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Proteolysis‐targeting chimeras (PROTACs) have accelerated drug development; however, some challenges still exist owing to their lack of tumor selectivity and on‐demand protein degradation. Here, we developed a miRNA‐initiated assembled pre‐PROTAC (miRiaTAC) platform that enables the on‐demand activation and termination of target degradation in a cell type‐specific manner. Using miRNA‐21 as a model, we engineered DNA hairpins labeled with JQ‐1 and pomalidomide and facilitated the modular assembly of DNA‐encoded pre‐PROTACs through a hybridization chain reaction. This configuration promoted the selective polyubiquitination and degradation of BRD4 upon miR‐21 initiation, highlighting significant tumor selectivity and minimal systemic toxicity. Furthermore, the platform incorporates photolabile groups, enabling the precise optical control of pre‐PROTACs during DNA assembly/disassembly, mitigating the risk of excessive protein degradation. Additionally, by introducing a secondary ligand targeting CDK6, these pre‐PROTACs were used as a modular scaffold for the programmable assembly of active miRiaTACs containing two different warheads in exact stoichiometry, enabling orthogonal multitarget degradation. The integration of near‐infrared light‐mediated photodynamic therapy through an upconversion nanosystem further enhanced the efficacy of the platform with potent in vivo anticancer activity. We anticipate that miRiaTAC represents a significant intersection between dynamic DNA nanotechnology and PROTAC, potentially expanding the versatility of PROTAC toolkit for cancer therapy. [ABSTRACT FROM AUTHOR]

In animals, limiting oxygen upregulates the hypoxia‐inducible factor (HIF) and promotes a metabolic shift towards glycolysis. Factor inhibiting HIF (FIH) is an asparaginyl hydroxylase that regulates HIF function by reducing its interaction with histone acetyl transferases. HIF levels are negatively regulated by the HIF prolyl hydroxylases (PHDs) which, like FIH, are 2‐oxoglutarate (2OG) oxygenases. Genetic loss of FIH promotes both glycolysis and aerobic metabolism. FIH has multiple non‐HIF substrates making it challenging to connect its biochemistry with physiology. A structure–mechanism guided approach identified a highly potent in vivo active FIH inhibitor, ZG‐2291, the binding of which promotes a conformational flip of a catalytically important tyrosine, enabling the selective inhibition of FIH over other Jumonji C subfamily 2OG oxygenases. Consistent with genetic studies, ZG‐2291 promotes thermogenesis and ameliorates symptoms of obesity and metabolic dysfunction in ob/ob mice. The results reveal ZG‐2291 as a useful probe for the physiological functions of FIH and identify FIH inhibition as a promising strategy for obesity treatment. [ABSTRACT FROM AUTHOR]

Efficient synthesis of H2O2 via photocatalytic oxygen reduction without sacrificial agents is challenging due to inadequate proton supply from water and difficulty in maintaining O−O bond during O2 activation. Herein, we developed a straightforward strategy involving a proton‐rich hydrogel cross‐linked by metal ions [M(n)], which is designed to facilitate the selective production of H2O2 through proton relay and metal ion‐assisted detachment of crucial intermediates. The hydrogel comprises CdS/graphene and alginate cross‐linked by metal ions via O=C−O−M(n) bonds. Efficient O2 reduction and hydrogenation occurred, benefitting from the collaboration between proton‐rich alginate and the photocatalytically active CdS/graphene. Meanwhile, the O=C−O−M(n) bonds enhance the electron density of α‐carbon sites on graphene, crucial for O2 activation and *OOH intermediate detachment, preventing deeper O−O bond cleavage. The role of metal ions in promoting *OOH desorption was demonstrated through Lewis acidity‐dependent activity, with Y(III) having the highest activity, followed by Lu(III), La(III), and Ca(II). [ABSTRACT FROM AUTHOR]

How to achieve CO2 electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal‐organic cages with multiple metal sites, tunable active centers, and well‐defined microenvironments may provide a promising catalyst model. Here, we report self‐assembly of Ag4L4 type cuboctahedral cages from coordination dynamic Ag+ ion and triangular imidazolyl ligand 1,3,5‐tris(1‐benzylbenzimidazol‐2‐yl) benzene (Ag‐MOC‐X, X=NO3, ClO4, BF4) via anion template effect. Notably, Ag‐MOC‐NO3 achieves the highest CO faradaic efficiency in pH‐universal electrolytes of 86.1 % (acidic), 94.1 % (neutral) and 95.3 % (alkaline), much higher than those of Ag‐MOC‐ClO4 and Ag‐MOC‐BF4 with just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation of vital intermediate *COOH for CO2‐to‐CO conversion. The density functional theory calculations suggest that the adsorption of CO2 on unsaturated Ag‐site is stabilized by C−H⋅⋅⋅O hydrogen‐bonding of CO2 in a microenvironment surrounded by three benzimidazole rings, and the activation of CO2 is dependent on the coordination dynamics of Ag‐centers modulated by the hosted anions through Ag⋅⋅⋅X interactions. This work offers a supramolecular electrocatalytic strategy based on Ag‐coordination geometry and host–guest interaction regulation of MOCs as high‐efficient electrocatalysts for CO2 reduction to CO which is a key intermediate in chemical industry process. [ABSTRACT FROM AUTHOR]

