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The in‐depth understanding of the composition‐property‐performance relationship of solid electrolyte interphase (SEI) is the basis of developing a reliable SEI to stablize the Zn anode‐electrolyte interface, but it remains unclear in rechargeable aqueous zinc ion batteries. Herein, a well‐designed electrolyte based on 2 M Zn(CF3SO3)2‐0.2 M acrylamide‐0.2 M ZnSO4 is proposed. A robust polymer (polyacrylamide)‐inorganic (Zn4SO4(OH)6.xH2O) hybrid SEI is in situ constructed on Zn anodes through controllable polymerization of acrylamide and coprecipitation of SO42− with Zn2+ and OH−. For the first time, the underlying SEI composition‐property‐performance relationship is systematically investigated and correlated. The results showed that the polymer‐inorganic hybrid SEI, which integrates the high modulus of the inorganic component with the high toughness of the polymer ingredient, can realize high reversibility and long‐term interfacial stability, even under ultrahigh areal current density and capacity (30 mA cm−2~30 mAh cm−2). The resultant Zn||NH4V4O10 cell also exhibits excellent cycling stability. This work will provide a guidance for the rational design of SEI layers in rechargeable aqueous zinc ion batteries. [ABSTRACT FROM AUTHOR]

Integrating aggregation‐induced emission (AIE) into thermally activated delayed fluorescence (TADF) emitters holds great promise for the advancement of highly efficient organic light emitting diodes (OLEDs). Despite recent advancements, a thorough comprehension of the underlying mechanisms remains imperative for the practical application of such materials. In this work, we introduce a novel approach aimed at modulating the TADF process by manipulating dynamic processes in excited states through aggregation effect. Our findings reveal that aggregation not only enhances both prompt and delayed fluorescence simultaneously but also imposes constraints on molecular reorientation. This constraint reinforces spin‐orbit coupling and reduces the energy gap between singlets and triplets. These insights deepen our understanding of the fundamental mechanisms governing the aggregation effect on TADF materials and provide valuable guidance for the design of high‐efficiency photoluminescent materials. [ABSTRACT FROM AUTHOR]

Transforming polyolefin waste into liquid alkanes through tandem cracking‐alkylation reactions catalyzed by Lewis‐acid chlorides offers an efficient route for single‐step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low‐density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline‐range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000 gLDPEmolcat-1h-1 ${{{\rm g}}_{{\rm L}{\rm D}{\rm P}{\rm E}}{{\rm \ }{\rm m}{\rm o}{\rm l}}_{{\rm c}{\rm a}{\rm t}}^{-1}{{\rm \ }{\rm h}}^{-1}}$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity. [ABSTRACT FROM AUTHOR]

Aptamer‐based probes are pivotal components in various sensing strategies, owing to their exceptional specificity and versatile programmable structure. Nevertheless, numerous aptamer‐based probes usually offer only a single function, limiting their capacity to meet the diverse requirements of multi‐faceted sensing systems. Here, we introduced supersandwich DNA probes (SSW‐DNA), designed and modified on the outer surface of nanochannels with hydrophobic inner walls, enabling dual functionality: qualitative detection for on‐site analysis and quantitative detection for precise analysis. The fragmented DNAs resulting from the target recognition, are subsequently identified through lateral flow assays, enabling robust on‐site qualitative detection of microcystin‐LR with an impressively low limit of detection (LOD) at 0.01 μg/L. Meanwhile, the nanochannels enable highly sensitive quantification of microcystin‐LR through the current analysis, achieving an exceptionally low LOD at 2.5×10−7 μg/L, with a broad dynamic range spanning from 1×10−6 to 1×102 μg/L. Furthermore, the process of target recognition introduces just a single potential error propagation, which reduces the overall risk of errors during the entire qualitative and quantitative detection process. This sensing strategy broadens the scope of applications for aptamer‐based composite probes, holding promising implications across diverse fields, such as medical diagnosis, food safety, and environmental protection. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

The development of flexible, room‐temperature phosphorescence (RTP) materials remains challenging owing to the quenching of their unstable triplet excitons via molecular motion. Therefore, a polymer matrix with Tg higher than room temperature is required to prevent polymer segment movement. In this study, a RTP material was developed by incorporating a 4‐biphenylboronic acid (BPBA) phosphor into a poly(vinylidene fluoride) (PVDF) matrix (Tg=−27.1 °C), which exhibits a remarkable UV‐light‐dependent oxygen consumption phosphorescence with a lifetime of 1275.7 ms. The adjustable RTP performance is influenced by the crystallinity and polymorph (α, β, and γ phases) fraction of PVDF, therefore, the low Tg of the PVDF matrix enables the polymeric segmental motion upon microwave irradiation. Consequently, a reduction in the crystallinity and an increase in the α phase fraction in PVDF film induces RTP after 2.45 GHz microwave irradiation. These findings open up new avenues for constructing crystalline and phase‐dependent RTP materials while demonstrating a promising approach toward microwave detection. [ABSTRACT FROM AUTHOR]

