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By synergistically employing four key strategies: (I) introducing tetraphenylethylene groups as the central core unit with aggregation‐induced emission (AIE) properties, (II) optimizing the π‐conjugated length by extending the building block branches, (III) incorporating flexible groups containing ethylenic bonds, and (IV) applying crystal engineering to attain dense stacking mode and highly twisty conformation, we successfully synthesized a series of hydrogen‐bonded organic frameworks (HOFs) exhibiting exceptional one/two‐photon excited fluorescence. Notably, when utilizing the fluorescently superior building block L2, HOF‐LIFM‐7 and HOF‐LIFM‐8 exhibiting high quantum yields (QY) of 82.1 % and 77.1 %, and ultrahigh two‐photon absorption (TPA) cross‐sections of 148959.5 GM and 123901.1 GM were achieved. These materials were successfully employed in one and two‐photon excited lysosome‐targeting cellular imaging. It is believed that this strategy, combining building block optimization and crystal engineering, holds significant potential for guiding the development of outstanding fluorescent HOF materials. [ABSTRACT FROM AUTHOR]

Piezo‐catalytic self‐Fenton (PSF) system has been emerging as a promising technique for wastewater treatment, while the competing O2 reductive hydrogen peroxide (H2O2) production and FeIII reduction seriously limited the reaction kinetics. Here, we develop a two‐electron water oxidative H2O2 production (WOR−H2O2) coupled with FeIII reduction over a FeIII/BiOIO3 piezo‐catalyst for highly efficient PSF. It is found that the presence of FeIII can simultaneously initiate the WOR−H2O2 and reduction of FeIII to FeII, thereby enabling a rapid reaction kinetics towards subsequent Fenton reaction of H2O2/FeII. The FeIII initiating PSF system offers exceptional self‐recyclable degradation of pollutants with a degradation rate constant for sulfamethoxazole (SMZ) over 3.5 times as that of the classic FeII‐PSF system. This study offers a new perspective for constructing efficient PSF systems and shatters the preconceived notion of FeIII in the Fenton reaction. [ABSTRACT FROM AUTHOR]

By designing a tetraphenylethylene (TPE)‐based AIEgen‐ligand with reduced symmetry, we obtained two alkaline‐earth metal‐based MOFs (LIFM‐102 and LIFM‐103) with dense packing structures and low porosity as proved by single‐crystal X‐ray diffraction and CO2 sorption data. Excitingly, the desolvated MOFs with rigid environment and reduced lattice free solvent exhibit high quantum yields (QY, 64.9 % and 79.4 %) and excellent two‐photon excited photoluminescence (TPA cross‐sections, 2946.6 GM and 2899.0 GM), while maintaining the external‐stimuli‐responsive properties suitable for anticounterfeit fields. The effect of ligand conformation was validated by comparing the structure and fluorescence properties of the samples before and after desolvation and further verified by theoretical calculations. This work expands the study on TPE‐cored materials to symmetry‐reduced ligand and might bring forward novel structures and excellent photoluminescent properties in the future. [ABSTRACT FROM AUTHOR]

Hierarchical zeolites integrating intrinsic micropores with secondary meso‐ and/or macropores afford superior catalytic properties for enhanced mass transportation and more accessible active sites. The mesopores generated by using mesoporogens or framework etching are usually irregular with abundant defective sites and low hydrothermal stability. Here, using protozeolite nanoparticles as seeds, we succeeded in the synthesis of single‐crystalline hierarchical ZSM‐5 zeolites with hexagonal mesopores faceted by complete microporous frameworks. The protozeolites played a key role in the formation of faceted mesopores achieved via intraparticle ripening process. Thanks to the unique texture properties and more accessible acid sites at the open location, the as‐prepared zeolites exhibited remarkedly long lifetime (18 h) and high propylene selectivity (52.7 %) with propylene/ethylene ratio of 3.64 in the methanol‐to‐propylene reaction (WHSV=12.5 h−1) compared to the counterparts. [ABSTRACT FROM AUTHOR]