Recycling of carbon fiber‐reinforced polymer composites (CFRCs) based on thermosetting plastics is difficult. In the present study, high‐performance CFRCs are fabricated through complexation of aromatic pinacol‐cross‐linked polyurethane (PU−AP) thermosets with carbon fiber (CF) cloths. PU−AP thermosets exhibit a breaking strength of 95.5 MPa and toughness of 473.6 MJ m−3 and contain abundant hydrogen‐bonding groups, which can have strong adhesion with CFs. Because of the high interfacial adhesion between CF cloths and PU−AP thermosets and high toughness of PU−AP thermosets, CF/PU−AP composites possess a high tensile strength of >870 MPa. Upon heating in N,N‐dimethylacetamide (DMAc) at 100 °C, the aromatic pinacols in the CF/PU−AP composites can be cleaved, generating non‐destructive CF cloths and linear polymers that can be converted to high‐performance elastomers. The elastomers are mechanically robust, healable, reprocessable, and damage‐resistant with an extremely high tensile strength of 74.2 MPa and fracture energy of 149.6 kJ m−2. As a result, dissociation of CF/PU−AP composites enables the recovery of reusable CF cloths and high‐performance elastomers, thus realizing the upcycling of CF/PU−AP composites. [ABSTRACT FROM AUTHOR]

Cytisine (CTS) is a useful medicine for treating nervous disorders and smoking addiction, and exploring a convenient method to detect CTS is of great significance for long‐term/home medication to avoid the risk of poisoning, but it is full of challenges. Here, a modified metal–organic framework sensor Tb@Zn‐TDA‐80 with dual emission centers was prepared using a post‐modified luminescence center strategy. The obtained Tb@Zn‐TDA‐80 can serve as a CTS sensor with high sensitivity and selectivity. To achieve portable detection, Tb@Zn‐TDA‐80 was further fabricated as a membrane sensor, M−Tb@Zn‐TDA‐80, which displayed an obvious CTS‐responsive color change by simply dropping a CTS solution onto its surface. Benefiting from this unique functionality, M−Tb@Zn‐TDA‐80 successfully realized the visual detection and quantitative monitoring of CTS in the range of 5.26–52.6 mM by simply scanning the color with a smartphone. The results of nuclear magnetic resonance spectroscopy and theoretical computation illustrated that the high sensing efficiency of Tb@Zn‐TDA‐80 for CTS was attributed to the N−H⋅⋅⋅π and π⋅⋅⋅π interactions between the ligand and CTS. And luminescence quenching may result from the intramolecular charge transfer. This study provides a convenient method for ensuring long‐term medication safety at home. [ABSTRACT FROM AUTHOR]

Luban locks with mortise and tenon structure have structural diversity and architectural stability, and it is extremely challenging to synthesize Luban lock‐like structures at the molecular level. In this work, we report the cocrystallization of two structurally related atom‐precise fcc silver nanoclusters Ag110(SPhF)48(PPh3)12 (Ag110) and Ag14(μ6‐S)(SPhF)12(PPh3)8 (Ag14). It is worth noting that the Ag110 cluster is the first compound to simulate the complex Luban lock structure at the molecular level. Meanwhile, Ag110 is the largest known fcc‐based silver nanocluster, so far, there is no precedent for fcc silver nanocluster with more than 100 silver atoms. DFT calculations show that Ag110 is a 58‐electron superatom with an electronically closed shell1S21P61D102S21F142P61G18. Ag110⋅Ag14 can rapidly catalyze the reduction of 4‐nitrophenol within 4 minutes. In addition, Ag110 presents clear structural evidence to reveal the critical size and mechanism of the transformation of metal core from fcc stacking to quasi‐spherical superatom. This research work provides an important structural model for studying the nucleation mechanism and structural assembly of silver nanoclusters. [ABSTRACT FROM AUTHOR]

Although closed‐loop recycling of dynamic covalent bond‐based plastics does not require catalysts, their mechanical strength and chemical stability remain a major concern. In this study, closed‐loop recyclable poly(aryl imine) (PAI) plastics with high mechanical strength and excellent chemical resistance are fabricated by copolymerizing aromatic amines and aromatic aldehydes through dynamic imine bonds. The resulting PAI plastic with a tensile strength of 58.2 MPa exhibits excellent chemical resistance and mechanical stability in acidic and basic aqueous solutions and various organic solvents. The PAI plastics can be depolymerized in a mixed solvent of tetrahydrofuran (THF)/HCl aqueous solution through the dissociation of imine bonds, and the monomers can be facilely recovered with high purity and isolated yields due to the solubility difference between the aromatic amines and aromatic aldehydes in selective solvents. The efficient closed‐loop recycling of the PAI plastic can also be realized through monomer conversion because the hydrolysis of the aromatic aldehydes generates aromatic amines. The recovered monomers can be used to re‐fabricate original PAI plastics. This PAI plastic can be selectively recovered from complicated mixed polymer waste streams due to the mild depolymerization conditions of the PAI plastic and its high stability in most organic solvents. [ABSTRACT FROM AUTHOR]

Inorganic Bi‐based perovskites have shown great potential in X‐ray detection for their large absorption to X‐rays, diverse low‐dimensional structures, and eco‐friendliness without toxic metals. However, they suffer from poor carrier transport properties compared to Pb‐based perovskites. Here, we propose a mixed‐halogen strategy to tune the structural dimensions and optoelectronic properties of Cs3Bi2I9−nBrn (0≤n≤9). Ten centimeter‐sized single crystals are successfully grown by the Bridgman technique. Upon doping bromine to zero‐dimensional Cs3Bi2I9, the crystal transforms into a two‐dimensional structure as the bromine content reaches Cs3Bi2I8Br. Correspondingly, the optoelectronic properties are adjusted. Among these crystals, Cs3Bi2I8Br exhibits negligible ion migration, moderate resistivity, and the best carrier transport capability. The sensitivities in 100 keV hard X‐ray detection are 1.33×104 and 1.74×104 μC Gyair−1 cm−2 at room temperature and 75 °C, respectively, which are the highest among all reported bismuth perovskites. Moreover, the lowest detection limit of 28.6 nGyair s−1 and ultralow dark current drift of 9.12×10−9 nA cm−1 s−1 V−1 are obtained owing to the high ionic activation energy. Our work demonstrates that Br incorporation is an effective strategy to enhance the X‐ray detection performance by tuning the dimensional and optoelectronic properties. [ABSTRACT FROM AUTHOR]

