocenter.

Metal–Organic Frameworks | Very Important Paper

Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal–Organic Frameworks

  • First Published: 30 January 2022
Description unavailable

Charge shifting via pore partition: A nine-nitrogen ligand simultaneously enables pore-space partition (via three N's) and charge reallocation (via six N's), thereby paving the way for multi-modular assembly of a huge family of tunable anionic porous materials with much enhanced chemical stability and selective gas and vapor sorption.

Dynamic Covalent Chemistry

Dynamic Timing Control over Multicolor Molecular Emission by Temporal Chemical Locking

  • First Published: 24 January 2022
Description unavailable

Multicolor molecular emission is controlled in a dynamic timing manner by introducing a temporal chemical lock. The temporal life-time of the systems can be encoded by molecularly engineering the structural information.

Organic Frameworks | Hot Paper

Binary Solvent Regulated Architecture of Ultra-Microporous Hydrogen-Bonded Organic Frameworks with Tunable Polarization for Highly-Selective Gas Separation

  • First Published: 13 January 2022
Description unavailable

A series of ultra-microporous hydrogen-bonded organic frameworks (HOFs) with controlled open coplanar carboxyl oxygen atoms within the pores have been constructed through an adaptable binary solvent synthetic strategy. Activated HOFs with enhanced surface polarization show highly selective adsorption of CO2 over N2 based on differences of molecule polarizability.

Radicals

Open Access

Preparation of Primary and Secondary Dialkylmagnesiums by a Radical I/Mg-Exchange Reaction Using sBu2Mg in Toluene

  • First Published: 19 January 2022
Description unavailable

Primary and secondary dialkylmagnesium reagents were prepared in toluene by the reaction of sBu2Mg with alkyl iodides (25–40 °C, 1–4 h). Stereoconvergent I/Mg-exchanges were observed for secondary cyclohexyl iodides leading after quenching reactions to products with high enantio- and diastereoselectivity, including homo-aldol products. Mechanistic studies confirmed radical pathways for these exchanges.

Covalent Organic Frameworks | Hot Paper

Three-Dimensional Triptycene-Functionalized Covalent Organic Frameworks with hea Net for Hydrogen Adsorption

  • First Published: 24 January 2022
Description unavailable

3D COFs with a non-interpenetrated hea net, JUC-596 and JUC-597, are designed and successfully synthesized for the first time. Remarkably, JUC-596 exhibits an exceptional performance in H2 adsorption up to 305 cm3 g−1 (or 2.72 wt%) at 77 K and 1 bar, which is higher than previous benchmarks from porous organic polymers reported so far.

Polyesters

A Facile and Unprecedented Route to a Library of Thermostable Formaldehyde-Derived Polyesters: Highly Active and Selective Copolymerization of Cyclic Acetals and Anhydrides

  • First Published: 18 January 2022
Description unavailable

This work discloses the alternating copolymerization of cyclic acetals and anhydrides for the first time, using 5 cyclic acetals and 9 cyclic anhydrides to afford 45 unprecedented polyesters that can flow at ambient temperature.

Light-Emitting Didoes | Hot Paper

Phosphonate/Phosphine Oxide Dyad Additive for Efficient Perovskite Light-Emitting Diodes

  • First Published: 25 January 2022
Description unavailable

A two-in-one dyad additive combining phosphonate and phosphine oxide groups for efficient perovskite light-emitting diodes (PeLEDs) is demonstrated. Owing to its dual roles of passivating defects and enhancing carrier radiative recombination, quasi-two-dimensional green PeLEDs with maximum external quantum efficiency of 25.1 % is obtained.

Electrocatalysis | Very Important Paper

Anchoring Ionic Liquid in Copper Electrocatalyst for Improving CO2 Conversion to Ethylene

  • First Published: 25 January 2022
Description unavailable

The ionic liquid 1-butyl-3-methylimidazolium nitrate (BmimNO3) was anchored into Cu, through which the atomic coordination and electronic properties of Cu can be optimized to facilitate C−C coupling. This electrocatalyst can reduce CO2 to C2H4 with high selectivity. The Faradaic efficiency of C2H4 reaches 77.3 % at −1.49 V (vs. RHE) in KHCO3 aqueous solution using a H-type cell, much higher than that over pure Cu catalyst (31.2 %).