Eco‐friendly lead‐free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo‐2D layered OIMH (MTP)2MnBr4 (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X‐ray excitation, with a near‐unity photoluminescence quantum yield, high resistance to thermal quenching (I150 °C=84.1 %) and good photochemical stability. These features enable (MTP)2MnBr4 as an efficient green phosphor for blue‐converted white light‐emitting diodes, demonstrating a commercial‐level luminous efficiency of 101 lm W−1 and a wide color gamut of 116 % NTSC. Moreover, these (MTP)2MnBr4 crystals showcase outstanding X‐ray scintillation properties, delivering a light yield of 67000 photon MeV−1, a detection limit of 82.4 nGy s−1, and a competitive spatial resolution of 6.2 lp mm−1 for X‐ray imaging. This work presents a new avenue for the exploration of eco‐friendly luminescent OIMHs towards multifunctional light‐emitting applications. [ABSTRACT FROM AUTHOR]

Carboxylation of easily available alkenes with CO2 is highly important to afford value‐added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3‐dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1,n‐dienes (n>3) with CO2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO2 to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) with encapsulated nanoparticles (NPs) enjoy a vastly expanded application potential in catalysis, filtration, and sensing. The selection of particular modified core‐NPs has yielded partial successes in overcoming lattice mismatch. However, restrictions on the choice of NPs not only limit the diversity, but also affect the properties of the hybrid materials. Here, we show a versatile synthesis strategy using a representative set of seven MOF‐shells and six NP‐cores that are fine‐tuned to incorporate from single to hundreds of cores in mono‐, bi‐, tri‐ and quaternary composites. This method does not require the presence of any specific surface structures or functionalities on the pre‐formed cores. Our key point is to regulate the diffusion rate of alkaline vapors that deprotonate organic linkers and trigger the controlled MOF‐growth and encapsulation of NPs. This strategy is expected to pave the way for the exploration of more sophisticated MOF‐nanohybrids. [ABSTRACT FROM AUTHOR]

The catalytic bis‐allylation of alkynes is an important but challenging protocol to construct all‐carbon tetra‐substituted alkenes. Particularly, the catalytic unsymmetrical bis‐allylation of alkynes remains as an underexplored task to date. We herein report an unprecedented unsymmetrical bis‐allylation by simultaneously utilizing electrophilic trifluoromethyl alkene and nucleophilic allylboronate as the allylic reagents. With the aid of robust Ni0/NHC catalysis, valuable skipped trienes can be obtained in high regio‐ and stereo‐selectivities under mild conditions. Mechanistic studies indicate that the reaction may proceed through a β‐fluorine elimination of a nickelacycle followed by a transmetalation step with allylboronate. The present method exhibits a good tolerance of various functional groups. Besides, the skipped triene products can undergo an array of elaborate transformations, which highlights the potential applications of this strategy. [ABSTRACT FROM AUTHOR]

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to the success is the design and use of glycosyl sulfinates as radical precursors, which are bench‐stable solids and can be readily prepared from commercial starting materials. This development allows the installation of glycosyl units onto pyridine rings directly by the Minisci reaction. We further demonstrate the utility of this method in the late‐stage modification of complex drug molecules, including the anticancer agent camptothecin. Experimental studies provide insight into the reaction mechanism. [ABSTRACT FROM AUTHOR]

Flavonoids are important plant natural products with variable structures and bioactivities. All known plant flavonoids are generated under the catalysis of a type III polyketide synthase (PKS) followed by a chalcone isomerase (CHI) and a flavone synthase (FNS). In this study, the biosynthetic gene cluster of chlorflavonin, a fungal flavonoid with acetolactate synthase inhibitory activity, was discovered using a self‐resistance‐gene‐directed strategy. A novel flavonoid biosynthetic pathway in fungi was revealed. A core nonribosomal peptide synthetase‐polyketide synthase (NRPS‐PKS) is responsible for the generation of the key precursor chalcone. Then, a new type of CHI catalyzes the conversion of a chalcone into a flavanone by a histidine‐mediated oxa‐Michael addition mechanism. Finally, the desaturation of flavanone to flavone is catalyzed by a new type of FNS, a flavin mononucleotide (FMN)‐dependent oxidoreductase. [ABSTRACT FROM AUTHOR]

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe3(As3)3(As4)]3−, present in both [K([2.2.2]crypt)]3[Fe3(As3)3(As4)] (1) and [K(18‐crown‐6)]3[Fe3(As3)3(As4)]⋅en (2). The cluster contains an Fe3 triangle with three short Fe−Fe bond lengths (2.494(1) Å, 2.459(1) Å and 2.668(2) Å for 1, 2.471(1) Å, 2.473(1) Å and 2.660(1) Å for 2), bridged by a 2‐butene‐like As4 unit. An analysis of the electronic structure using DFT reveals a triplet ground state with direct Fe−Fe bonds stabilizing the Fe3 core. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries have drawn increasing attention due to the intrinsic safety, cost‐effectiveness and high energy density. However, parasitic reactions and non‐uniform dendrite growth on the Zn anode side impede their application. Herein, a multifunctional additive, ammonium dihydrogen phosphate (NHP), is introduced to regulate uniform zinc deposition and to suppress side reactions. The results show that the NH4+ tends to be preferably absorbed on the Zn surface to form a "shielding effect" and blocks the direct contact of water with Zn. Moreover, NH4+ and (H2PO4)− jointly maintain pH values of the electrode‐electrolyte interface. Consequently, the NHP additive enables highly reversible Zn plating/stripping behaviors in Zn//Zn and Zn//Cu cells. Furthermore, the electrochemical performances of Zn//MnO2 full cells and Zn//active carbon (AC) capacitors are improved. This work provides an efficient and general strategy for modifying Zn plating/stripping behaviors and suppressing side reactions in mild aqueous electrolyte. [ABSTRACT FROM AUTHOR]