Cuproptosis is a new form of programmed cell death and exhibits enormous potential in cancer treatment. However, reducing the undesirable Cu ion release in normal tissue and maximizing the copper‐induced therapeutic effect in cancer sites are two main challenges. In this study, we constructed a photothermally triggered nanoplatform (Au@MSN‐Cu/PEG/DSF) to realize on‐demand delivery for synergistic therapy. The released disulfiram (DSF) chelated with Cu2+ in situ to generate highly cytotoxic bis(diethyldithiocarbamate)copper (CuET), causing cell apoptosis, and the formed Cu+ species promoted toxic mitochondrial protein aggregation, leading to cell cuproptosis. Synergistic with photothermal therapy, Au@MSN‐Cu/PEG/DSF could effectively kill tumor cells and inhibit tumor growth (inhibition rate up to 80.1 %). These results provide a promising perspective for potential cancer treatment based on cuproptosis, and may also inspire the design of advanced nano‐therapeutic platforms. [ABSTRACT FROM AUTHOR]

The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual‐metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN6 moieties with double‐N‐bridged adjacent metal‐N4 clusters decorated on a nitrogen‐doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ gmetal−1 ⋅ h−1) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so‐called formate pathway with the C−H dissociation of HCOO* as the rate‐determining step. Theoretical calculations reveal that Cu in the CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d‐band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier. [ABSTRACT FROM AUTHOR]

Programmable assembly of gold nanoparticle superstructures with precise spatial arrangement has drawn much attention for their unique characteristics in plasmonics and biomedicine. Bio‐inspired methods have already provided programmable, molecular approaches to direct AuNP assemblies using biopolymers. The existing methods, however, predominantly use DNA as scaffolds to directly guide the AuNP interactions to produce intended superstructures. New paradigms for regulating AuNP assembly will greatly enrich the toolbox for DNA‐directed AuNP manipulation and fabrication. Here, we developed a strategy of using a spatially programmable enzymatic nanorobot arm to modulate anisotropic DNA surface modifications and assembly of AuNPs. Through spatial controls of the proximity of the reactants, the locations of the modifications were precisely regulated. We demonstrated the control of the modifications on a single 15 nm AuNP, as well as on a rectangular DNA origami platform, to direct unique anisotropic AuNP assemblies. This method adds an alternative enzymatic manipulation to DNA‐directed AuNP superstructure assembly. [ABSTRACT FROM AUTHOR]

Thermocatalysis of CO2 into high valuable products is an efficient and green method for mitigating global warming and other environmental problems, of which Noble‐metal‐free metal–organic frameworks (MOFs) are one of the most promising heterogeneous catalysts for CO2 thermocatalysis, and many excellent researches have been published. Hence, this review focuses on the valuable products obtained from various CO2 conversion reactions catalyzed by noble‐metal‐free MOFs, such as cyclic carbonates, oxazolidinones, carboxylic acids, N‐phenylformamide, methanol, ethanol, and methane. We classified these published references according to the types of products, and analyzed the methods for improving the catalytic efficiency of MOFs in CO2 reaction. The advantages of using noble‐metal‐free MOF catalysts for CO2 conversion were also discussed along the text. This review concludes with future perspectives on the challenges to be addressed and potential research directions. We believe that this review will be helpful to readers and attract more scientists to join the topic of CO2 conversion. [ABSTRACT FROM AUTHOR]

Self‐renewal and differentiation of embryonic stem cells (ESCs) are influenced by protein O‐linked β‐N‐acetylglucosamine (O‐GlcNAc) modification, but the underlying mechanism remains incompletely understood. Herein, we report the identification of 979 O‐GlcNAcylated proteins and 1340 modification sites in mouse ESCs (mESCs) by using a chemoproteomics method. In addition to OCT4 and SOX2, the third core pluripotency transcription factor (PTF) NANOG was found to be modified and functionally regulated by O‐GlcNAc. Upon differentiation along the neuronal lineage, the O‐GlcNAc stoichiometry at 123 sites of 83 proteins—several of which were PTFs—was found to decline. Transcriptomic profiling reveals 2456 differentially expressed genes responsive to OGT inhibition during differentiation, of which 901 are target genes of core PTFs. By acting on the core PTF network, suppression of O‐GlcNAcylation upregulates neuron‐related genes, thus contributing to mESC fate determination. [ABSTRACT FROM AUTHOR]

Here we report the first palladium‐catalyzed asymmetric hydrogenolysis of readily available aryl triflates via desymmetrization and kinetic resolution for facile construction of axially chiral biaryl scaffolds with excellent enantioselectivities and s selectivity factors. The axially chiral monophosphine ligands could be prepared from these chiral biaryl compounds and were further applied to palladium‐catalyzed asymmetric allylic alkylation with excellent ee values and high branched and linear ratio, which demonstrated the potential utility of this methodology. [ABSTRACT FROM AUTHOR]

