Search

Rising global temperatures and critical energy shortages have spurred researches into CO2 fixation and conversion within the realm of energy storage such as Zn−CO2 batteries. However, traditional Zn−CO2 batteries employ double‐compartment electrolytic cells with separate carriers for catholytes and anolytes, diverging from the "rocking chair" battery mechanism. The specific energy of these conventional batteries is constrained by the solubility of discharge reactants/products in the electrolyte. Additionally, H2O molecules tend to trigger parasitic reactions at the electrolyte/electrode interfaces, undermining the long‐term stability of Zn anodes. In this report, we introduce an innovative "rocking chair" type Zn−CO2 battery that utilizes a weak‐acidic zinc trifluoromethanesulfonate aqueous electrolyte compatible with both cathode and anode. This design minimizes side reactions on the Zn surface and leverages the high catalytic activity of the cathode material, allowing the battery to achieve a substantial discharge capacity of 6734 mAh g−1 and maintain performance over 65 cycles. Moreover, the successful production of pouch cells demonstrates the practical applicability of Zn−CO2 batteries. Electrode characterizations confirm superior electrochemical reversibility, facilitated by solid discharge products of ZnCO3 and C. This work advances a "rocking chair" Zn−CO2 battery with an enhanced specific energy and a reversible pathway, providing a foundation for developing high‐performance metal‐CO2 batteries. [ABSTRACT FROM AUTHOR]

Herein, we propose a regional functionalization molecular design strategy that enables independent control of distinct pivotal parameters through different molecule segments. Three novel multiple resonances thermally activated delayed fluorescence (MR‐TADF) emitters A‐BN, DA‐BN, and A‐DBN, have been successfully synthesized by integrating highly rigid and three‐dimensional adamantane‐containing spirofluorene units into the MR framework. These molecules form two distinctive functional parts: part 1 comprises a boron‐nitrogen (BN)‐MR framework with adjacent benzene and fluorene units forming a central luminescent core characterized by an exceptionally rigid planar geometry, allowing for narrow FWHM values; part 2 includes peripheral mesitylene, benzene, and adamantyl groups, creating a unique three‐dimensional "umbrella‐like" conformation to mitigate intermolecular interactions and suppress exciton annihilation. The resulting A‐BN, DA‐BN, and A‐DBN exhibit remarkably narrow FWHM values ranging from 18 to 14 nm and near‐unity photoluminescence quantum yields. Particularly, OLEDs based on DA‐BN and A‐DBN demonstrate outstanding efficiencies of 35.0 % and 34.3 %, with FWHM values as low as 22 nm and 25 nm, respectively, effectively accomplishing the integration of high color purity and high device performance. [ABSTRACT FROM AUTHOR]

Developing large‐scale monolithic perovskite/silicon tandem devices based on industrial Czochralski silicon wafers will likely have to adopt double‐side textured architecture, given their optical benefits and low manufacturing costs. However, the surface engineering strategies that are widely used in solution‐processed perovskites to regulate the interface properties are not directly applicable to micrometric textures. Here, we devise a surface passivation strategy by dynamic spray coating (DSC) fluorinated thiophenethylammonium ligands, combining the advantages of providing conformal coverage and suppressing phase conversion on textured surfaces. From the viewpoint of molecular engineering, theoretical calculation and experimental results demonstrate that introducing trifluoromethyl group provide more effective surface passivation through strong interaction and energy alignment by forming a dipole layer. Consequently, the DSC treatment of this bifunctional molecule enables the tandem cells based on industrial silicon wafers to achieve a certified stabilized power conversion efficiency of 30.89 %. In addition, encapsulated devices display excellent operational stability by retaining over 97 % of their initial performance after 600 h continuous illumination. [ABSTRACT FROM AUTHOR]

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three‐dimensional architectures, the case for simple arenes remains largely underdeveloped owing to the high aromatic stabilization energy. We herein report a dearomative sequential addition of two nucleophiles to arene π‐bonds through umpolung of chromium–arene complexes. This mode enables divergent dearomative carbonylation reactions of benzene derivatives by tolerating various nucleophiles in combination with alcohols or amines under CO‐gas‐free conditions, thus providing modular access to functionalized esters or amides. The tunable synthesis of 1,3‐ or 1,4‐cyclohexadienes as well as the construction of carbon quaternary centers further highlight the versatility of this dearomatization. Diverse late‐stage modifications and derivatizations towards synthetically challenging and bioactive molecules reveal the synthetic utility. A possible mechanism was proposed based on control experiments and intermediate tracking. [ABSTRACT FROM AUTHOR]

Clear delineation of tumor margins is essential for accurate resection and decreased recurrence rate in the clinic. Fluorescence imaging is emerging as a promising alternative to traditional visual inspection by surgeons for intraoperative imaging. However, traditional probes lack accuracy in tumor diagnosis, making it difficult to depict tumor boundaries accurately. Herein, we proposed an offensive and defensive integration (ODI) strategy based on the "attack systems (invasive peptidase) and defense systems (reductive microenvironment)" of multi‐dimensional tumor characteristics to design activatable fluorescent probes for imaging tumor boundaries precisely. Screened out from a series of ODI strategy‐based probes, ANQ performed better than traditional probes based on tumor unilateral correlation by distinguishing between tumor cells and normal cells and minimizing false‐positive signals from living metabolic organs. To further improve the signal‐to‐background ratio in vivo, derivatized FANQ, was prepared and successfully applied to distinguish orthotopic hepatocellular carcinoma tissues from adjacent tissues in mice models and clinical samples. This work highlights an innovative strategy to develop activatable probes for rapid diagnosis of tumors and high‐precision imaging of tumor boundaries, providing more efficient tools for future clinical applications in intraoperative assisted resection. [ABSTRACT FROM AUTHOR]