Organic LPL (long‐persistent luminescence) materials have sparked extensive research interest due to the ultralong‐lived triplet states. Although numerous organic LPL materials have been reported, most of the triplet emission was static and monotonous. Therefore, LPL materials with dynamic triplet emission are urgently required. A triamino‐s‐triazine derivative 1 with dynamic LPL was fabricated. The single‐crystal structure shows that the abundant intermolecular interactions and small free volume restrict the molecular motion and avoid the quenchers. Spectral and theoretical calculations upheld the existence of multiple excited states in 1, and the migration of electrons between multiple excited states is very sensitive to external stimuli. By modulating the stimulus, the residence of electrons in different triplet states can be manipulated to achieve RGB LPL. Importantly, blue LPL was achieved by manipulating the anti‐Kasha emission. And the red LPL can still be observed at high temperature. [ABSTRACT FROM AUTHOR]

Subcellular stimulation by free radicals is crucial for deeper insight of cell behaviors. However, it remains a tough challenge due to the high spatial precision requirement and short life of radicals. Herein, we report a versatile open microfluidic probe for stable generation of free radical and subcellular stimulation. By optimizing parameters, the chemical reaction can be confined in a microregion with a diameter of several μm, and the real‐time produced reactive radicals can attack the desired subcellular region of a single cell. In order to reveal the attacked region, fluorescent cyanine 3 labeled tyramide free radicals are synthesized, and the target microregion on a single cell is successfully stained by the covalent linking reaction between radicals and membrane proteins, which proves the feasibility of our method. We believe this method will open new avenues for short‐lived reactive intermediates stimulation at the single‐cell/sub‐cell level and selective membrane labeling. [ABSTRACT FROM AUTHOR]

Redox‐active esters (RAEs) as active radical precursors have been extensively studied for C−B bond formations. However, the analogous transformations of stabilized radicals from the corresponding acid precursors remain challenging owing to the strong preference towards single‐electron oxidation to the stable carbocations. This work describes a general strategy for rapid access to various aliphatic and aromatic boronic esters by mild photoinduced decarboxylative borylation. Both aryl and alkyl radicals could be generated from the leaving group‐assisted N‐hydroxybenzimidoyl chloride esters, even α‐CF3 substituted substrates could be activated for further elaboration. [ABSTRACT FROM AUTHOR]

Abstract: Micrometer‐sized functional nucleic acid (FNA) superstructures (denoted as 3D DNA) were examined as a unique class of biorecognition elements to produce highly functional bioactive paper surfaces. 3D DNA containing repeating sequences of either a DNA aptamer or DNAzyme was created from long‐chain products of rolling circle amplification followed by salt aging. The resulting 3D DNA retained its original spherical shape upon inkjet printing and adhered strongly to the paper surface via physisorption. 3D DNA paper sensors showed resistance to degradation by nucleases, suppressed nonspecific protein adsorption, and provided a much higher surface density of functional DNA relative to monomeric FNAs, making such species ideally suited for development of paper‐based biosensors. [ABSTRACT FROM AUTHOR]

Abstract: A facile strategy is presented to form 3D porous Cu@Cu2O aerogel networks by self‐assembling Cu@Cu2O nanoparticles with the diameters of ca. 40 nm for constructing catalytic interfaces. Unexpectedly, the prepared Cu@Cu2O aerogel networks display excellent electrocatalytic activity to glucose oxidation at a low onset potential of ca. 0.25 V. Moreover, the Cu@Cu2O aerogels also can act as mimicking‐enzymes including horseradish peroxidase and NADH peroxidase, and show obvious enzymatic catalytic activities to the oxidation of dopamine (DA), o‐phenyldiamine (OPD), 3,3,5,5‐tetramethylbenzidine (TMB), and dihydronicotinamide adenine dinucleotide (NADH) in the presence of H2O2. These 3D Cu@Cu2O aerogel networks are a new class of porous catalytic materials as mimic peroxidases and electrocatalysts and offer a novel platform to construct catalytic interfaces for promising applications in electrochemical sensors and artificial enzymatic catalytic systems. [ABSTRACT FROM AUTHOR]