Total syntheses of (+)‐cinereain and (−)‐janoxepin, two fungal cyclotripeptides featuring a complex heterocyclic core and interesting phytotoxic and antimalarial activities, have been achieved in a convergent manner. A key step in this synthesis is a one‐pot cascade initiated by the cyclocondensation of two fragments—a hindered 2‐vinylcyclopropane‐1‐acyl fluoride and an electron‐deficient cyclic amidine—to release a reactive spiro[2‐vinylcyclopropane‐1,5′‐pyrimidine‐4′,6′‐dione]. This intermediate underwent a spontaneous retro‐Claisen rearrangement that was rationalized by DFT calculations. The cascade directly afforded a 2,5‐dihydrooxepin‐fused heterotricyclic product, and the challenging oxepin ring was finally forged by the palladium‐catalyzed β‐hydride elimination of an allylic fluoride intermediate. [ABSTRACT FROM AUTHOR]

Aqueous zinc metal batteries (AZMBs) are deemed a promising technology for electrochemical energy storage due to their high safety, low cost, and high energy density. However, AZMBs still suffer from severe side reactions, including Zn dendrite formation and intrinsic hydrogen evolution reaction. In contrast to the solid‐electrolyte interphase (SEI) layer that stabilizes Li/Na/K metal anodes in organic electrolytes, it is difficult to form an SEI layer on the Zn surface because of the difficulty in decomposing the salt anions within the narrow electrochemical potential window of water. A team from the University of Adelaide reports a novel pure or hybrid electrolyte with H2O by using dimethyl methylphosphonate (DMMP) as solvent or co‐solvent to construct a uniform and stable phosphate‐based SEI layer (ZnP2O6 and Zn3(PO4)2). As a result, high Coulombic efficiencies and improved capacity retentions are obtained. [ABSTRACT FROM AUTHOR]

Luminescent metal halides have attracted considerable attention in next‐generation solid‐state lighting because of their superior optical properties and easy solution processibility. Herein, we report a new class of highly efficient and dual‐band‐tunable white‐light emitters based on Bi3+/Te4+ co‐doped perovskite derivative Cs2SnCl6 microcrystals. Owing to the strong electron‐phonon coupling and efficient energy transfer from Bi3+ to Te4+, the microcrystals exhibited broad dual‐band white‐light emission originating from the inter‐configurational 3P0,1→1S0 transitions of Bi3+ and Te4+, with good stability and a high photoluminescence (PL) quantum yield of up to 68.3 %. Specifically, a remarkable transition in Bi3+‐PL lifetime from milliseconds at 10 K to microseconds at 300 K was observed, as solid evidence for the isolated Bi3+ emission. These findings provide not only new insights into the excited‐state dynamics of Bi3+ and Te4+ in Cs2SnCl6, but also a general approach to achieve single‐composition white‐light emitters based on lead‐free metal halides through ns2‐metal ion co‐doping. [ABSTRACT FROM AUTHOR]

A recent research article published in Angewandte Chemie International Edition describes the development of a multi-function biosensing system for on-site detection. The system utilizes supersandwich DNA probes and solid-state nanochannels with hydrophobic partition modification. By introducing fluorescent molecules on the DNA probes and using test strips, the system achieves qualitative and ultra-sensitive quantitative detection. The authors highlight that the system reduces the risk of errors by involving only one target identification process. The research was conducted by Yu Huang, Fan Xia, and their team. [Extracted from the article]

Metal halide perovskite materials (MHPMs) have attracted significant attention because of their superior optoelectronic properties and versatile applications. The power conversion efficiency of MHPM solar cells (PSCs) has skyrocketed to 25.5 %. Although the performance of PSCs is already competitive, several important challenges still need to be solved to realize commercial applications. A thorough understanding of surface atomic structures and structure–property relationships is at the heart of these remaining issues. Scanning tunneling microscopy (STM) and spectroscopy (STS) can be used to characterize the surface properties of MHPMs, which can offer crucial insights into MHPMs at the atomic scale. This Review summarizes recent progress in STM and STS studies on MHPMs, with a focus on the surface properties. We provide understanding from the comparative perspective of several different MHPMs. We also highlight a series of novel phenomena observed by STM and STS. Finally, we outline a few research topics of primary importance for future studies. [ABSTRACT FROM AUTHOR]

The electrochemical reduction of CO2 to hydrocarbons involves a multistep proton‐coupled electron transfer (PCET) reaction. Second coordination sphere engineering is reported to be effective in the PCET process; however, little is known about the actual catalytic active sites under realistic operating conditions. We have designed a defect‐containing metal–organic framework, HKUST‐1, through a facile "atomized trimesic acid" strategy, in which Cu atoms are modified by unsaturated carboxylate ligands, producing coordinatively unsaturated Cu paddle wheel (CU−CPW) clusters. We investigate the dynamic behavior of the CU−CPW during electrochemical reconstruction through the comprehensive analysis of in situ characterization results. It is demonstrated that Cu2(HCOO)3 is maintained after electrochemical reconstruction and that is behaves as an active site. Mechanistic studies reveal that CU−CPW accelerates the proton‐coupled multi‐electron transfer (PCMET) reaction, resulting in a deep CO2 reduction reaction. [ABSTRACT FROM AUTHOR]