The control of noncarbon stereogenic centers is of profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved for construction of S‐, P‐, Si‐ and B‐stereocenters over the past decades, the catalyst‐controlled strategies to govern the formation of N‐stereogenic compounds have garnered less attention. Here, we disclose the first organocatalytic approach for efficient access to a wide range of nitrogen‐stereogenic compounds through a desymmetrization approach. Intriguingly, the pro‐chiral remote diols, which are previously not well addressed with enantiocontrol, are well differentiated by potent chiral carbene‐bound acyl azolium intermediates. Preliminary studies shed insights on the critical importance of the ionic hydrogen bond (IHB) formed between the dimer aggregate of diols to afford the chiral N‐oxide products that feature a tetrahedral nitrogen as the sole stereogenic element with good yields and excellent enantioselectivities. Notably, the chiral N‐oxide products could offer an attractive strategy for chiral ligand design and discovery of potential antibacterial agrochemicals. [ABSTRACT FROM AUTHOR]

Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu−NSO4/CN, with highly dispersed Cu(II)−SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (−0.5 V vs. RHE, FEformate=87.4 %). Pure HCOOH is produced with an energy conversion efficiency of 44.3 % at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production. [ABSTRACT FROM AUTHOR]

Catalytic upcycling of polyolefins into high‐value chemicals represents the direction in end‐of‐life plastics valorization, but poses great challenges. Here, we report the synthesis of a tandem porous catalyst via a micelle cascade assembly strategy for selectively catalytic cracking of polyethylene into olefins at a low temperature. A hierarchically porous silica layer from mesopore to macropore is constructed on the surface of microporous ZSM‐5 nanosheets through cascade assembly of dynamic micelles. The outer macropore arrays can adsorb bulky polyolefins quickly by the capillary and hydrophobic effects, enhancing the diffusion and access to active sites. The middle mesopores present a nanoconfinement space, pre‐cracking polyolefins into intermediates by weak acid sites, which then transport into zeolites micropores for further cracking by strong Brønsted acid sites. The hierarchically porous and acidic structures, mimicking biomimetic protease catalytic clefts, ideally match the tandem cracking steps of polyolefins, thus suppressing coke formation and facilitating product escape. As a result, light hydrocarbons (C1‐C7) are produced with a yield of 443 mmol gZSM‐5−1, where 74.3 % of them are C3‐C6 olefins, much superior to ZSM‐5 and porous silica catalysts. This tandem porous catalyst exemplifies a superstructure design of catalytic cracking catalysts for industrial and economical upcycling of plastic wastes. [ABSTRACT FROM AUTHOR]

Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g. Mg, Al, etc.) is energy‐intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of >99.9 %. H2 is produced in the same electrolyte by constructing a Zn‐H2O hydrolysis battery consisting of a Zn anode and a Raney‐Ni cathode to unlock the Zn‐H2O reaction. The entire two‐step water splitting reaction with a net energy efficiency of 70.4 % at 80 °C and 50 mA cm−2. Additionally, the Zn‐H2O system can be charged using renewable energy to produce H2 on demand and runs for 600 cycles only sacrificing 3.76 % energy efficiency. DFT calculations reveal that the desorption of H* on Raney‐Ni (−0.30 eV) is closer to zero compared with that on Zn (−0.87 eV), indicating a faster desorption of H* at low overpotential. Further, a 24 Ah electrolyzer is demonstrated to produce H2 with a net energy efficiency of 65.5 %, which holds promise for its real application. [ABSTRACT FROM AUTHOR]

The encapsulation of functional colloidal nanoparticles (100 nm) into single‐crystalline ZSM‐5 zeolites, aiming to create uniform core–shell structures, is a highly sought‐after yet formidable objective due to significant lattice mismatch and distinct crystallization properties. In this study, we demonstrate the fabrication of a core–shell structured single‐crystal zeolite encompassing an Fe3O4 colloidal core via a novel confinement stepwise crystallization methodology. By engineering a confined nanocavity, anchoring nucleation sites, and executing stepwise crystallization, we have successfully encapsulated colloidal nanoparticles (CN) within single‐crystal zeolites. These grafted sites, alongside the controlled crystallization process, compel the zeolite seed to nucleate and expand along the Fe3O4 colloidal nanoparticle surface, within a meticulously defined volume (1.5×107≤V≤1.3×108 nm3). Our strategy exhibits versatility and adaptability to an array of zeolites, including but not restricted to ZSM‐5, NaA, ZSM‐11, and TS‐1 with polycrystalline zeolite shell. We highlight the uniformly structured magnetic‐nucleus single‐crystalline zeolite, which displays pronounced superparamagnetism (14 emu/g) and robust acidity (~0.83 mmol/g). This innovative material has been effectively utilized in a magnetically stabilized bed (MSB) reactor for the dehydration of ethanol, delivering an exceptional conversion rate (98 %), supreme ethylene selectivity (98 %), and superior catalytic endurance (in excess of 100 hours). [ABSTRACT FROM AUTHOR]

Organic piezochromic materials that manifest pressure‐stimuli‐responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non‐luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation‐induced emission (AIE) chromophores, termed Cage 1–3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non‐luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa−1 was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure‐based luminescence. [ABSTRACT FROM AUTHOR]

Zinc‐based aqueous batteries (ZABs) are attracting extensive attention due to the low cost, high capacity, and environmental benignity of the zinc anode. However, their application is still hindered by the undesired zinc dendrites. Despite Zn‐surface modification being promising in relieving dendrites, a thick separator (i.e. glass fiber, 250–700 μm) is still required to resist the dendrite puncture, which limits volumetric energy density of battery. Here, we pivot from the traditional interphase plus extra separator categories, proposing an all‐in‐one ligand buffer layer (ca. 20 μm) to effectively modulate the Zn2+ transfer and deposition behaviors proved by in situ electrochemical digital holography. Experimental characterizations and density functional theory simulations further reveal that the catechol groups in the buffer layer can accelerate the Zn2+ reduction reaction (ZRR) through the electron‐donating p‐π conjugation effect, decreasing the negative charge in the coordination environment. Without extra separators, the elaborated system endows low polarization below 28.2 mV, long lifespan of 4950 h at 5 mA cm−2 in symmetric batteries, and an unprecedented volumetric energy density of 99.2 Wh L−1 based on the whole pouch cells. The concomitantly "separator‐free" and "dendrite‐free" conjugation effect with an accelerated ZRR process could foster the progression of metallic anodes and benefit energetic aqueous batteries. [ABSTRACT FROM AUTHOR]