Water Harvesting | Very Important Paper

Polyzwitterionic Hydrogels for Efficient Atmospheric Water Harvesting

  • First Published: 28 January 2022
Description unavailable

A novel polyzwitterionic hydrogel with efficient atmospheric water harvesting is developed based on anti-polyelectrolyte effects. The as-prepared hydrogel could achieve 0.62 g g−1 water vapor sorption within 120 minutes at 30 % relative humidity and produce 5.87 L kg−1 freshwater per day. This tactful designed polyzwitterionic hydrogel provides new insight on how to fabricate efficient atmospheric water harvesting materials.

Covalent Organic Frameworks | Hot Paper

Gating Effects for Ion Transport in Three-Dimensional Functionalized Covalent Organic Frameworks

  • First Published: 24 January 2022
Description unavailable

Crown ether-functionalized 3D COFs can efficiently gate ion transport with an excellent gating ratio up to 23.6 are reported, which is among the highest values in metal ion-activated solid-state nanochannels reported so far.

Research Articles

NMR Spectroscopy | Hot Paper

A Cholesterol Dimer Stabilizes the Inactivated State of an Inward-Rectifier Potassium Channel

  • First Published: 05 January 2022
Description unavailable

The structure of a cholesterol dimer-inward rectifier (Kir) channel complex using solid-state NMR and simulated annealing calculations is solved. The identified cholesterol binding pocket is directly linked to the mechanism of cholesterol-mediated inactivation of Kir channels. This work is one of the most detailed structural-functional studies of cholesterol dimer-protein interactions within a biological membrane.

Theranostics

Coordinating the Mechanisms of Action of Ferroptosis and the Photothermal Effect for Cancer Theranostics

  • First Published: 21 December 2021
Description unavailable

A cancer theranostic nanomedicine (denoted as Cro-Fe@BSA) was designed by attentively considering the mechanisms of action of ferroptosis and the photothermal effect to promote maximum synergy of the therapeutic effects in combination therapy. The pH/GSH-responsive therapeutic and imaging characteristics of the Cro-Fe@BSA nanoparticles in the tumor enabled safe and reliable cancer theranostics.

Therapeutic Oligonucleotides | Hot Paper

Open Access

Engineering Enzyme-Cleavable Oligonucleotides by Automated Solid-Phase Incorporation of Cathepsin B Sensitive Dipeptide Linkers

  • First Published: 25 December 2021
Description unavailable

Cathepsin B-sensitive dipeptide phosphoramidites were developed for automated synthesis of enzyme-cleavable oligonucleotides. The enzymatic cleavage of Val-Ala-02 by cathepsin B is efficient in the context of single-stranded DNA, but is sterically hindered by double-stranded DNA and short hairpin loops. The design of Val-Ala-Chalcone allows the construction of oligonucleotide–drug conjugates which release their small-molecule payload after enzymatic cleavage.

Homogeneous Catalysis | Hot Paper

Mapping Ambiphile Reactivity Trends in the Anti-(Hetero)annulation of Non-Conjugated Alkenes via PdII/PdIV Catalysis

  • First Published: 10 January 2022
Description unavailable

A method to access 5-, 6- and 7-membered carbo- and heterocycles from non-conjugated alkenyl amides and ambiphilic organohalides is described. Under PdII/PdIV catalysis, this [n+2] annulation proceeds in an anti-selective fashion and tolerates a wide array of ambiphiles, which are systematically benchmarked with respect to nucleophile identity, electrophile identity, and product ring-size. Otherwise unreactive ambiphilic ortho-haloacetophenones can be activated using an amine co-catalyst.

Organic Semiconductors | Very Important Paper

Open Access

Real-time Observation of Structural Dynamics Triggering Excimer Formation in a Perylene Bisimide Folda-dimer by Ultrafast Time-Domain Raman Spectroscopy

  • First Published: 26 December 2021
Description unavailable

The term “excimer”, a contraction of an excited dimer, is the most classical photoproduct in organic materials. In this work, vibrational snapshots showing ultrafast structural dynamics triggering the excimer formation and its relaxation are presented based on ultrafast time-domain Raman spectroscopy. It is demonstrated that interchromophore vibrational modes are related to perturbing the excited-state potential surface of a dimer stack.

Heterogeneous Catalysis | Very Important Paper

Highly Enhanced Aromatics Selectivity by Coupling of Chloromethane and Carbon Monoxide over H-ZSM-5

  • First Published: 01 February 2022
Description unavailable

A reaction strategy for the transformation of methane into aromatics by coupling of CH3Cl with CO over H-zeolites is presented, which achieved 82.2 % aromatic selectivity with ca. 60 % BTX (benzene, toluene, and xylene) selectivity over HZSM-5. 2,3-Dimethyl-2-cyclopentene-1-one is detected as an intermediate generated from acetyl group and olefins resulting in a new aromatization.