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light‐induced instability and the difficulty of utilizing the photogenerated carriers for photocatalysis pose significant challenges. Here, MAg24 (M=Ag, Pd, Pt, and Au) NCs doped with diverse single heteroatoms have been encapsulated in a metal–organic framework (MOF), UiO‐66‐NH2, affording MAg24@UiO‐66‐NH2. Strikingly, compared with Ag25@UiO‐66‐NH2, the MAg24@UiO‐66‐NH2 doped with heteroatom exhibits much enhanced activity in photocatalytic hydrogen production, among which AuAg24@UiO‐66‐NH2 presents the best activity up to 3.6 mmol g−1 h−1, far superior to all other counterparts. Moreover, they display excellent photocatalytic recyclability and stability. X‐ray photoelectron spectroscopy and ultrafast transient absorption spectroscopy demonstrate that MAg24 NCs encapsulated into the MOF create a favorable charge transfer pathway, similar to a Z‐scheme heterojunction, when exposed to visible light. This promotes charge separation, along with optimized Ag electronic state, which are responsible for the superior activity in photocatalytic hydrogen production. [ABSTRACT FROM AUTHOR]

Due to multidrug resistance and the high risk of recurrence, effective and less toxic alternative pancreatic cancer treatments are urgently needed. Pancreatic cancer cells are highly resistant to apoptosis but sensitive to ferroptosis. In this study, an innovative nanoplatform (AsIr@PDA) was developed by electrostatic adsorption of a cationic iridium complex (IrFN) onto two‐dimensional (2D) arsenene nanosheets. This nanoplatform exhibits superior ferroptosis‐inducing effects with high drug loading capacity and, importantly, excellent anti‐cancer immune activation function, leading to efficient elimination of pancreatic tumors with no observable side effects. Interestingly, AsIr@PDA significantly prevents the recurrence of pancreatic cancer in vivo when compared with a cisplatin‐loaded nanoplatform. This designed nanoplatform demonstrated superior therapeutic efficacy by synergistic ferroptosis‐induced chemotherapy with immunotherapy via an all‐in‐one strategy, providing new insights for future pancreatic cancer therapy. [ABSTRACT FROM AUTHOR]

Hot electrons activate reactants and reduce the activation energy barrier (Ea) of a reaction through electron donation. However, a comprehensive understanding of the intrinsic driving force of this electron‐donating effect is lacking, let alone the precise manipulation of electron donation processes. Herein, the essential and promotional role of hot electron energy on the electron‐donating effect was elucidated using molecular oxygen activation (MOA) as a model reaction. Through providing an available electron source to the conventional photo‐thermal conversion system, the high energy carried by hot electrons was liberated and greatly enhanced the electron donation towards the LUMO (π*) orbit of O2. The energy was also transferred to O2 and elevated the potential energy surface (PES) of MOA, which was reflected by the enhanced formation of superoxide oxygen anions. As predicted, the Ea of MOA decreased by 45.1 % and exhibited a substantial light dependence, demonstrating that MOA became energy‐efficient due to improved exploitation and conversion of photon energies. [ABSTRACT FROM AUTHOR]

Dynamic and on‐site analysis of serum from human blood is crucial, however, state‐of‐the‐art blood‐assay methods can only collect single or discrete data of physiological analytes; thus, the online reports of the dynamic fluctuation of key analytes remains a great challenge. Here, we propose a novel separation‐sensing membrane by constructing a heterogeneous‐nanostructured architecture, wherein a surface nanoporous layer continuously extracts serum, while the biosensing nanochannels underneath dynamically recognise biotargets, thereby achieving a continuous testing of vital clinical indices as blood is drawn. By precisely controlling the pore structure and nanoshape of biosensing crystals, this membrane achieved accurate and online glucose and lactate monitoring in patients with a variety of medical conditions within 1 min, which is one order of magnitude faster than state‐of‐the‐art techniques. Moreover, various kinds of bio‐recognisers can be introduced into this membrane to accurately detect glutamate, transaminase, and cancer biomarkers. [ABSTRACT FROM AUTHOR]

Full quantum mechanical (FQM) calculation of the excited state of aggregation‐induced‐emission (AIE) materials is highly sought but still a challenging task. Herein, we employed the recently developed electrostatically embedded generalized molecular fractionation (EE‐GMF) method, a method based on the systematic fragmentation approach, to predict, for the first time, the spectra of a prototype AIE fluorophore: di(p‐methoxylphenyl)dibenzofulvene (FTPE). Compared to the single molecular or QM/MM calculations, the EE‐GMF method shows significantly improved accuracy, nearly reproducing the experimental optical spectra of FTPE in both condensed phases. Importantly, we show that the conventional restriction of the intramolecular rotation mechanism cannot fully account for AIE, whereas the two‐body intermolecular quantum mechanical interaction plays a crucial role in AIE. [ABSTRACT FROM AUTHOR]