A general approach to constructing room temperature phosphorescence (RTP) materials involves the incorporation of a phosphorescent emitter into a rigid host or polymers with high glass transition temperature. However, these materials often suffer from poor processability and suboptimal mechanical properties, limiting their practical applications. In this work, we developed benzothiadiazole‐based dialkene (BTD‐HEA), a multifunctional phosphorescent emitter with a remarkable yield of intersystem crossing (ΦISC, 99.83 %). Its high triplet exciton generation ability and dialkene structure enable BTD‐HEA to act as a photoinitiator and crosslinker, efficiently initiating the polymerization of various monomers within 120 seconds. A range of flexible phosphorescence gels, including hydrogels, organogels, ionogels, and aerogels were fabricated, which exhibit outstanding stretchability and recoverability. Furthermore, the unique fluorescent‐phosphorescent colorimetric properties of the gels provide a more sensitive method for the visual determination of the polymerization process. Notably, the phosphorescent emission intensity of the hydrogel can be increased by the formation of ice, allowing for the precise detection of hydrogel freezing. The versatility of this emitter paves the way for fabricating various flexible phosphorescence gels with diverse morphologies using microfluidics, film‐shearing, roll coating process, and two/three‐dimensional printing, showcasing its potential applications in the fields of bioimaging and bioengineering. [ABSTRACT FROM AUTHOR]

Piezochromic materials that exhibit pressure‐dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high‐contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage‐based πOF (Cage‐πOF‐1) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage‐πOF‐1 displays linear pressure‐dependent emission and achieves a high‐contrast emission difference up to 154 nm. Pressure‐responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π–π interactions‐dominated controllable structural shrinkage and porous‐spring‐structure‐mediated elasticity is responsible for the outstanding piezofluorochromism. [ABSTRACT FROM AUTHOR]

Aiming at the construction of novel stimuli‐responsive fluorescent system with precisely tunable emissions, the typical 9,14‐diphenyl‐9,14‐dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration‐induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli‐responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC‐functionalized [2]rotaxanes display interesting VIE behaviors including white‐light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion‐induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors (glum) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5‐fold increase in glum values up to −0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use. [ABSTRACT FROM AUTHOR]

A key task in today's inorganic synthetic chemistry is to develop effective reactions, routes, and associated techniques aiming to create new functional materials with specifically desired multilevel structures and properties. Herein, we report an ultrathin two‐dimensional layered composite of graphene ribbon and silicate via a simple and scalable one‐pot reaction, which leads to the creation of a novel carbon‐metal‐silicate hybrid family: carbosilicate. The graphene ribbon is in situ formed by unzipping carbon nanotubes, while the ultrathin silicate is in situ obtained from bulk silica or commercial glass; transition metals (Fe or Ni) oxidized by water act as bridging agent, covalently bonding the two structures. The unprecedented structure combines the superior properties of the silicate and the nanocarbon, which triggers some specific novel properties. All processes during synthesis are complementary to each other. The associated synergistic chemistry could stimulate the discovery of a large class of more interesting, functionalized structures and materials. [ABSTRACT FROM AUTHOR]

Nanohybrid photosystems have advantages in converting solar energy into electricity, while natural photosystems based solar‐powered energy‐storage device is still under developed. Here, we fabricate a new kind of photo‐rechargeable zinc‐ion hybrid capacitor (ZHC) benefiting from light‐harvesting carbon dots (CDs) and natural thylakoids for realizing solar energy harvesting and storage simultaneously. Under solar light irradiation, the embedded CDs in thylakoids (CDs/Thy) can convert the less absorbed green light into highly absorbed red light for thylakoids, besides, Förster resonance energy transfer (FRET) between CDs and Thy also occurs, which facilitates the photoelectrons generation during thylakoids photosynthesis, thereby resulting in 6‐fold photocurrent output in CDs/Thy hybrid photosystem, compared to pristine thylakoids. Using CDs/Thy as the photocathode in ZHCs, the photonic hybrid capacitor shows photoelectric conversion and storage features. CDs can improve the photo‐charging voltage response of ZHCs to ≈1.2 V with a remarkable capacitance enhancement of 144 % under solar light. This study provides a promising strategy for designing plant‐based photonic and electric device for solar energy harvesting and storage. [ABSTRACT FROM AUTHOR]

Enzyme‐prodrug therapies have shown unique advantages in efficiency, selectivity, and specificity of in vivo prodrug activation. However, precise spatiotemporal control of both the enzyme and its substrate at the target site, preservation of enzyme activity, and in situ substrate depletion due to low prodrug delivery efficiency continue to be great challenges. Here, we propose a novel core–shell reactor partitioning enzyme and prodrug by ZIF‐8, which integrates an enzyme with its substrate and increases the drug loading capacity (DLC) using a prodrug as the building ligand to form a Zn‐prodrug shell. Cytochrome P450 (CYP450) is immobilized in ZIF‐8, and the antitumor drug dacarbazine (DTIC) is coordinated and deposited in its outer layer with a high DLC of 43.6±0.8 %. With this configuration, a much higher prodrug conversion efficiency of CYP450 (36.5±1.5 %) and lower IC50 value (26.3±2.6 μg/mL) are measured for B16‐F10 cells with a higher NADPH concentration than those of L02 cells and HUVECs. With the tumor targeting ability of hyaluronic acid, this core–shell enzyme reactor shows a high tumor suppression rate of 96.6±1.9 % and provides a simple and versatile strategy for enabling in vivo biocatalysis to be more efficient, selective, and safer. [ABSTRACT FROM AUTHOR]

Protein therapeutics targeting intracellular machineries hold profound potential for disease treatment, and hence robust cytosolic protein delivery technologies are imperatively demanded. Inspired by the super‐negatively charged, nucleotide‐enriched structure of nucleic acids, adenylated pro‐proteins (A‐proteins) with dramatically enhanced negative surface charges have been engineered for the first time via facile green synthesis. Then, thymidine‐modified polyethyleneimine is developed, which exhibits strong electrostatic attraction, complementary base pairing, and hydrophobic interaction with A‐proteins to form salt‐resistant nanocomplexes with robust cytosolic delivery efficiencies. The acidic endolysosomal environment enables traceless restoration of the A‐proteins and consequently promotes the intracellular release of the native proteins. This strategy shows high efficiency and universality for a variety of proteins with different molecular weights and isoelectric points in mammalian cells. Moreover, it enables highly efficient delivery of CRISPR‐Cas9 ribonucleoproteins targeting fusion oncogene EWSR1‐FLI1, leading to pronounced anti‐tumor efficacy against Ewing sarcoma. This study provides a potent and versatile platform for cytosolic protein delivery and gene editing, and may benefit the development of protein pharmaceuticals. [ABSTRACT FROM AUTHOR]