A quadrupolar compound Pyr‐BA with two pyrrole‐type nitrogen atoms doped externally was prepared in this work. In high contrast with other π ionic radicals, its cationic radical Pyr‐BA⋅+ undergoes unusual symmetry‐broken charge separation (SB‐CS), generating the mixed valence complex of Pyr‐BA+1−q⋅⋅⋅Pyr‐BA+1+q, where q is the degree of charge transfer. Variable‐temperature (VT) single‐crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB‐CS process. Gibbs energy calculations and gauge‐including magnetically induced current simulation both validate that, for Pyr‐BA⋅+, SB‐CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single‐crystal evidence for spontaneous SB‐CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science. [ABSTRACT FROM AUTHOR]

We address a critical challenge of recovering and recycling homogeneous organocatalysts by designing photoswitchable catalyst structures that display a reversible solubility change in response to light. Initially insoluble catalysts are UV‐switched to a soluble isomeric state, which catalyzes the reaction, then back‐isomerizes to the insoluble state upon completion of the reaction to be filtered and recycled. The molecular design principles that allow for the drastic solubility change over 10 times between the isomeric states, 87 % recovery by the light‐induced precipitation, and multiple rounds of catalyst recycling are revealed. This proof of concept will open up opportunities to develop highly recyclable homogeneous catalysts that are important for the synthesis of critical compounds in various industries, which is anticipated to significantly reduce environmental impact and costs. [ABSTRACT FROM AUTHOR]

The chemical diversity and structural flexibility of lead halide perovskites (LHPs) offer tremendous opportunities to tune their optical properties through internal molecular engineering and external stimuli. Herein, we report the wide‐range and ultrapure photoluminescence emissions in a family of homologous 2D LHPs, [MeOPEA]2PbBr4−4xI4x (MeOPEA=4‐methoxyphenethylammonium; x=0, 0.2, 0.425, 0.575, 1) enabled through internal chemical pressure and external hydrostatic pressure. The chemical pressure, induced by the C−H⋅⋅⋅π interactions and halogen doping/substitution strengthens the structural rigidity to give sustained narrow emissions, and regulates the emission energy, respectively. Further manipulation of physical pressure leads to wide‐range emission tuning from 412 to 647 nm in a continuous and reversible manner. This work could open up new pathways for developing 2D LHP emitters with ultra‐wide color gamut and high color purity which are highly useful for pressure sensing. [ABSTRACT FROM AUTHOR]

Currently, less favorable C=O hydrogenation and weak concerted acid catalysis cause unsatisfactory catalytic performance in the upgrading of biomass‐derived furfurals (i.e., furfural, 5‐methyl furfural, and 5‐hydroxymethyl furfural) to ketones (i.e., cyclopentanone, 2,5‐hexanedione, and 1‐hydroxyl‐2,5‐hexanedione). A series of partially oxidized MAX phase (i.e., Ti3AlC2, Ti2AlC, Ti3SiC2) supporting Pd catalysts were fabricated, which showed high catalytic activity; Pd/Ti3AlC2 in particular displayed high performance for conversion of furfurals into targeted ketones. Detailed studies of the catalytic mechanism confirm that in situ hydrogen spillover generates Frustrated Lewis H+−H− pairs, which not only act as the hydrogenation sites for selective C=O hydrogenation but also provide acid sites for ring opening. The close intimate hydrogenation and acid sites promote bifunctional catalytic reactions, substantially reducing the reported minimum reaction temperature of various furfurals by at least 30–60 °C. [ABSTRACT FROM AUTHOR]

Ultra‐flexible stretchable organic light‐emitting diodes (OLEDs) are emerging as a basic component of flexible electronics and human‐machine interfaces. However, the brightness and efficiency of stretchable OLEDs remain still far inferior to their rigid counterparts, owing to the scarcity of satisfactory stretchable electroluminescent materials. Herein, we explore a general concept based on the self‐confinement effect to dramatically improve the stretchability of elastomers, without affecting electroluminescent properties. The balanced rigid/flexible chain dynamics under self‐confinement significantly reduces the modulus of the elastomers, resulting in the maximum strain reaching 806 %. Ultra‐flexible stretchable OLEDs have been constructed based on the resulting ISEEs, achieving unprecedented high‐performance non‐blended stretchable OLEDs. The results suggest an effective molecular design strategy for highly deformable stretchable displays and flexible electronics. [ABSTRACT FROM AUTHOR]

Chemical synthesis of proteins bearing base‐labile post‐translational modifications (PTMs) is a challenging task. For instance, O‐acetylation and S‐palmitoylation PTMs cannot survive Fmoc removal conditions during Fmoc‐solid phase peptide synthesis (SPPS). In this work, we developed a new Boc‐SPPS‐based strategy for the synthesis of peptide C‐terminal salicylaldehyde (SAL) esters, which are the key reaction partner in Ser/Thr ligation and Cys/Pen ligation. The strategy utilized the semicarbazone‐modified aminomethyl (AM) resin, which could support the Boc‐SPPS and release the peptide SAL ester upon treatment with TFA/H2O and pyruvic acid. The non‐oxidative aldehyde regeneration was fully compatible with all the canonical amino acids. Armed with this strategy, we finished the syntheses of the O‐acetylated protein histone H3(S10ac, T22ac) and the hydrophobic S‐palmitoylated peptide derived from caveolin‐1. [ABSTRACT FROM AUTHOR]

The combination of carbon‐based nanohoops with other functional organic molecular structures should lead to the design of new molecular configurations with interesting properties. Here, necklace‐like nanohoops embedded with carborane were synthesized for the first time. The unique deboronization of o‐carborane has led to the facile preparation of ionic nanohoop compounds. Nanohoops functionalized by nido‐o‐carborane show excellent fluorescence emission, with a solution quantum yield of up to 90.0 % in THF and a solid‐state quantum efficiency of 87.3 %, which opens an avenue for the applications of the nanohoops in OLEDs and bioimaging. [ABSTRACT FROM AUTHOR]