Azaphilones are a family of fungal polyketide metabolites with diverse chemical structures and biological activities with a highly oxygenated pyranoquinone bicyclic core. Here, a class of azaphilones possessing a 6/6/6/6 tetracyclic ring system was identified in Aspergillus terreus, and exhibited potential anticancer activities. The gene deletions and biochemical investigations demonstrated that these azaphilones were collaboratively synthesized by two separate clusters containing four core‐enzymes, two nonreducing PKSs, one highly reducing PKS, and one NRPS‐like. More interestingly, we found that the biosynthesis is coordinately regulated by a crosstalk mechanism between these two gene clusters based on three transcriptional factors. This is a meaningful mechanism of fungal secondary metabolism, which allows fungi to synthesize more complex compounds and gain new physiological functions. The results provide a new insight into fungal natural product biosynthesis. [ABSTRACT FROM AUTHOR]

Harvesting energy directly in oceans by electrochemical devices is essential for driving underwater appliances such as underwater vehicles or detectors. Owing to the extreme undersea environment, it is important but difficult to use the devices with both a high energy density and power density simultaneously. Inspired by marine organisms that have switchable energy extraction modes (aerobic respiration for long‐term living or anaerobic respiration to provide instantaneously high output power for fast movement), an auto‐switchable dual‐mode seawater energy extraction system is presented to provide high energy density and power density both by initiatively choosing different solutes in seawater as electron acceptors. With assistance from metal–organic frameworks, this device had a theoretical energy density of 3960 Wh kg−1, and a high practical power density of 100±4 mW cm−2 with exceptional stability and low cost, making practical applications in seawater to be possible. [ABSTRACT FROM AUTHOR]

In photodynamic therapy (PDT), the level of reactive oxygen species (ROS) produced in the cell directly determines the therapeutic effect. Improvement in ROS concentration can be realized by reducing the glutathione (GSH) level or increasing the amount of photosensitizer. However, excessive amounts photosensitizer may cause side effects. Therefore, the development of photosensitizers that reduce GSH levels through synergistically improving ROS concentration in order to strengthen the efficacy of PDT for tumor is important. We report a nano‐metal–organic framework (CuII‐metalated nano‐MOF {CuL‐[AlOH]2}n (MOF‐2, H6L=mesotetrakis(4‐carboxylphenyl)porphyrin)) based on CuII as the active center for PDT. This MOF‐2 is readily taken up by breast cancer cells, and high levels of ROS are generated under light irradiation. Meanwhile, intracellular GSH is considerably decreased owing to absorption on MOF‐2; this synergistically increases ROS concentration and accelerates apoptosis, thereby enhancing the effect of PDT. Notably, based on the direct adsorption of GSH, MOF‐2 showed a comparable effect with the commercial antitumor drug camptothecin in a mouse breast cancer model. This work provides strong evidence for MOF‐2 as a promising new PDT candidate and anticancer drug. [ABSTRACT FROM AUTHOR]

Although controlling the primary structure of synthetic polymers is itself a great challenge, the potential of sequence control for tailoring hierarchical structures remains to be exploited, especially in the creation of new and unconventional phases. A series of model amphiphilic chain-like giant molecules was designed and synthesized by interconnecting both hydrophobic and hydrophilic molecular nanoparticles in precisely defined sequence and composition to investigate their sequence-dependent phase structures. Not only compositional variation changed the self-assembled supramolecular phases, but also specific sequences induce unconventional phase formation, including Frank-Kasper phases. The formation mechanism was attributed to the conformational change driven by the collective hydrogen bonding and the sequence-mandated topology of the molecules. These results show that sequence control in synthetic polymers can have a dramatic impact on polymer properties and self-assembly. [ABSTRACT FROM AUTHOR]

Monitoring the early stage of atherosclerosis (AS) without plaque formation is of great significance. Herein, we developed a metal organic framework (MOF)‐based fluorescence nanoprobe to analyze the progression of AS by assessing the levels of protein phosphorylation and glucose in blood and tissue. The probe was prepared by post‐modification of the MOF with iodine (I3−)‐rhodamine B (RhB) associate, which realizes the specific recognition of target object through the metal joint ZrIV and I3−‐RhB, respectively. We investigated different stages of target object changes in the early non‐plaque stage of AS in blood. It was found that the levels of phosphate and glucose in the blood were higher than those of the normal mice. The results of two‐photon images showed that early AS mice had higher levels of protein phosphorylation and glucose than that of the normal mice. The present study provides a suitable fluorescence tool for further revealing the pathogenesis and progression of AS. [ABSTRACT FROM AUTHOR]

Three-dimensional (3D) networks of graphitic carbon are promising materials for energy storage and conversion devices because of their high electrical conductivity, which is promoted by the good interconnection between the carbon particles. However, it is still difficult to directly synthesize such carbon networks. Herein, we report the novel synthesis of 3D graphitic carbon networks through the pyrolysis of nanosized ZIF-67 crystals. Interestingly, the unusual effect of downsizing the ZIF-67 crystals and the incorporation of catalytic Co nanoparticles was the spontaneous formation of graphitic networks. The obtained graphitic carbon networks show excellent electrochemical performance for the insertion and extraction of potassium ions. [ABSTRACT FROM AUTHOR]

Ansellane-type sesterterpenoids including, ansellones A-G and (+)-phorbadione are structurally novel marine secondary metabolites which exhibit anticancer and anti-HIV activity. The first, asymmetric total syntheses of three structurally representative members, (−)-ansellones A and B and (+)-phorbadione, were accomplished in 16-23 steps from (+)-sclareolide. The route features the first regioselective cyclization of vinyl epoxides with internal alcohol nucleophiles in a 1,4-addition manner (SN2′). Additionally, the allylic C−H oxidation was exploited at a late stage of the synthesis of (−)-ansellone A and (+)-phorbadione. This strategy is expected to be applicable to the synthesis of other ansellane sesterterpenoids. [ABSTRACT FROM AUTHOR]