Solar water oxidation is a critical step in artificial photosynthesis. Successful completion of the process requires four holes and releases four protons. It depends on the consecutive accumulation of charges at the active site. While recent research has shown an obvious dependence of the reaction kinetics on the hole concentrations on the surface of heterogeneous (photo)electrodes, little is known about how the catalyst density impacts the reaction rate. Using atomically dispersed Ir catalysts on hematite, we report a study on how the interplay between the catalyst density and the surface hole concentration influences the reaction kinetics. At low photon flux, where surface hole concentrations are low, faster charge transfer was observed on photoelectrodes with low catalyst density compared to high catalyst density; at high photon flux and high applied potentials, where surface hole concentrations are moderate or high, slower surface charge recombination was afforded by low‐density catalysts. The results support that charge transfer between the light absorber and the catalyst is reversible; they reveal the unexpected benefits of low‐density catalyst loading in facilitating forward charge transfer for desired chemical reactions. It is implied that for practical solar water splitting devices, a suitable catalyst loading is important for maximized performance. [ABSTRACT FROM AUTHOR]

The surface area of anisotropic polymeric assemblies is a critical parameter concerning their properties. However, it is still a grand challenge for traditional techniques to determine the surface area. Here, a molecular probe loading (MPL) method is developed to measure the surface area of anisotropic polymersomes in the shape of tube, disc, and stomatocyte. This method uses an amphiphilic molecular probe, comprising hydrophobic pyrene as the anchor and hydrophilic tetraethylene glycol (EG4) as the float. The surface area of spherical polymersomes determined by dynamic light scattering is quantitatively correlated with the loading amount of probes, allowing the calculation of the average separation distance between the loaded probes. With the separation distance, we successfully determine the surface area of anisotropic polymersomes by measuring the loading amount. We envision that the MPL method will assist in the real‐time surface area characterization, enabling the customization of functions. [ABSTRACT FROM AUTHOR]

The frequent mutation of KRAS oncogene in some of the most lethal human cancers has spurred incredible efforts to develop KRAS inhibitors, yet only one covalent inhibitor for the KRASG12C mutant has been approved to date. New venues to interfere with KRAS signaling are desperately needed. Here, we report a "localized oxidation‐coupling" strategy to achieve protein‐specific glycan editing on living cells for disrupting KRAS signaling. This glycan remodeling method exhibits excellent protein and sugar specificity and is applicable to different donor sugars and cell types. Attachment of mannotriose to the terminal galactose/N‐acetyl‐D‐galactosamine epitopes of integrin αvβ3, a membrane receptor upstream of KRAS, blocks its binding to galectin‐3, suppresses the activation of KRAS and downstream effectors, and mitigates KRAS‐driven malignant phenotypes. Our work represents the first successful attempt to interfere with KRAS activity by manipulating membrane receptor glycosylation. [ABSTRACT FROM AUTHOR]

Increasing selectivity without the expense of activity is desired but challenging in heterogeneous catalysis. By revealing the molecule saturation and adsorption sensitivity on overlayer thickness, strain, and coordination of Pd‐based catalysts from first‐principles calculations, we designed a stable Pd monolayer (ML) catalyst on a Ru terrace to boost both activity and selectivity of acetylene semihydrogenation. The least saturated molecule is most sensitive to the change in catalyst electronic and geometric properties. By simultaneously compressing the Pd ML and exposing the high coordination sites, the adsorption of more saturated ethylene is considerably weakened to facilitate the desorption for high selectivity. The even stronger weakening to the least saturated acetylene drives its hydrogenation such that it is more exothermic, thereby boosting the activity. Tailoring the molecule saturation and its sensitivity to structure and composition provides a tool for rational design of efficient catalysts. [ABSTRACT FROM AUTHOR]

The mismatched fast‐electron‐slow‐proton process in the electrocatalytic oxygen evolution reaction (OER) severely restricts the catalytic efficiency. To overcome these issues, accelerating the proton transfer and elucidating the kinetic mechanism are highly sought after. Herein, inspired by photosystem II, we develop a family of OER electrocatalysts with FeO6/NiO6 units and carboxylate anions (TA2−) in the first and second coordination sphere, respectively. Benefiting from the synergistic effect of the metal units and TA2−, the optimized catalyst delivers superior activity with a low overpotential of 270 mV at 200 mA cm−2 and excellent cycling stability over 300 h. A proton‐transfer‐promotion mechanism is proposed by in situ Raman, catalytic tests, and theoretical calculations. The TA2− (proton acceptor) can mediate proton transfer pathways by preferentially accepting protons, which optimizes the O−H adsorption/activation process and reduces the kinetic barrier for O−O bond formation. [ABSTRACT FROM AUTHOR]

Herein, a general strategy for chemo‐ and regioselective 1,2‐reduction of chromium‐bound arenes was developed, thus providing rapid access to 1,3‐cyclohexadienes. Selective arene activation via π‐complexation along with the use of mild hydride Ph3SiH can overcome the inherently low reactivity of arene π‐bonds while tolerating various reduction‐sensitive functional groups. Its versatility further enables a regiodivergent deuteration. Using different sequences of (non)deuterated hydride and acid reagents, the deuterated positions as well as the degrees of deuterium incorporation can be controlled precisely, which leads to a large and previously inaccessible chemical space for 1,3‐cyclohexadiene isotopologues. A reasonable mechanism was proposed based on intermediate capture and control experiments. The synthetic value of this selective 1,2‐reduction was demonstrated in the formal total synthesis of (±)‐galanthamine and (±)‐lycoramine. [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]