Prodrugs are one of the most common strategies for the design of targeted anticancer agents. However, their application is often hampered by the modifiable groups available on parent drugs. Herein, a carbon‐carbon (C−C) bond cleavage‐based prodrug activation strategy is reported, which was successfully used to design prodrugs of β‐lapachone (β‐lap), an ortho‐quinone natural product without traditional modifiable groups for the construction of C−N/C−O bond cleavage‐based prodrugs. The designed β‐lap prodrug with a reactive oxygen species‐specific trigger was quickly activated, releasing β‐lap. It exerted anticancer efficacy via NAD(P)H:quinone oxidoreductase 1 (NQO1)‐mediated futile redox cycling, resulting in potent cytotoxicity that was highly selective for NQO1‐rich cancer cells over normal cells both in vitro and in vivo. This significantly amplified the therapeutic window of β‐lap. This study provides a practical strategy for the design of prodrugs for parent drugs that do not contain traditional modifiable groups. [ABSTRACT FROM AUTHOR]

Efficient cathode interfacial layers (CILs) are becoming essential elements for organic solar cells (OSCs). However, the absorption of commonly used cathode interfacial materials (CIMs) is either too weak or overlaps too much with that of photoactive materials, hindering their contribution to the light absorption. In this work, we demonstrate the construction of highly efficient CIMs based on 2,7‐di‐tert‐butyl‐4,5,9,10‐pyrene diimide (t‐PyDI) framework. By introducing amino, amino N‐oxide and quaternary ammonium bromide as functional groups, three novel self‐doped CIMs named t‐PyDIN, t‐PyDINO and t‐PyDINBr are synthesized. These CIMs are capable of boosting the device performances by broadening the absorption, forming ohmic contact at the interface of active layer and electrode, as well as facilitating electron collection. Notably, the device based on t‐PyDIN achieved a power conversion efficiency of 18.25 %, which is among the top efficiencies reported to date in binary OSCs. [ABSTRACT FROM AUTHOR]

The article titled "Inside Back Cover: A Small-Molecule Inhibitor of Factor Inhibiting HIF Binding to a Tyrosine-Flip Pocket for the Treatment of Obesity" discusses the study conducted by Christopher Schofield, Xiaojin Zhang, and their colleagues on the tyrosine-flip pocket in FIH. This pocket is crucial for the development of selective FIH inhibitors, and the researchers have discovered a potent and selective FIH inhibitor called ZG-2291. This inhibitor can be used as a probe to study the physiological functions of FIH, and it shows promise as a strategy for treating obesity. The article is authored by Yue Wu, Yafen Chen, Thomas P. Corner, Yu Nakashima, Eidarus Salah, Zhihong Li, Linjian Zhang, Le Yang, Anthony Tumber, Zhuoli Sun, Yukang Wen, Ailin Zhong, Fulai Yang, Xiang Li, Zhihong Zhang, Christopher J. Schofield, and Xiaojin Zhang. [Extracted from the article]

We developed o‐carborane as a new mechanophore by showing that the o‐carborane cluster is the preferred scission site in chain‐centered polymers through ultrasonication mechanochemistry. Mechanistic studies are consistent with a predominately homolytic mechanism of chain scission. The mechanically generated monocarbaborane fragments are highly reactive toward alcohol nucleophiles. By contrast, carborane with a different regiochemistry (m‐carborane) maintained its high mechanical stability. DFT simulations provide insights into the origins of carborane's mechanical lability. This fundamental research provides a new stimulus for carborane cage activation. [ABSTRACT FROM AUTHOR]

Dual‐ion batteries (DIBs) have attracted much attention owing to their low cost, high voltage, and environmental friendliness. As the source of active ions during the charging/discharging process, the electrolyte plays a critical role in the performance of DIBs, including capacity, energy density, and cycling life. However, most used electrolyte systems based on the LiPF6 salt demonstrate unsatisfactory performance in DIBs. We have successfully developed a 7.5 mol kg−1 lithium bis(fluorosulfonyl)imide (LiFSI) in a carbonate electrolyte system. Compared with diluted electrolytes, this highly concentrated electrolyte exhibits several advantages: 1) enhanced intercalation capacity and cycling stability of the graphite cathode, 2) optimized structural stability of the Al anode, and 3) significantly increased battery energy density. A proof‐of‐concept DIB based on this concentrated electrolyte exhibits a discharge capacity of 94.0 mAh g−1 at 200 mA g−1 and 96.8 % capacity retention after 500 cycles. By counting both the electrode materials and electrolyte, the energy density of this DIB reaches up to ≈180 Wh kg−1, which is among the best performances of DIBs reported to date. [ABSTRACT FROM AUTHOR]

A strategy for modifying the structure of solid‐state electrolytes (SSEs) to reduce the cation diffusion activation energy is presented. Two heavily W‐doped sodium thioantimonate SSEs, Na2.895W0.3Sb0.7S4 and Na2.7W0.3Sb0.7S4 are designed, both exhibiting exceptionally low activation energy and enhanced room temperature (RT) ionic conductivity; 0.09 eV, 24.2 mS/cm and 0.12 eV, 14.5 mS/cm. At −15 °C the Na2.895W0.3Sb0.7S4 displays a total ionic conductivity of 5.5 mS/cm. The 30 % W content goes far beyond the 10–12 % reported in the prior studies, and results in novel pseudo‐cubic or orthorhombic structures. Calculations reveal that these properties result from a combination of multiple diffusion mechanisms, including vacancy defects, strongly correlated modes and excessive Na‐ions. An all‐solid‐state battery (ASSB) using Na2.895W0.3Sb0.7S4 as the primary SSE and a sodium sulfide (Na2S) cathode achieves a reversible capacity of 400 mAh g−1. [ABSTRACT FROM AUTHOR]