Detailed understanding of the interaction between a chiral molecule and a noble metal surface is essential to rationalize and advance interfacial self-assembly of amino acids and metal-mediated anchoring of proteins. Here we demonstrate that individual Au@Ag core-shell nanocuboids can serve as a plasmonic reporter of an extended helical network formed among chemisorbed cysteine molecules, through generating an interband absorption enhanced, Ag-surface-exclusive circular dichroism (CD) band in the UV region. The observed unusual, strong CD response in the hybrid Au@Ag-cysteine system can be used to probe in real time conformational evolution and structural rearrangement of biomolecules in general and also monitor the interfacial interaction between a metal surface and an adsorbed molecule, opening up the possibility of using Ag nanostructures as promising stereochemically attuned nanosensors. [ABSTRACT FROM AUTHOR]

Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic‐level Zn deposition. Here, based on underpotential deposition (UPD), we propose an "escort effect" of electrolyte additives for uniform Zn deposition at the atomic level. With nickel ion (Ni2+) additives, we found that metallic Ni deposits preferentially and triggers the UPD of Zn on Ni. This facilitates firm nucleation and uniform growth of Zn while suppressing side reactions. Besides, Ni dissolves back into the electrolyte after Zn stripping with no influence on interfacial charge transfer resistance. Consequently, the optimized cell operates for over 900 h at 1 mA cm−2 (more than 4 times longer than the blank one). Moreover, the universality of "escort effect" is identified by using Cr3+ and Co2+ additives. This work would inspire a wide range of atomic‐level principles by controlling interfacial electrochemistry for various metal batteries. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) have great potential for large‐scale energy storage. Cellulose is an attractive material for sustainable separators, but some key issues still exist affecting its application. Herein, a cellulose‐based composite separator (CP@PPC) was prepared by immersion curing of cellulose‐based separators (CP) with poly(propylene carbonate) (PPC). With the assistance of PPC, the CP@PPC separator is able to operate the cell stably at high voltages (up to 4.95 V). The "pore‐hopping" ion transport mechanism in CP@PPC opens up extra Na+ migration paths, resulting in a high Na+ transference number (0.613). The separator can also tolerate folding, bending and extreme temperature under certain circumstances. Full cells with CP@PPC reveal one‐up capacity retention (96.97 %) at 2C after 500 cycles compared to cells with CP. The mechanism highlights the merits of electrolyte analogs in separator modification, making a rational design for durable devices in advanced energy storage systems. [ABSTRACT FROM AUTHOR]

Melt‐quenched glasses of organic–inorganic hybrid crystals, i.e., hybrid glasses, have attracted increasing attention as an emerging class of hybrid materials with beneficial processability and formability in the past years. Herein, we present a new hybrid crystal, (Ph3PEt)3[Ni(NCS)5] (1, Ph3PEt+=ethyl(triphenyl)phosphonium), crystallizing in a polar space group P1 and exhibiting thermal‐induced reversible crystal‐liquid‐glass‐crystal transitions with relatively low melting temperature of 132 °C, glass‐transition temperature of 40 °C, and recrystallization on‐set temperature of 78 °C, respectively. Taking advantage of such mild conditions, we fabricated an unprecedented hybrid glass‐ceramic thin film, i.e., a thin glass uniformly embedding inner polar micro‐crystals, which exhibits a much enhanced intrinsic second‐order nonlinear optical effect, being ca. 25.6 and 3.1 times those of poly‐crystalline 1 and KH2PO4, respectively, without any poling treatments. [ABSTRACT FROM AUTHOR]

In aqueous aluminum‐ion batteries (AAIBs), the insertion/extraction chemistry of Al3+ often leads to poor kinetics, whereas the rapid diffusion kinetics of hydronium ions (H3O+) may offer the solution. However, the presence of considerable Al3+ in the electrolyte hinders the insertion reaction of H3O+. Herein, we report how oxygen‐deficient α‐MoO3 nanosheets unlock selective H3O+ insertion in a mild aluminum‐ion electrolyte. The abundant oxygen defects impede the insertion of Al3+ due to excessively strong adsorption, while allowing H3O+ to be inserted/diffused through the Grotthuss proton conduction mechanism. This research advances our understanding of the mechanism behind selective H3O+ insertion in mild electrolytes. [ABSTRACT FROM AUTHOR]

Electrically conducting two‐dimensional (2D) metal–organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high‐performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched D3h symmetrical planar conjugated ligand, dodechydroxylhexabenzotrinaphthylene (DHHBTN) to fabricate a series of 2D conductive MOFs, named M–DHHBTN (M=Co, Ni, and Cu). This new family of MOFs offers two distinct types of pores, elevating the structural complexity of 2D conductive MOFs to a more advanced level. The intricate tessellation patterns of the M–DHHBTN are elucidated through comprehensive analyses involving powder X‐ray diffraction, theoretical simulations, and high‐resolution transmission electron microscope. Optical‐pump terahertz‐probe spectroscopic measurements unveiled carrier mobility in DHHBTN‐based 2D MOFs spanning from 0.69 to 3.10 cm2 V−1 s−1. Among M–DHHBTN famility, Cu‐DHHBTN displayed high electrical conductivity reaching 0.21 S cm−1 at 298 K with thermal activation behavior. This work leverages the "branched conjugation" of the ligand to encode heteroporosity into highly conductive 2D MOFs, underscoring the significant potential of heterogeneous double‐pore structures for future applications. [ABSTRACT FROM AUTHOR]