Lanthanide metal–organic frameworks (Ln‐MOFs) are promising for luminescence detection of volatile organic compound (VOC) vapors, but usually suffer from the silent or quenched Ln3+ emission. Herein, we report a new dual‐emissive Eu‐MOF composed of the coordinatively unsaturated Eu9 clusters that afford abundant open metal sites to form a confined "binding pocket" to facilitate the preconcentration and recognition of VOCs. Single‐crystal structural analyses reveal that specific analytes can replace the OH oscillators in the first coordination sphere of Eu3+ and form a unique hydrogen‐bonding second‐sphere adduct tying adjacent Eu9 clusters together to minimize their nonradiative vibrational decay. With the promoted Eu3+ luminescence, the MOF realizes real‐time in situ visual sensing of THF vapor (<1 s) and shows a quantitative ratiometric response to the vapor pressure with a limit of detection down to 17.33 Pa. Also, it represents a top‐performing ratiometric luminescent thermometer. [ABSTRACT FROM AUTHOR]

Synthetic single‐stranded (ss) DNA is a cornerstone for life and materials science, yet the purity, quantity, length, and customizability of synthetic DNA are still limiting in various applications. Here, we present PECAN, paired‐end cutting assisted by DNAzymes (DNA enzymes or deoxyribozymes), which enables mass production of ssDNA of arbitrary sequence (up to 7000 nucleotides, or nt) with single‐base precision. At the core of PECAN technique are two newly identified classes of DNAzymes, each robustly self‐hydrolyzing with minimal sequence requirement up‐ or down‐stream of its cleavage site. Flanking the target ssDNA with a pair of such DNAzymes generates a precursor ssDNA amplifiable by pseudogene‐recombinant bacteriophage, which subsequently releases the target ssDNA in large quantities after efficient auto‐processing. PECAN produces ssDNA of virtually any terminal bases and compositions with >98.5 % purity at the milligram‐to‐gram scale. We demonstrate the feasibility of using PECAN ssDNA for RNA in situ detection, homology‐directed genome editing, and DNA‐based data storage. [ABSTRACT FROM AUTHOR]

Aiming at the construction of novel circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (glum), topologically chiral [2]catenanes were employed as the key platform to construct a novel multistate CPL switching system. Taking advantage of the precise co‐conformation regulations of the resultant pyrene‐functionalized [2]catenanes under different external stimuli, reversible transformations between three emission states with different CPL performances, i.e. the initial "closed" form with a |glum| value of 0.012, the "open" form with an almost complete turn‐off of CPL emission, and the "protonated" form with a boosted |glum| value of 0.022, were successfully realized. This study demonstrates the successful construction of not only the first topological chirality‐based CPL switch, but also a novel bidirectional CPL switch, thus providing a promising platform for the construction of novel chiral materials. [ABSTRACT FROM AUTHOR]

Under cold pressure sp1/sp2‐to‐sp3 hybridization transformation has been exclusively observed in covalent or molecular crystals overwhelmingly above ≈10 GPa, and the approaches to lower the transition pressure are limited on external heat‐treatment and/or catalyzers. Herein we demonstrate that, by internal‐lattice stress‐transfer from ionic to covalent groups, the transformation can be significantly prompted, as shown in a crystal of LiBO2 under 2.85 GPa for the first case in ionic crystals. This unprecedentedly low transformation pressure is ascribed to the enhanced localized stress on covalent B−O frames transferred from ionic Li−O bonds in LiBO2, and accordingly the corresponding structural feature is summarized. This work provides an internal structural regulation strategy for pressure‐reduction of the s‐p orbital hybridization transformation and extends the sp1/sp2‐to‐sp3 transformation landscape from molecular and covalent compounds to ionic systems. [ABSTRACT FROM AUTHOR]

A sulfhydryl monomicelles interfacial assembly strategy is presented for the synthesis of fully exposed single‐atom‐layer Pt clusters on 2D mesoporous TiO2 (SAL‐Pt@mTiO2) nanosheets. This synthesis features the introduction of the sulfhydryl group in monomicelles to finely realize the controllable co‐assembly process of Pt precursors within ordered mesostructures. The resultant SAL‐Pt@mTiO2 shows uniform SAL Pt clusters (≈1.2 nm) anchored in ultrathin 2D nanosheets (≈7 nm) with a high surface area (139 m2 g−1), a large pore size (≈25 nm) and a high dispersion (≈99 %). Moreover, this strategy is universal for the synthesis of other SAL metal clusters (Pd and Au) on 2D mTiO2 with high exposure and accessibility. When used as a catalyst for hydrogenation of 4‐nitrostyrene, the SAL‐Pt@mTiO2 shows a high catalytic activity (TOF up to 2424 h−1), 100 % selectivity for 4‐aminostyrene, good stability, and anti‐resistance to thiourea poisoning under relatively mild conditions (25 °C, 10 bar). [ABSTRACT FROM AUTHOR]

Constructing organic near‐infrared (NIR) luminescent materials to confront the formidable barrier of "energy gap law" remains challenging. Herein, two NIR thermally activated delayed fluorescence (TADF) molecules named T‐β‐IQD and TIQD were developed by connecting N,N‐diphenylnaphthalen‐2‐amine and triphenylamine with a novel electron withdrawing unit 6‐(4‐(tert‐butyl)phenyl)‐6H‐indolo[2,3‐b]quinoxaline‐2,3‐dicarbonitrile. It is confirmed NIR‐TADF emitters concurrent with aggregation‐induced emission effect, J‐aggregate with intra‐ and intermolecular CN⋅⋅⋅H−C and C−H⋅⋅⋅π interactions, and large center‐to‐center distance in solid states can boost the emissive efficiencies both in thin films and non‐doped organic light‐emitting diodes (OLEDs). Consequently, the T‐β‐IQD‐based non‐doped NIR‐OLED achieved the maximum external quantum efficiency (EQEmax) of 9.44 % with emission peak at 711 nm, which is one of the highest efficiencies reported to date for non‐doped NIR‐OLEDs. [ABSTRACT FROM AUTHOR]