Engineering near-infrared (NIR) light-sensitive enzymes remains a huge challenge. A photothermal effect-associated method is developed for tailoring the enzymatic activity of enzymes by exposure to NIR light. An ultrasmall platinum nanoparticle was anchored in an enzyme to generate local heating upon NIR irradiation, which enhanced the enzyme activity without increasing bulk temperature. Following NIR irradiation, the enzyme activity was tailored rapidly and reversibly, and was modulated by varying laser power density and irradiation time. Four enzymes were engineered, including glucoamylase, glucose oxidase, catalase, and proteinase K with NIR-light sensitivity, and demonstrated their utility in practical applications such as photolithography and NIR light-responsive antibacterial or anticancer actions. Our investigation suggests that this approach could be broadly used to engineer enzymes with NIR-light sensitivity for many biological applications. [ABSTRACT FROM AUTHOR]

We report a signal amplification strategy termed DNAzyme feedback amplification (DFA) that takes advantage of rolling-circle amplification (RCA) and an RNA-cleaving DNAzyme (RCD). DFA employs two specially programmed DNA complexes, one composed of a primer and a circular template containing the antisense sequence of an RCD, and the other composed of the same circular template and an RNA-containing substrate for the RCD. RCA is initiated at the first complex to produce RCD elements that go on to cleave the substrate in the second complex. This cleavage event triggers the production of more input complexes for RCA. This reaction circuit continues autonomously, resulting in exponential DNA amplification. We demonstrate the versatility of this approach for biosensing through the design of DFA systems capable of detecting a microRNA sequence and a bacterium, with sensitivity improvements of 3-6 orders of magnitude over conventional methods. [ABSTRACT FROM AUTHOR]

The utilization of the greenhouse gas CO2 in energy-storage systems is highly desirable. It is now shown that the introduction of graphene as a cathode material significantly improves the performance of Li-CO2 batteries. Such batteries display a superior discharge capacity and enhanced cycle stability. Therefore, graphene can act as an efficient cathode in Li-CO2 batteries, and it provides a novel approach for simultaneously capturing CO2 and storing energy. [ABSTRACT FROM AUTHOR]

Novel multiresponsive microgels based on poly( N-isopropylacrylamide) were synthesized to contain triphenylmethane leucohydroxide, and used to construct etalons. The optical properties of the resultant etalons were investigated, and their response to ultraviolet and visible irradiation, solution pH changes, and the presence of a mimic of the nerve agent Tabun characterized. We clearly show that the optical properties of the device depended dramatically on these stimuli. This investigation illustrates the versatility of the microgel-based etalon structure, and showcases the clear utility of such devices for remote actuation, color tunable optics, sensing, and potential remotely triggered drug delivery applications. [ABSTRACT FROM AUTHOR]

Schwefelaffin: Neue Trägermaterialien für Schwefelkathoden in Lithium ‐ Schwefel ‐ Batterien zeichnen sich durch eine sulfophile Oberfläche bei zugleich hoher elektrischer Leitfähigkeit aus. Die neuartigen Systeme liefern höhere Kapazitäten und sind stabiler als bisherige Materialien, bei denen der Schwefel physikalisch abgesperrt wird. [ABSTRACT FROM AUTHOR]