Antimicrobial Peptides

Open Access

A Multiplexed Cell-Free Assay to Screen for Antimicrobial Peptides in Double Emulsion Droplets

  • First Published: 06 January 2022
Description unavailable

A novel microfluidic system for the cell-free production and screening of antimicrobial peptides for their membrane specificity is introduced. On the device, the peptides are cell-free produced within water-in-oil-in-water double emulsion droplets. Within each droplet, the peptides can interact with different liposomes, generating a membrane-specific fluorescent signal. The droplets can be analyzed via fluorescence microscopy of flow cytometry.

Mechanochemical Synthesis

Metal-Catalyzed Organic Reactions by Resonant Acoustic Mixing

  • First Published: 20 January 2022
Description unavailable

Resonant Acoustic Mixing (RAM) enables mechanochemical organic synthesis that avoids milling or crushing media, as well as bulk solvents. The RAM methodology enables significant simplification and improvement of mechanochemical olefin metathesis, the first mechanochemical strategy for ene-yne metathesis, and permits the direct, 200-fold scaling-up of the mechanochemical synthesis of pharmaceutically active sulfonylureas, without any significant changes to reaction conditions or conversion.

Electrocatalysis | Hot Paper

Open Access

Interfacial Atom-Substitution Engineered Transition-Metal Hydroxide Nanofibers with High-Valence Fe for Efficient Electrochemical Water Oxidation

  • First Published: 22 December 2021
Description unavailable

An electrocatalytic oxygen-evolving NiFeV nanofiber was synthesized by an interfacial atom-substitution strategy to boost the activity of the NiFe centers. The electronic structure analyses suggest that the NiFeV nanofiber exhibits abundant high-valence Fe via a charge transfer from Fe to V. The reported substitutional growth strategy offers an effective and new pathway for the design of efficient and durable non-noble metal-based oxygen evolution reaction (OER) catalysts.

Thin Films | Hot Paper

Open Access

Electrochemical Deposition of a Single-Crystalline Nanorod Polycyclic Aromatic Hydrocarbon Film with Efficient Charge and Exciton Transport

  • First Published: 20 December 2021
Description unavailable

Electrochemical film deposition of a single-crystalline polycyclic aromatic hydrocarbon on electrodes, with synthetically controlled crystal structure, film thickness, and crystal orientations is reported. The film supports exceptionally efficient migration of both charges and excitons, with a free carrier mobility over 30 cm2 V−1 s−1, a low exciton binding energy of 118.5 meV, and a remarkable exciton diffusion length of 45 nm.

Halogen Bonding

“Click”-Like η6-Metalation/Demetalation of Aryl Iodides as a Means of Turning “ON/OFF” Halogen Bond Donor Functionality

  • First Published: 18 January 2022
Description unavailable

Click On! η6-Coordination of cationic cyclopentadienylruthenium(II) moieties is demonstrated to be a convenient, quantitative method for the click-like activation of aryl iodides as halogen bond donors. Photochemical demetalation using violet LEDs in MeCN returns the metal to its starting material form and supresses halogen bonding functionality. The cycle provides a reversible “ON/OFF” switch for controlling the halogen bond donor strength of aryl iodides.

Li-Metal Batteries | Very Important Paper

Quantification of the Dynamic Interface Evolution in High-Efficiency Working Li-Metal Batteries

  • First Published: 23 December 2021
Description unavailable

The fundamental interplay among Li dynamic loss behavior, electrolyte composition, and the structure of the solid electrolyte interphase (SEI) layer was quantitatively elucidated. The actual dominant form in inactive Li loss is determined by the relative growth rates of dead Li0 and SEI Li+ as the anode interface undergoes processive evolution during cycling. The mechanistic studies shed fresh light on the interfacial dynamics of the Li-metal anode.

Perovskites | Hot Paper

Open Access

Interfacial Chemistry Triggers Ultrafast Radiative Recombination in Metal Halide Perovskites

  • First Published: 23 January 2022
Description unavailable

An interfacial chemistry strategy is developed to dramatically increase radiative recombination of perovskites. The oxide-bonded perovskite has a large exciton binding energy and a high localized density of electronic state, exhibiting an unprecedented 5000 fold increase in the radiative recombination rate. The enormously enhanced radiative recombination promises to significantly promote the perovskite optoelectronic performance.