Amides are ubiquitous in physical and life sciences. Given the significant abundance of arenes, dearomative aminocarbonylation of arenes would lead to a large and underexplored chemical space for amide discovery. However, such reactions are challenging due to the high degree of resonance stabilization and selectivity issues. Herein, we disclose an unprecedented dearomative trifluoromethylative aminocarbonylation of arenes via bifunctional coordination to chromium, providing a modular platform for the construction of amides possessing trifluoromethyl (CF3) groups and three‐dimensional rings. Its versatility further enabled a switchable difluoromethylation or trifluoromethylation aminocarbonylation of arene C−H bonds. A possible mechanism was proposed based on control experiments. Finally, the synthetic utility was well demonstrated by diverse applications in the total synthesis of CF3‐functionalized amide‐type drugs, including praziquantel, nateglinide, maraviroc and alloyohimbane. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes (SPEs) with LiTFSI (lithium bis(trifluoromethane sulfonimide)) are promising candidates for solid‐state batteries, owing to their good interfacial contact with solid electrodes. Here, three copolymerized polyethers were prepared as SPEs, using the catalysts of SnF2 or SnF2‐LiPF6. The thermal depolymerization of these polyethers was observed at elevated temperatures, which limits their operating temperature ranges. Once the catalyst is removed, the thermal degradation temperatures of these SPEs are raised by 30–55 °C, together with improved thermal performance in cells. For SPEs, the high price of LiTFSI is an obstacle for their large‐scale application, and it's recycling is hindered by the strong interaction with polymers. By the thermal depolymerization of polyethers, LiTFSI can be easier reclaimed from above mentioned SPEs and even the commercial PEO(poly(ethylene‐oxide)) based SPE in rates of 70–80 %, providing a low‐cost strategy for the recycling of LiTFSI. [ABSTRACT FROM AUTHOR]

Tumor‐specific, hypoxia‐activated prodrugs have been developed to alleviate the side effects of chemotherapy drugs. However, the release efficiency of hypoxia‐activated prodrugs is restricted by the degree of tumor hypoxia, which further leads to poor cancer treatment effects. On the other hand, oxygen is consumed gradually in photodynamic therapy (PDT), which aggravates hypoxia at the tumor site. In this study, we combined hypoxia‐activated prodrugs with PDT agents to promote the prodrugs release, thereby improving their bioavailability and therapeutic effects. As a proof of concept, a mitochondria‐targeted molecular prodrug, CS‐P, was designed and synthesized. It can be selectively activated by tumor hypoxia to release chemotherapeutic drugs and photosensitizers, and then further discharge drugs after light irradiation. The design strategy proposed in this paper provides a new idea for enhancing hypoxia‐activated prodrug release and real‐time monitoring prodrug release. [ABSTRACT FROM AUTHOR]

Anomeric stereocontrol is usually one of the major issues in the synthesis of complex carbohydrates, particularly those involving β‐configured 2,6‐dideoxyglycoside and d/l‐rhamnoside moieties. Herein, we report that 2‐(diphenylphosphinoyl)acetyl is highly effective as a remote stereodirecting group in the direct synthesis of these challenging β‐glycosides under mild conditions. A deoxy‐trisaccharide as a mimic of the sugar chain of landomycin E was prepared stereospecifically in high yield. The synthetic potential was also highlighted in the synthesis of Citrobacter freundii O‐antigens composed of a [→4)‐α‐d‐Manp‐(1→3)‐β‐d‐Rhap(1→4)‐β‐d‐Rhap‐(1→] repeating unit, wherein the convergent assembly up to a nonasaccharide was realized with a strongly β‐directing trisaccharide donor. Variable‐temperature NMR studies indicate the presence of intermolecular H‐bonding between the donor and the bulky acceptor as direct spectral evidence in support of the concept of hydrogen‐bond‐mediated aglycone delivery. [ABSTRACT FROM AUTHOR]

Mimicking natural nitrogenase to create highly efficient single‐atom catalysts (SACs) for ambient N2 fixation is highly desired, but still challenging. Herein, S‐coordinated Fe SACs on mesoporous TiO2 have been constructed by a lattice‐confined strategy. The extended X‐ray absorption fine structure and X‐ray photoelectron spectroscopy spectra demonstrate that Fe atoms are anchored in TiO2 lattice via the FeS2O2 coordination configuration. Theoretical calculations reveal that FeS2O2 sites are the active centers for electrocatalytic nitrogen reduction reaction (NRR). Moreover, the finite element analysis shows that confinement of opened and ordered mesopores can facilitate the mass transport and offer an enlarged active surface area for NRR. As a result, this catalyst delivers a favorable NH3 yield rate of 18.3 μg h−1 mgcat.−1 with a high Faradaic efficiency of 17.3 % at −0.20 V versus a reversible hydrogen electrode. Most importantly, this lattice‐confined strategy is universal and can also be applied to Ni1Sx@TiO2, Co1Sx@TiO2, Mo1Sx@TiO2, and Cu1Sx@TiO2 SACs. Our study provides new hints for the design and biomimetic synthesis of highly efficient NRR electrocatalysts. [ABSTRACT FROM AUTHOR]

Cyanines have been widely used as the photosensitizers (PSs) in the biomedical field, but controlling their molecular aggregates in nanoparticles (NPs) remains a major challenge. Moreover, the impact of aggregate behaviors of cyanines on the photosensitization is still unclear. Herein, the first anionic cyanine PSs based on a tricyanofuran end group have been designed by achieving supramolecular J‐type aggregates in NPs via counterion engineering. Our results indicate that J‐type aggregates in NPs can not only bring significantly red‐shifted emission, negatively charged surface, and high photostability, but also enable a significant 5‐fold increase in singlet oxygen generation efficiency compared to that in the nonaggregate state, providing strong experimental evidence for the superiority of J‐aggregates in enhancing photosensitization. Thus, combined with the mitochondria‐targeting ability, the J‐type aggregate NPs show remarkable in vivo antitumor phototheranostic efficacy, making them have a potential for clinical use. [ABSTRACT FROM AUTHOR]