The development of improved and less costly catalysts for dehydrogenation of formic acid (HCOOH) is of general interest for renewable energy technologies involving hydrogen storage and release. Theoretical calculations reveal that ruthenium (Ru) nanoparticles supported on nitrogen‐doped carbon should be appropriate catalysts for such transformations. It is predicted that nitrogen doping significantly decreases the formation of CO, but at the same time increases CO tolerance of the catalysts. To prove these hypotheses heterogeneous ruthenium catalysts supported on porous nitrogen‐doped carbon (Rux/CN) with hierarchical structure were synthesized using carbon nitride (C3N4) as template and phenanthroline (Phen) as ligand. Experimental tests in HCOOH dehydrogenation revealed that the optimal catalyst Ru7/CN exhibited good thermal stability at 140 °C and a high turnover frequency (TOF >1300 h−1), which is more than one order of magnitude higher than that of the commercial Ru5/C catalyst. [ABSTRACT FROM AUTHOR]

A novel PdII‐catalyzed enantioselective oxycarbonylation of alkenes has been established. The ligand with an ethyl group at the C‐6 position of Pyox plays a significant role in the intermolecular oxypalladation process, leading to high reactivity and excellent enantioselective control. Compared to the conventional methods, the reaction itself features alkenes as easily prepared starting materials, mild and operationally simple reaction conditions, and insensitivities to air and water. Moreover, this method allows for broad alkene substrate scope, excellent regio‐ and enantioselectivities, scalabilities and a wide array of applications, and provides a useful route for the convenient and straightforward synthesis of chiral β‐hydroxy alkylcarboxylic acids/esters. [ABSTRACT FROM AUTHOR]

Temperature‐programmed reduction of transition‐metal phosphate precursors is the most commonly used method for the preparation of transition‐metal phosphides (a new class of versatile metal catalysts), but the reduction processes are still not clear. Here we describe the construction of a temperature‐programmed reduction‐infrared spectroscopy apparatus (TPR‐IR) to analyze the gas flows during the reduction of nickel, molybdenum, and tungsten phosphates. PH3 and Pn+ species already appeared in the gas flows at low temperature (ca. 200 °C), and PH3 was involved in the formation of phosphides. The emission of PH3 and Pn+ during the reduction of the molybdenum and tungsten phosphates was smaller than that of the nickel phosphate. Ni2P drastically accelerated the formation of the PH3 and Pn+. These results explain why excess phosphorus is needed for the preparation of Ni2P, and also demonstrate that the TPR‐IR technique is an efficient method to understand the complex processes of catalyst preparation. [ABSTRACT FROM AUTHOR]

Manganese‐rich layered oxide materials hold great potential as low‐cost and high‐capacity cathodes for Na‐ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn‐rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn‐rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g−1. It delivers ca. 160 mAh g−1 specific capacity between 2–3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre‐formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de‐sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3‐P3 phase transition. [ABSTRACT FROM AUTHOR]

The advent of SELEX (systematic evolution of ligands by exponential enrichment) technology has shown the ability to evolve artificial ligands with affinity and specificity able to meet growing clinical demand for probes that can, for example, distinguish between the target leukemia cells and other cancer cells within the matrix of heterogeneity, which characterizes cancer cells. Though antibodies are the conventional and ideal choice as a molecular recognition tool for many applications, aptamers complement the use of antibodies due to many unique advantages, such as small size, low cost, and facile chemical modification. This Minireview will focus on the novel applications of aptamers and SELEX, as well as opportunities to develop molecular tools able to meet future clinical needs in biomedicine. [ABSTRACT FROM AUTHOR]

Herein, we report that highly chemoselective and enantioselective reduction of 2‐vinyl‐substituted pyridines has been achieved for the first time. The reaction, which uses chiral spiro‐bicyclic bisboranes as catalysts and HBpin and an acidic amide as reducing reagents, proceeds through a cascade process involving 1,4‐hydroboration followed by transfer hydrogenation of a dihydropyridine intermediate. The retained double bond in the reduction products permits their conversion to natural products and other useful heterocyclic compounds by simple transformations. [ABSTRACT FROM AUTHOR]

Alkaline phosphatase (ALP) is an important biomarker, as high levels of ALP in blood can indicate liver disease or bone disorders. However, current clinical blood tests only measure the total concentration of ALP but are unable to distinguish enzyme isotypes. Here, we demonstrate a novel and rapid approach to profile various ALP isozymes in blood via a single‐molecule‐analysis platform. The microarray platform provides enzyme kinetics of hundreds of individual molecules at high throughput. Using these single molecule kinetics, we characterize the different activity profiles of ALP isotypes. By analyzing both healthy and disease samples, we found the single molecule activity distribution of ALP in serum reflects the health status of patients. This result demonstrates the potential utility of the method for improving the conventional ALP test, as well as for analyzing other enzymatic biomarkers, including enzyme isotypes. [ABSTRACT FROM AUTHOR]

Metal–organic framework (MOF)‐derived Co‐N‐C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co‐N‐C catalyst achieves superior activity, better acid resistance, and improved long‐term stability compared with nanoparticles synthesized by a similar route. High‐angle annular dark‐field–scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and X‐ray absorption fine structure characterizations reveal the formation of CoIINx centers as active sites. The optimal low‐cost catalyst is a promising candidate for liquid H2 generation. [ABSTRACT FROM AUTHOR]