DNA Nanotechnology | Hot Paper

Finite Assembly of Three-Dimensional DNA Hierarchical Nanoarchitectures through Orthogonal and Directional Bonding

  • First Published: 30 January 2022
Description unavailable

Establishing robust orthogonal and directional bonding lays the foundation for the construction of finite DNA origami superstructures with complex shapes. By employing a twelve-valence hexagonal prism DNA origami as the building block, versatile superstructures were obtained from different combinations of building blocks with appropriate valences. All of these superstructures are fully addressable and could guide the assembly of guest molecules to produce functional devices.

Artificial Enzymes

Controlled Uptake of an Iridium Complex inside Engineered apo-Ferritin Nanocages: Study of Structure and Catalysis

  • First Published: 10 January 2022
Description unavailable

A stable hybrid bio-nanocage with selective immobilization of an iridium complex inside the self-assembly protein, ferritin has been developed. These hybrid bio-catalysts reduce substituted acetophenones into the corresponding chiral alcohols with high enantioselectivity.

Data Storage | Hot Paper

Rewritable Macromolecular Data Storage with Automated Read-out

  • First Published: 01 February 2022
Description unavailable

The rewriting of information stored on synthetic macromolecules is achieved via the introduction of an editable position tag. The automated read-out is facilitated by making use of an algorithm that is able to decode large portions of macromolecular information without interference from the operator.

Computational Chemistry

The Role of Copper Salts and O2 in the Mechanism of C≡N Bond Activation for Facilitating Nitrogen Transfer Reactions

  • First Published: 19 January 2022
Description unavailable

A detailed theoretical study on the intricate mechanism and electron transfer landscape of oxygen-assisted copper-promoted formation of aryl nitrile species starting from aryl aldehyde. In this reaction the major driving force is the redox cycle of the copper center (CuII/CuI), which acts as the electron source and sink whenever necessary along the course of reaction.

Sodium-Ion Batteries | Hot Paper

Sodium-Ion Battery with a Wide Operation-Temperature Range from −70 to 100 °C

  • First Published: 19 January 2022
Description unavailable

A wide-temperature range sodium-ion battery (SIB), which involves a Bi anode, a NFPP@C cathode and a diglyme-based electrolyte is successfully fabricated. Owing to the solvent co-intercalation mechanism of the Bi anode, the high Na+ diffusion coefficient of the NFPP@C cathode at low temperature and the electrolyte with a high boiling point and low freezing point, the prepared SIB can operate in a wide temperature range from −70 to 100 °C.

Metal–Organic Frameworks | Hot Paper

Dehydrated UiO-66(SH)2: The Zr−O Cluster and Its Photocatalytic Role Mimicking the Biological Nitrogen Fixation

  • First Published: 26 January 2022
Description unavailable

A dehydrated Zr-based MOF, UiO-66(SH)2, was found to show efficient conversion of N2 into NH3 under visible light. The revealed synergetic action of the photoelectron supported by the proton was analogous to that in molybdenum nitrogenase, however, with characteristic μ-N−Zr type interactions inside the [Zr6O6] cluster, which sheds new light on understanding the mechanism of nitrogenase.

Olefin Metathesis

Open Access

Hydrogen Bonding Networks Enable Brønsted Acid-Catalyzed Carbonyl-Olefin Metathesis

  • First Published: 05 January 2022
Description unavailable

H-bonding network: Hexafluoroisopropanol (HFIP) can act as a hydrogen-bond donor to enhance the catalytic efficiency of simple Brønsted acid catalysts in carbonyl-olefin metathesis reactions by stabilization of all transition states and intermediates along the reaction pathway.

Asymmetric Catalysis | Hot Paper

Copper(I)-Catalyzed Asymmetric Synthesis of P-Chiral Aminophosphinites

  • First Published: 25 January 2022
Description unavailable

A copper(I)-catalyzed asymmetric synthesis of P-chiral aminophosphinites with esters of hydroxylamines is achieved by means of the dynamic kinetic transformation of unsymmetrical diarylphosphines. A two-electron redox process is proposed for this reaction based on mechanistic studies.

Biomass | Hot Paper

Electrochemical Hydrogenation of Furfural in Aqueous Acetic Acid Media with Enhanced 2-Methylfuran Selectivity Using CuPd Bimetallic Catalysts

  • First Published: 18 January 2022
Description unavailable

Incorporation of Pd enhanced the selectivity of Cu catalysts for the electrochemical hydrogenation of furfural to 2-methylfuran in an aqueous 0.1 M acidic acid solution. The origin of the superior performance was revealed by in situ surface enhanced Raman spectroscopic and kinetic isotopic measurements and density functional theory calculations.