The active site of the industrial Cu/ZnO/Al2O3 catalyst used in CO2 hydrogenation to methanol has been debated for decades. Grand challenges remain in the characterization of structure, composition, and chemical state, both microscopically and spectroscopically, and complete theoretical calculations are limited when it comes to describing the intrinsic activity of the catalyst over the diverse range of structures that emerge under realistic conditions. Here a series of inverse model catalysts of ZnO on copper hydroxide were prepared where the size of ZnO was precisely tuned from atomically dispersed species to nanoparticles using atomic layer deposition. ZnO decoration boosted methanol formation to a rate of 877 gMeOH kgcat−1 h−1 with ≈80 % selectivity at 493 K. High pressure in situ X‐ray absorption spectroscopy demonstrated that the atomically dispersed ZnO species are prone to aggregate at oxygen‐deficient ZnO ensembles instead of forming CuZn metal alloys. By modeling various potential active structures, density functional theory calculations and microkinetic simulations revealed that ZnO/Cu interfaces with oxygen vacancies, rather than stoichiometric interfaces, Cu and CuZn alloys were essential to catalytic activation. [ABSTRACT FROM AUTHOR]

The anomeric configuration can greatly affect the biological functions and activities of carbohydrates. Herein, we report that N‐phenyltrifluoroacetimidoyl (PTFAI), a well‐known leaving group for catalytic glycosylation, can act as a stereodirecting group for the challenging 1,2‐cis α‐glycosylation. Utilizing rapidly accessible 1,6‐di‐OPTFAI glycosyl donors, TMSOTf‐catalyzed glycosylation occurred with excellent α‐selectivity and broad substrate scope, and the remaining 6‐OPTFAI group can be cleaved chemoselectively. The remote participation of 6‐OPTFAI is supported by the first characterization of the crucial 1,6‐bridged bicyclic oxazepinium ion intermediates by low‐temperature NMR spectroscopy. These cations were found to be relatively stable and mainly responsible for the present stereoselectivities. Further application is highlighted in glycosylation reactions toward trisaccharide heparins as well as the convergent synthesis of chacotriose derivatives using a bulky 2,4‐di‐O‐glycosylated donor. [ABSTRACT FROM AUTHOR]

Circularly polarized light (CPL) is key to asymmetric photochemistry as it could impart the chiral organization information into chemical products. Here, we demonstrate the circular polarization capacity of chiral cellulose nanocrystal (CNC) films to trigger photo‐alignment of achiral supramolecular polymers into helical structures. Right‐handed transmitted (T‐) CPL was generated from self‐assembled CNC films, which induced amorphous azobenzene (Azo) supramolecular polymers into chiral structures. The chiral induction effect of T‐CPL is enhanced on Azo polymers with longer spacers. The absorptive dissymmetry factor (gabs) values of liquid‐crystal supramolecular polymers can be amplified significantly (over 10 times) after T‐CPL irradiation. Moreover, by integrating carbon dots into CNC films, CPL emission with a considerable luminescence dissymmetry factor (glum) up to −0.66 was achieved, and it could be used for the photo‐alignment of Azo polymers with high chiroptical properties. This work provides new insight for the photo modulation of supramolecular polymers by CPL‐active materials. [ABSTRACT FROM AUTHOR]

Developing universal stimuli‐responsive materials capable of emitting a broad spectrum of colors is highly desirable. Herein, we deliberately grafted a conformation‐adaptable organic chromophore into the established coordination space of a flexible metal–organic framework (MOF). In terms of the coupled structural transformations and the space confinement, the chromophore in the MOF matrix underwent well‐regulated conformational changes under physical and chemical stimuli, simultaneously displaying thermo‐, piezo‐, and solvato‐fluoro‐chromism with color tunability over the visible range. Owing to the resilient nature and the reduced dimensionality of the selected coordination space, all three color modulations behaved in a sensitive and self‐reversible manner, each following a linear correlation of the emission maximum with stimulus. Single‐crystal X‐ray diffraction of the variable‐temperature structures and solvent‐inclusion crystals elucidated the intricate color varying mechanisms. [ABSTRACT FROM AUTHOR]

Polymerized‐dioxolane(P‐DOL) is of potential as a solid‐polymer‐electrolyte(SPE) due to its high Li+‐conductivity, good compatibility with Li‐metal and desired preparation method of in situ polymerization in cells. In this study, SnF2 was demonstrated not only to be an efficient catalyst for the polymerization of DOL at room temperature, but also an effective additive for improving interfacial wettability and suppressing dendrite through the reaction with Li‐metal and the formation of LiF/LixSn based composite solid electrolyte interlayer(SEI). Using the SnF2 polymerized P‐DOL containing 1 M LiTFSI as SPE(P‐DOL‐SPE), obviously denser Li‐deposition was obtained, and the all‐solid‐state(ASS) Li/LiFePO4 cell delivered stable cycling over 350 cycles at 45 °C. At the same time, the irreversible decomposition of P‐DOL‐SPE into formaldehyde and small molecule epoxides are observed at 110 °C, which is even initiated at lower temperature of 40 °C under vacuum. This thermal decomposition of P‐DOL‐SPE in pouch cell causes huge volume swell, and therefore putting a strict limitation on the operating temperature window for the P‐DOL based electrolytes. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) hold great potentials for addressing the challenge of highly efficient oil–water separation, but they are restricted by the poor wettability and processability as crystalline membranes. Here we report the design and synthesis of two‐dimensional (2D) robust COFs with controllable hydrophobicity and processability, allowing the COF layers to be directly grown on the support surfaces. Three 2D COFs with AA or ABC stacking are prepared by condensation of triamines with fluorine and/or isopropyl groups and perfluorodialdehyde. They all show excellent tolerance to water, acid, and base, with water contact angles (CA) of 111.5–145.8°. The two COFs with isopropyl and fluorine mixtures can grow as a coating on a stainless‐steel net (SSN) substrate, whereas the one with only fluorine substituents cannot. The superhydrophobic COF@SSN coating with water CA of up to 150.1° displays high water‐resistance and self‐cleaning properties, enabling high oil–water separation performances with an efficiency of over 99.5 % and a permeation flux of 2.84×105 L m−2 h−1, which are among the highest values reported for state‐of‐the‐art membranes. [ABSTRACT FROM AUTHOR]