Nanozymes have demonstrated significant potential in combating malignant tumor proliferation through catalytic therapy. However, the therapeutic effect is often limited by insufficient catalytic performance. In this study, we propose the utilization of strain engineering in metallenes to fully expose the active regions due to their ultrathin nature. Here, we present the first report on a novel tensile strain‐mediated local amorphous RhRu (la‐RhRu) bimetallene with exceptional intrinsic photothermal effect and photo‐enhanced multiple enzyme‐like activities. Through geometric phase analysis, electron diffraction profile, and X‐ray diffraction, it is revealed that crystalline‐amorphous heterophase boundaries can generate approximately 2 % tensile strain in the bimetallene. The ultrathin structure and in‐plane strain of the bimetallene induce an amplified strain effect. Both experimental and theoretical evidence support the notion that tensile strain promotes multiple enzyme‐like activities. Functioning as a tumor microenvironment (TME)‐responsive nanozyme, la‐RhRu exhibits remarkable therapeutic efficacy both in vitro and in vivo. This work highlights the tremendous potential of atomic‐scale tensile strain engineering strategy in enhancing tumor catalytic therapy. [ABSTRACT FROM AUTHOR]

Naturally occurring polymeric structures often consist of 1D polymer chains intricately folded and entwined through non‐covalent bonds, adopting precise topologies crucial for their functionality. The exploration of crystalline 1D polymers through dynamic covalent chemistry (DCvC) and supramolecular interactions represents a novel approach for developing crystalline polymers. This study shows that sub‐angstrom differences in the counter‐ion size can lead to various helical covalent polymer (HCP) topologies, including a novel metal‐coordination HCP (m‐HCP) motif. Single‐crystal X‐ray diffraction (SCXRD) analysis of HCP−Na revealed that double helical pairs are formed by sodium ions coordinating to spiroborate linkages to form rectangular pores. The double helices are interpenetrated by the unreacted diols coordinating sodium ions. The reticulation of the m‐HCP structure was demonstrated by the successful synthesis of HCP−K. Finally, ion‐exchange studies were conducted to show the interconversion between HCP structures. This research illustrates how seemingly simple modifications, such as changes in counter‐ion size, can significantly influence the polymer topology and determine which supramolecular interactions dominate the crystal lattice. [ABSTRACT FROM AUTHOR]

Integrating controllable spin states into single‐molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d–4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4) ⋅ 4H2O (H2quinha=quinaldichydroxamic acid, HClsal=5‐chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post‐synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4) ⋅ 3H2O (HClsaldt=4‐chloro‐2‐(1,3‐dithiolan‐2‐yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination‐induced spin state switching (CISSS) took place with spin state altering from low‐spin S=0 to high‐spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm−1 to 423 cm−1, along with hysteresis opening and an over 200‐fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire‐new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach. [ABSTRACT FROM AUTHOR]

Novel hexa- peri-hexabenzocoronene (HBC) derivatives, FHBC and FHBC*, which carry perfluoroalkyl segments on one side of the HBC core and long alkyl tails on the other, were synthesized. Their perfluoroalkyl segments are highly solvated in C6F6 (solvophilic effect) and do not assemble, whereas in CH2Cl2, they are excluded (solvophobic effect) and assemble together consequently. For example, the use of C6F6 and CH2Cl2 as assembling media for FHBC leads to the selective formation of single- and multi-walled nanotubes, respectively. When a higher monomer concentration is applied in CH2Cl2, multi-walled nanotubes with a larger number of walls result. FHBC in CH2Cl2 self-assembles rather slowly, thereby allowing for the observation of coil-on-tube structures, which are possible intermediates for the stepwise radial growth of the nanotubular wall. Casting of the multi-walled nanotubes onto a quartz plate yields a superhydrophobic thin film with a water contact angle of 161±2°. [ABSTRACT FROM AUTHOR]

The inflammatory microenvironment involves changes in pH and protein phosphorylation state and is closely related to the occurrence and development of atherosclerosis (AS). Herein, we constructed a dual‐detection fluorescence nanosensor PCN‐NP‐HPZ based on post modification of MOFs, which realized the simultaneous detection and imaging of pH and phosphorylation through the pH‐sensitive group piperazine and the ZrIV node of the MOFs. The sensors were used to monitor changes in blood pH and phosphate levels at different time stages during atherosclerotic plaque formation. Two‐photon fluorescence imaging was also performed in the vascular endothelium. Blood tests combined with two‐photon fluorescence images indicated that in the early stage of AS, blood and tissue pH levels were lower than that of the normal mice, while phosphate and tissue phosphorylation levels were higher than that of the normal mice. The present study provides a new analysis method for the assessment of early atherosclerotic disease. [ABSTRACT FROM AUTHOR]