Polymer networks usually contain numerous inhomogeneities that deteriorate their physical properties and should be eliminated to create reliable, high‐performance materials. A simple method is introduced for the production of nearly ideal networks from various vinyl polymers through controlled polymerization and subsequent crosslinking. Monodisperse star polymers with bromide end groups were synthesized by atom‐transfer radical polymerization and end‐linked with dithiol linkers using thiol–bromide chemistry. This simple procedure formed nearly ideal polymer networks, as revealed from elasticity of the formed gel and model conjugation reactions involving linear polymers. The versatility of this method was demonstrated by preparing networks of common vinyl polymers, including polyacrylates, polymethacrylate, and polystyrene. This method can be used to prepare multiple functional nearly ideal gels and elastomers and to explore fundamental aspects of polymer networks. [ABSTRACT FROM AUTHOR]

Heteronuclear Group 3 metal/iron carbonyl anion complexes ScFe(CO)3−, YFe(CO)3−, and LaFe(CO)3− are prepared in the gas phase and studied by mass‐selective infrared (IR) photodissociation spectroscopy as well as quantum‐chemical calculations. All three anion complexes are characterized to have a metal–metal‐bonded C3v equilibrium geometry with all three carbonyl ligands bonded to the iron center and a closed‐shell singlet electronic ground state. Bonding analyses reveal that there are multiple bonding interactions between the bare group‐3 elements and the Fe(CO)3− fragment. Besides one covalent electron‐sharing metal–metal σ bond and two dative π bonds from Fe to the Group 3 metal, there is additional multicenter covalent bonding with the Group 3 atom bonded to Fe and the carbon atoms. [ABSTRACT FROM AUTHOR]

The assembly of pH‐responsive DNA‐based, phase‐separated microdroplets (MDs) coacervates, consisting of frameworks composed of Y‐shaped nucleic acid modules crosslinked by pH‐responsive strands, is introduced. The phase‐separated MDs reveal dynamic pH‐stimulated switchable or oscillatory transient depletion and reformation. In one system, a photoisomerizable merocyanine/spiropyran photoacid is used for the light‐induced pH switchable modulation of the reaction medium between the values pH=6.0–4.4. The dynamic transient photochemically‐induced switchable depletion/reformation of phase‐separated MDs, follows the rhythm of pH changes in solution. In a second system, the Landolt oscillatory reaction mixture pH 7.5→4.2→7.5 is applied to stimulate the oscillatory depletion/reformation of the MDs. The autonomous dynamic oscillation of the assembly/disassembly of the MDs follows the oscillating pH rhythm of the reaction medium. [ABSTRACT FROM AUTHOR]

Two‐dimensional (2D) hybrid perovskites have shown many attractive properties associated with their soft lattices and multiple quantum well structure. Herein, we report the synthesis and characterization of two new multifunctional 2D hybrid perovskites, (PED)CuCl4 and (BED)2CuCl6, which show reversible thermochromic behavior, dramatic temperature‐dependent conductivity change, and strong ferromagnetism. Upon temperature change, the (PED)CuCl4 and (BED)2CuCl6 crystals exhibit a reversible color change between yellow and red‐brown. The associated structural changes were monitored by in situ temperature‐dependent powder X‐ray diffraction (PXRD). The (BED)2CuCl6 exhibits superior thermal stability, with a thermochromic working temperature up to 443 K. The conductivity of (BED)2CuCl6 changes over six orders of magnitude upon temperature change. The 2D perovskites exhibit ferromagnetic properties with Curie temperatures around 13 K. [ABSTRACT FROM AUTHOR]

π‐d Conjugated coordination polymers (CCPs) have attracted much attention for various applications, although the chemical states and structures of many CCPs are still blurry. Now, a one‐dimensional (1D) π‐d conjugated coordination polymer for high performance sodium‐ion batteries is presented. The chemical states of the obtained coordination polymer are clearly revealed. The electrochemical process undergoes a three‐electron reaction and the structure transforms from C=N double bonds and NiII to C−N single bonds and NiI, respectively. Our unintentional experiments provided visual confirmation of NiI. The existence of NiI was further corroborated by its X‐ray absorption near‐edge structure (XANES) and its catalytic activity in Negishi cross‐coupling. [ABSTRACT FROM AUTHOR]

A new series of spiro‐bicyclic bisborane catalysts has been prepared by means of hydroboration reactions of C2‐symmetric spiro‐bicyclic dienes with HB(C6F5)2 and HB(p‐C6F4H)2. When used for hydrogenation of quinolines, these catalysts give excellent yields and enantiomeric excesses, and show turnover numbers of up to 460. The most attractive feature of these metal‐free hydrogenation reactions was the broad functional‐group tolerance, making this method complementary to existing methods for quinoline hydrogenation. B,B bicycles: A series of C2‐symmetric spiro‐bicyclic bisboranes has been prepared. These bisboranes demonstrate highly effective and selective asymmetric hydrogenation of quinolines. The exceedingly broad functional‐group tolerance allows access to various enantioenriched and functionalized tetrahydroquinilines, which are inaccessible by previous methods using either borane or transition‐metal catalysts. [ABSTRACT FROM AUTHOR]