Defects have been found to enhance the electrocatalytic performance of NiFe‐LDH for oxygen evolution reaction (OER). Nevertheless, their specific configuration and the role played in regulating the surface reconstruction of electrocatalysts remain ambiguous. Herein, cationic vacancy defects are generated via aprotic‐solvent‐solvation‐induced leaking of metal cations from NiFe‐LDH nanosheets. DFT calculation and in situ Raman spectroscopic observation both reveal that the as‐generated cationic vacancy defects tend to exist as VM (M=Ni/Fe); under increasing applied voltage, they tend to assume the configuration VMOH, and eventually transform into VMOH‐H which is the most active yet most difficult to form thermodynamically. Meanwhile, with increasing voltage the surface crystalline Ni(OH)x in the NiFe‐LDH is gradually converted into disordered status; under sufficiently high voltage when oxygen bubbles start to evolve, local NiOOH species become appearing, which is the residual product from the formation of vacancy VMOH‐H. Thus, we demonstrate that the cationic defects evolve along with increasing applied voltage (VM → VMOH → VMOH‐H), and reveal the essential motif for the surface restructuration process of NiFe‐LDH (crystalline Ni(OH)x → disordered Ni(OH)x → NiOOH). Our work provides insight into defect‐induced surface restructuration behaviors of NiFe‐LDH as a typical precatalyst for efficient OER electrocatalysis. [ABSTRACT FROM AUTHOR]

Owing to undesired Zn corrosion and the formation of Zn dendrites in aqueous electrolytes, most of the examples of aqueous Zn batteries with reported excellent performance are achieved with low Zn‐utilization (<0.6 %) in the anode and low mass‐loading (<3 mg cm−2) in the cathode. Herein, we propose a new organic electrolyte for Zn batteries, which contains a zinc trifluoromethanesulfonate (Zn‐TFMS) salt and a mixed solvent consisting of propylene carbonate (PC) and triethyl phosphate (TEP). We demonstrate that this electrolyte with an optimized PC/TEP ratio not only exhibits high ionic conductivity and a wide stable potential window, but also facilitates dendrite‐free Zn plating/stripping. In particular, the TEP solvent makes the electrolyte nonflammable. Finally, a 2 V Zn//polytriphenylamine composite (PTPAn) battery is fabricated with the optimized electrolyte; it shows a high rate and a long lifetime (2400 cycles) even with a high mass‐loading (16 mg cm−2) of PTPAn in the cathode and with a high Zn‐utilization (3.5 %). [ABSTRACT FROM AUTHOR]

Aiming at the construction of novel platform for efficient light harvesting, the precise synthesis of a new family of AIEgen‐branched rotaxane dendrimers was successful realized from an AIEgen‐functionalized [2]rotaxane through a controllable divergent approach. In the resultant AIE macromolecules, up to twenty‐one AIEgens located at the tails of each branches, thus making them the first successful example of AIEgen‐branched dendrimers. Attributed to the solvent‐induced switching feature of the rotaxane branches, the integrated rotaxane dendrimers displayed interesting dynamic feature upon the aggregation‐induced emission (AIE) process. Moreover, novel artificial light‐harvesting systems were further constructed based on these AIEgen‐branched rotaxane dendrimers, which revealed impressive generation‐dependent photocatalytic performances for both photooxidation reaction and aerobic cross‐dehydrogenative coupling (CDC) reaction. [ABSTRACT FROM AUTHOR]

2D conjugated metal–organic frameworks (2D c‐MOFs) are emerging as electroactive materials for chemiresistive sensors, but selective sensing with fast response/recovery is a challenge. Phthalocyanine‐based Ni2[MPc(NH)8] 2D c‐MOF films are presented as active layers for polarity‐selective chemiresisitors toward water and volatile organic compounds (VOCs). Surface‐hydrophobic modification by grafting aliphatic alkyl chains on 2D c‐MOF films decreases diffused analytes into the MOF backbone, resulting in a considerably accelerated recovery progress (from ca. 50 to ca. 10 s) during humidity sensing. Toward VOCs, the sensors deliver a polarity‐selective response among alcohols but no signal for low‐polarity aprotic hydrocarbons. The octadecyltrimethoxysilane‐modified Ni2[MPc(NH)8] based sensor displays high‐performance methanol sensing with fast response (36 s)/recovery (13 s) and a detection limit as low as 10 ppm, surpassing reported room‐temperature chemiresistors. [ABSTRACT FROM AUTHOR]

Layered double hydroxides (LDHs) are among the most active and studied catalysts for the oxygen evolution reaction (OER) in alkaline electrolytes. However, previous studies have generally either focused on a small number of LDHs, applied synthetic routes with limited structural control, or used non‐intrinsic activity metrics, thus hampering the construction of consistent structure–activity‐relations. Herein, by employing new individually developed synthesis strategies with atomic structural control, we obtained a broad series of crystalline α‐MA(II)MB(III) LDH and β‐MA(OH)2 electrocatalysts (MA=Ni, Co, and MB=Co, Fe, Mn). We further derived their intrinsic activity through electrochemical active surface area normalization, yielding the trend NiFe LDH > CoFe LDH > Fe‐free Co‐containing catalysts > Fe‐Co‐free Ni‐based catalysts. Our theoretical reactivity analysis revealed that these intrinsic activity trends originate from the dual‐metal‐site nature of the reaction centers, which lead to composition‐dependent synergies and diverse scaling relationships that may be used to design catalysts with improved performance. [ABSTRACT FROM AUTHOR]

We report herein a facile and generalized approach to the modification of solid surfaces with polymer brushes under ambient conditions: filter paper‐assisted surface‐initiated Cu0‐mediated controlled radical polymerization (PSI‐CuCRP). The polymerization solution wetted filter paper is sandwiched between a copper plate and an initiator‐modified substrate, which allows the creation of a surface‐initiated polymerization (SIP) "band‐aid" so that everyone can perform the surface grafting selectively with good control over the quality of the polymer brushes employing low concentration and microliter amounts of the monomer solution. The versatility of this method is demonstrated by grafting different homo‐, block‐, and multicomponent polymer brushes by using the same activation system and reaction conditions, the polymerization process can be precisely controlled to yield uniform polymers and show high chain‐end functionality which is exemplified by in situ tetra‐copolymerization. The combination of photolithography and paper cutting enables to prepare arbitrary three‐dimensional patterned polymer brushes on the surface. [ABSTRACT FROM AUTHOR]