Organic Phosphorescence | Very Important Paper

Halogen Bonding: A New Platform for Achieving Multi-Stimuli-Responsive Persistent Phosphorescence

  • First Published: 31 January 2022
Description unavailable

Intermolecular halogen bonding (CN⋅⋅⋅Br) was introduced into the host–guest room-temperature phosphorescence (RTP) system, achieving fluorescence–phosphorescence dual-emission. The weak intermolecular interactions of the halogen bond are sensitive to external stimuli (heat, mechanical force and X-rays), realizing the colorimetric multi-stimuli response behaviors.

Antitumor Agents

Ferrocene-Containing Nucleic Acid-Based Energy-Storage Nanoagent for Continuously Photo-Induced Oxidative Stress Amplification

  • First Published: 22 January 2022
Description unavailable

The siRNA-aptamer-ferrocene modified persistent luminescence nanoparticle (siRNA-ApFe-PLNP) was designed as an energy-storage nanoagent to achieve continuous amplification of oxidative stress after photo-activation, eliminating the need for constant light irradiation and further avoiding the photo-induced tissue damage.

COF Membranes | Hot Paper

Open Access

Solvent-Influenced Fragmentations in Free-Standing Three-Dimensional Covalent Organic Framework Membranes for Hydrophobicity Switching

  • First Published: 23 January 2022
Description unavailable

A novel pre-synthetically controlled framework growth strategy to tune the hydrophobicity of the 3D-COF membranes without changing the building blocks or post-synthetic modifications is demonstrated. The hydrophobic 3D-COF membrane was utilized for the demulsification of an oil–water mixture.

Amidation | Hot Paper

Mapping Dual-Base-Enabled Nickel-Catalyzed Aryl Amidations: Application in the Synthesis of 4-Quinolones

  • First Published: 27 January 2022
Description unavailable

A nickel-catalyzed C−N cross-coupling of amides with 2′-(pseudo)halide-substituted acetophenones enabled the synthesis of sought-after 4-quinolones. The use of a new pre-catalyst supported by PAd2-DalPhos in combination with a DBU/NaTFA dual-base system, along with a thorough mechanistic investigation led to a successful demonstration of room-temperature amide cross-couplings.

Surface Chemistry

Reversible Self-Assembly of an N-Heterocyclic Carbene on Metal Surfaces

  • First Published: 05 January 2022
Description unavailable

The reversible self-assembly of an N-heterocyclic carbene mediated by conformational switching can be tuned via controllable experimental conditions, leaving behind different largely ordered structures. Such method provides a new alternative and convenient method to influence the self-assembled structure of NHC-metal monolayers, a still missing but essential tool towards catalytic applications.

Low-Valent Complexes

Open Access

Calix[4]pyrrolato Stannate(II): A Tetraamido Tin(II) Dianion and Strong Metal-Centered σ-Donor

  • First Published: 12 January 2022
Description unavailable

The macrocyclic calix[4]pyrrole enables the synthesis of the first tetraamido tin(II) dianion. The compound is a very strong metal-centered σ-donor with a Tolman electronic parameter (TEP) value exceeding that of carbenes and electron-rich phosphines. The coordinative and nucleophilic features are demonstrated with transition metals and organic substrates.

Enzyme Catalysis | Hot Paper

Open Access

Mechanism of the Bifunctional Multiple Product Sesterterpene Synthase AcAS from Aspergillus calidoustus

  • First Published: 24 January 2022
Description unavailable

A sesterterpene synthase from Aspergillus calidoustus was characterised that produces calidoustene, a compound with a new skeleton, besides five known compounds. A deep mechanistic investigation through isotopic labelling experiments, site-directed mutagenesis and DFT calculations is presented. The substrate analog 8-hydroxy-FPP was converted into several oxygenated terpenoids.

Organic Photoswitch

Open Access

A DNA-Based Two-Component Excitonic Switch Utilizing High-Performance Diarylethenes

  • First Published: 25 January 2022
Description unavailable

Doubly methylated diarylethenes derived from 2′-deoxyuridine are reported with high thermal stability, fatigue resistance, and fluorogenicity. With these, an all-optical excitonic switch consisting of two oligonucleotides has been designed: one containing the fluorogenic diarylethene as a fluorescence donor and the other a tricyclic cytidine (tC) as acceptor, which together form an efficient conditional Förster-Resonance-Energy-Transfer pair.