Cell migration is a ubiquitous and important cell behaviour. Construction of an interface that can guide and induce cell migration is of significance for studying cell behaviour and carrying out the transplantation of biological materials. Herein, we prepare a micropillar array by precise modification of two different functional groups on each micropillar unit to obtain a "Janus" structure with anisotropic cell‐adhesion properties. This anisotropic structure was capable of influencing the focal adhesion pathway of melanoma cells as shown by transcriptome sequencing and bioinformatics analysis. This the anisotropic substrate can considerably affect the migration ability of highly invasive melanoma cells. The anisotropic structure with Janus micropillar arrays could also affect the cell division cycle. The experiments showed that the anisotropic microstructures regulate cell migration and are thus of use in the research of cell migration without drug stimulation. On the move: An anisotropic substrate for cell adhesion is formed by a Janus micropillar arrays and guides cell migration by regulating the cellular focal adhesion pathway. It can also promote the cell division cycle and be used to study cell migration without drug stimulation. [ABSTRACT FROM AUTHOR]

A palladium‐catalyzed intermolecular arylcarbonylation of unactivated alkenes has been developed. Unsymmetrical diaryliodonium salts (DAISs) were used as arylation reagents, the bulky aryl group (ArL) of which was exclusively incorporated into the arylcarbonylated products, which contained the ArL group and a carboxylic ester group at the α‐ and β‐carbon position, respectively, of the original terminal C−C double bond. The reaction features excellent chemo‐ and regioselectivity, high functional‐group tolerance, and very mild reaction conditions. Bulking up: The bulky aryl group (ArL) of unsymmetrical diaryliodonium salts was exclusively incorporated at the α‐position of unactivated terminal alkenes in a palladium‐catalyzed intermolecular arylcarbonylation reaction (see scheme). The reaction occurs under very mild conditions and features excellent chemo‐ and regioselectivity and high functional‐group tolerance. [ABSTRACT FROM AUTHOR]

This manuscript reports an effort to stabilize self-assembled DNA crystals. Owing to their weak inter-unit cohesion, self-assembled DNA crystals are fragile, which limits the potential applications of such crystals. To overcome this problem, another molecule was introduced, which binds to the cohesive sites and stabilizes the inter-unit interactions. The extra interactions greatly improve the stability of the DNA crystals. The original DNA crystals are only stable in solutions of high ionic strength (e.g., ≥1.2 M (NH4)2SO4); in contrast, the stabilized crystals can be stable at ionic strengths as low as that of a 0.02 M solution of (NH4)2SO4. The current strategy is expected to represent a general approach for increasing the stability of self-assembled DNA nanostructures for potential applications, for example, as structural scaffolds and molecular sieves. [ABSTRACT FROM AUTHOR]

As a unique and unappreciated protein posttranslational modification, arginine N-glycosylation was recently discovered to play an important role in the process that bacteria counteract host defenses. To provide chemical tools for further proteomic and biochemical studies on arginine N-glycosylation, we report the first general strategy for a rapid and cost-effective synthesis of glycopeptides carrying single or multiple arginine N-GlcNAcyl groups. These glycopeptides were successfully utilized to generate the first antibodies that can specifically recognize arginine N-GlcNAcylated peptides or proteins in a sequence-independent manner. [ABSTRACT FROM AUTHOR]

Catalytic amounts of B(C6F5)3 promote the ring opening and subsequent isomerization of a series of unactivated cyclopropanes to afford terminal olefins in good yields when a hydrosilane and 2,6-dibromopyridine are employed as additives. [ABSTRACT FROM AUTHOR]

A stimuli-responsive lanthanide-based smart nanocomposite has been fabricated by supramolecular assembly and applied as an active material in multidimensional memory materials. Conjugation of the lanthanide complexes with carbon dots provides a stimuli response that is based on the modulation of the energy level of the ligand and affords microsecond-to-nanosecond fluorescence lifetimes, giving rise to intriguing memory performance in the spatial and temporal dimension. The present study points to a new direction for the future development of multidimensional memory materials based on inorganic-organic hybrid nanosystems. [ABSTRACT FROM AUTHOR]

Preparation of Ni2P by temperature-programmed reduction (TPR) of a phosphate precursor is challenging because the P−O bond is strong. An alternative approach to synthesizing Ni2P, by reduction of nickel hexathiodiphosphate (Ni2P2S6), is presented. Conversion of Ni2P2S6 into Ni2P occurs at 200-220 °C, a temperature much lower than that required by the conventional TPR method (typically 500 °C). A sulfur-containing layer with a thickness of about 4.7 nm, composed of tiny crystallites, was observed at the surface of the obtained Ni2P catalyst (Ni2P−S). This is a direct observation of the sulfur-containing layer of Ni2P, or the so-called nickel phosphosulfide phase. Both the hydrodesulfurization activity and the selective hydrogenation performance of Ni2P-S were superior to that of the catalyst prepared by the TPR method, suggesting a positive role of sulfur on the surface of Ni2P-S. These features render Ni2P-S a legitimate alternative non-precious metal catalyst for hydrogenation reactions. [ABSTRACT FROM AUTHOR]

Preparation of Ni2P by temperature-programmed reduction (TPR) of a phosphate precursor is challenging because the P−O bond is strong. An alternative approach to synthesizing Ni2P, by reduction of nickel hexathiodiphosphate (Ni2P2S6), is presented. Conversion of Ni2P2S6 into Ni2P occurs at 200-220 °C, a temperature much lower than that required by the conventional TPR method (typically 500 °C). A sulfur-containing layer with a thickness of about 4.7 nm, composed of tiny crystallites, was observed at the surface of the obtained Ni2P catalyst (Ni2P−S). This is a direct observation of the sulfur-containing layer of Ni2P, or the so-called nickel phosphosulfide phase. Both the hydrodesulfurization activity and the selective hydrogenation performance of Ni2P-S were superior to that of the catalyst prepared by the TPR method, suggesting a positive role of sulfur on the surface of Ni2P-S. These features render Ni2P-S a legitimate alternative non-precious metal catalyst for hydrogenation reactions. [ABSTRACT FROM AUTHOR]