The doped organic hole transport layer (HTL) is crucial for achieving high‐efficiency perovskite solar cells (PSCs). However, the traditional doping strategy undergoes a time‐consuming and environment‐dependent oxidation process, which hinders the technology upgrades and commercialization of PSCs. Here, we reported a new strategy by introducing a cascade reaction in traditional doped Spiro‐OMeTAD, which can simultaneously achieve rapid oxidation and overcome the erosion of perovskite by 4‐tert‐butylpyridine (tBP) in organic HTL. The ideal dopant iodobenzene diacetate was utilized as the initiator that can react with Spiro to generate Spiro⋅+ radicals quickly and efficiently without the participation of ambient air, with the byproduct of iodobenzene (DB). Then, the DB can coordinate with tBP through a halogen bond to form a tBP‐DB complex, minimizing the sustained erosion from tBP to perovskite. Based on the above cascade reaction, the resulting Spiro‐based PSCs have a champion PCE of 25.76 % (certificated of 25.38 %). This new oxidation process of HTL is less environment‐dependent and produces PSCs with higher reproducibility. Moreover, the PTAA‐based PSCs obtain a PCE of 23.76 %, demonstrating the excellent applicability of this doping strategy on organic HTL. [ABSTRACT FROM AUTHOR]

Lithium polysulfides (LiPSs) are pivotal intermediates involved in all the cathodic reactions in lithium–sulfur (Li−S) batteries. Elucidating the solvation structure of LiPSs is the first step for rational design of electrolyte and improving Li−S battery performances. Herein, we investigate the solvation structure of LiPSs and find that Li salt anions tend to enter the first solvation sheath of LiPSs and form contact ion pairs in electrolyte. The anion‐involved solvation structure of LiPSs significantly influences the intrinsic kinetics of the sulfur redox reactions. In particular, the LiPS solvation structure modified by lithium bis(fluorosulfonyl)imide endows Li−S batteries with reduced polarization and enhanced rate performances under high sulfur areal loading and lean electrolyte volume conditions. This work updates the fundamental understanding of the solvation chemistry of LiPSs and highlights electrolyte engineering for promoting the performances of Li−S batteries. [ABSTRACT FROM AUTHOR]

In solid‐state lithium metal batteries (SSLMBs), the inhomogeneous electrolyte‐electrode interphase layer aggravates the interfacial stability, leading to discontinuous interfacial ion/charge transport and continuous degradation of the electrolyte. Herein, we constructed an anion‐modulated ionic conductor (AMIC) that enables in situ construction of electrolyte/electrode interphases for high‐voltage SSLMBs by exploiting conformational transitions under multiple interactions between polymer and lithium salt anions. Anions modulate the decomposition behavior of supramolecular poly (vinylene carbonate) (PVC) at the electrode interface by changing the spatial conformation of the polymer chains, which further enhances ion transport and stabilizes the interfacial morphology. In addition, the AMIC weakens the "Li+‐solvation" and increases Li+ vehicle sites, thereby enhancing the lithium‐ion transport number (tLi+=~0.67). Consequently, Li || LiNi0.8Co0.1Mn0.1O2 cell maintains about 85 % capacity retention and Coulombic efficiency >99.8 % in 200 cycles at a charge cut‐off voltage of 4.5 V. This study provides a new understanding of lithium salt anions regulating polymer chain segment behavior in the solid‐state polymer electrolyte (SPE) and highlights the importance of the ion environment in the construction of interfacial phases and ionic conduction. [ABSTRACT FROM AUTHOR]