Coherent light signals generated at the nanoscale are crucial to the realization of photonic integrated circuits. Self-assembled nanowires from organic dyes can provide both a gain medium and an effective resonant cavity, which have been utilized for fulfilling miniaturized lasers. Excited-state intramolecular proton transfer (ESIPT), a classical molecular photoisomerization process, can be used to build a typical four-level system, which is more favorable for population inversion. Low-power driven lasing in proton-transfer molecular nanowires with an optimized ESIPT energy-level process has been achieved. With high gain and low loss from the ESIPT, the wires can be applied as effective FP-type resonators, which generated single-mode lasing with a very low threshold. The lasing wavelength can be reversibly switched based on a conformation conversion of the excited keto form in the ESIPT process. [ABSTRACT FROM AUTHOR]

Forming uniform metal oxide nanocoatings is a well-known challenge in the construction of core-shell type nanomaterials. Herein, by using buffer solution as a specific reaction medium, we demonstrate the possibility to grow thin nanoshells of metal oxides, typically Al2O3, on different kinds of core materials, forming a uniform surface-coating layer with thicknesses achieving one nanometer precision. The application of this methodology for the surface modification of LiCoO2 shows that a thin nanoshell of Al2O3 can be readily tuned on the surface for an optimized battery performance. [ABSTRACT FROM AUTHOR]

Despite its simple chemical constitution and unparalleled technological importance, the phase-change material germanium telluride (GeTe) still poses fundamental questions. In particular, the bonding mechanisms in amorphous GeTe have remained elusive to date, owing to the lack of suitable bond-analysis tools. Herein, we introduce a bonding indicator for amorphous structures, dubbed 'bond-weighted distribution function' (BWDF), and we apply this method to amorphous GeTe. The results underline a peculiar role of homopolar GeGe bonds, which locally stabilize tetrahedral fragments but not the global network. This atom-resolved (i.e., chemical) perspective has implications for the stability of amorphous 'zero bits' and thus for the technologically relevant resistance-drift phenomenon. [ABSTRACT FROM AUTHOR]

The quest of the active species in copper‐mediated difluoromethylation of aryl halides led to the discovery of a powerful difluoromethylating reagent [Ph4P]+[Cu(CF2H)2]−2. Complex 2 was able to difluoromethylate a variety of electrophiles including electron‐deficient and electron‐rich aryl iodides, heteroaryl iodides, activated heteroaryl bromides, chloride and aryl bromides with a directing group, as well as other electrophiles such as alkenyl iodide, benzyl bromides, allyl bromides, alkyl iodide, allyl carbonates and acid chloride. In addition, in the presence of an oxidant, complex 2 reacted with various lithium nbutyl arylboronic acid pinacol esters, alkyne and heteroarene. Moreover, complex 2 could transmetalate the difluoromethyl reagent to other metals such as [Ph4P]+[CuCl2]− and [(DPPF)PdCl2]. [ABSTRACT FROM AUTHOR]

Revealing the dynamic processes at the electrode–solution interface is imperative for understanding electrochemical phenomena. Most techniques have been developed to sense the electrode surface changes at the nanoscale, but provide limited information on potential‐induced interfacial ion redistribution at the mesoscale. Herein, we present an in operando visualization method utilizing a microfabricated electrochemical cell combined with a laser scanning confocal microscope to observe high‐resolution and fast‐response interfacial processes. We report potential‐induced formation and transformation of the Nernst diffusion layer, demonstrating that pulsed voltage dynamically perturbs the interface and promotes ion diffusion. This provides an additional insight into developing a dynamic manipulation method to control the electrochemical process. Our novel visualization method can easily be applied to monitor different ionic behaviors in electrochemical reactions at the mesoscale. [ABSTRACT FROM AUTHOR]

A symbiosis of advanced scanning probe and electron microscopy and a well-defined model system may provide a detailed picture of interfaces on nanostructured catalytic systems. This was demonstrated for Pt nanoparticles supported on iron oxide thin films which undergo encapsulation by supporting oxide as a result of strong metal-support interactions. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescence (CPL) plays a pivotal role in cutting‐edge display and information technologies. Currently achieving precise color control and dynamic signal regulation in CPL still remains challenging due to the elusory relationship between fluorescence and chirality. Inspired by the natural mechanisms governing color formation and chiral interaction, we proposed an addition‐subtraction principle theory to address this issue. Three fluorene‐based polymers synthesized by Suzuki polycondensation with different electron‐deficient monomers exhibit similar structures and UV/Vis absorption, but distinct fluorescence emissions due to intramolecular charge transfer. Based on this, precise‐color CPL‐active films are obtained through quantitative supramolecular co‐assembly directed by addition principle. Particularly, an ideal white‐emitting CPL film (CIE coordinates: (0.33, 0.33)) is facilely fabricated with a high quantum yield of 80.8 % and a dissymmetry factor (glum) of 1.4×10−2. Structural analysis reveals that the ordered stacking orientation favors higher glum. Furthermore, to address the dynamically regulated challenge, the comparable subtraction principle is proposed, involving a contactless chiral communication between excited and ground states. The representative system consisting of as‐prepared fluorene‐based polymers and chirality‐selective absorption azobenzene (Azo)‐containing polymers is constructed, achieving CPL weakening, reversal, and enhancement. Finally, a switchable quick response code is realized based on trans‐cis isomerization of Azo moiety. [ABSTRACT FROM AUTHOR]