Bipolar membranes (BPMs) have emerged as a promising solution for mitigating CO2 losses, salt precipitation and high maintenance costs associated with the commonly used anion‐exchange membrane electrode assembly for CO2 reduction reaction (CO2RR). However, the industrial implementation of BPM‐based zero‐gap electrolyzer is hampered by the poor CO2RR performance, largely attributed to the local acidic environment. Here, we report a backbone engineering strategy to improve the CO2RR performance of molecular catalysts in BPM‐based zero‐gap electrolyzers by covalently grafting cobalt tetraaminophthalocyanine onto a positively charged polyfluorene backbone (PF‐CoTAPc). PF‐CoTAPc shows a high acid tolerance in BPM electrode assembly (BPMEA), achieving a high FE of 82.6 % for CO at 100 mA/cm2 and a high CO2 utilization efficiency of 87.8 %. Notably, the CO2RR selectivity, carbon utilization efficiency and long‐term stability of PF‐CoTAPc in BPMEA outperform reported BPM systems. We attribute the enhancement to the stable cationic shield in the double layer and suppression of proton migration, ultimately inhibiting the undesired hydrogen evolution and improving the CO2RR selectivity. Techno‐economic analysis shows the least energy consumption (957 kJ/mol) for the PF‐CoTAPc catalyst in BPMEA. Our findings provide a viable strategy for designing efficient CO2RR catalysts in acidic environments. [ABSTRACT FROM AUTHOR]

Creation of intrapenetrated mesopores with open highway from external surface into the interior of zeolite crystals are highly desirable that can significantly improve the molecular transport and active sites accessibility of microporous zeolites to afford enhanced catalytic properties. Here, different from traditional zeolite‐seeded methods that generally produced isolated mesopores in zeolites, nanosized amorphous protozeolites with embryo structure of zeolites were used as seeds for the construction of single‐crystalline hierarchical ZSM‐5 zeolites with intrapenetrated mesopores (mesopore volume of 0.51 cm3 g−1) and highly complete framework. In this strategy, in contrast to the conventional synthesis, only a small amount of organic structure directing agents and a low crystallization temperature were adopted to promise the protozeolites as the dominant growth directing sites to induce crystallization. The protozeolite nanoseeds provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as‐prepared hierarchical ZSM‐5 zeolites exhibited ultra‐long lifetime of 443.9 hours and a high propylene selectivity of 47.92 % at a WHSV of 2 h−1 in the methanol‐to‐propylene reaction. This work provides a facile protozeolite‐seeded strategy for the synthesis of intrapenetrated hierarchical zeolites that are highly effective for catalytic applications. [ABSTRACT FROM AUTHOR]

Coordination engineering for single‐atom sites has drawn increasing attention, yet its chemical synthesis remains a tough issue, especially for tailorable coordination structures. Herein, a molecular recognition strategy is proposed to fabricate single‐atom sites with regulable local coordination structures. Specifically, a heteroatom‐containing ligand serves as the guest molecule to induce coordination interaction with the metal‐containing host, precisely settling the heteroatoms into the local structure of single‐atom sites. As a proof of concept, thiophene is selected as the guest molecule, and sulfur atoms are successfully introduced into the local coordination structure of iron single‐atom sites. Ultrahigh oxygen reduction electrocatalytic activity is achieved with a half‐wave potential of 0.93 V versus reversible hydrogen electrode. Furthermore, the strategy possesses excellent universality towards diversified types of single‐atom sites. This work makes breakthroughs in the fabrication of single‐atom sites and affords new opportunities in structural regulation at the atomic level. [ABSTRACT FROM AUTHOR]

Potassium–sulfur (K−S) batteries have attracted wide attention owing to their high theoretical energy density and low cost. However, the intractable shuttle effect of K polysulfides results in poor cyclability of K−S batteries, which severely limits their practical application. Herein, a bifunctional concentrated electrolyte (3 mol L−1 potassium bis(trifluoromethanesulfonyl)imide in ethylene carbonate (EC)) with high ionic conductivity and low viscosity is developed to regulate the dissolution behavior of polysulfides and induce uniform K deposition. The organic groups in the cathode electrolyte interphase layer derived from EC can effectively block the polysulfide shuttle and realize a "solid–liquid–solid" reaction mechanism. The KF‐riched solid‐electrolyte interphase inhibits K dendrite growth during cycling. As a result, the achieved K−S batteries display a high reversible capacity of 654 mAh g−1 at 0.5 A g−1 after 800 cycles and a long lifespan over 2000 cycles at 1 A g−1. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li−S) batteries are promising due to ultrahigh theoretical energy density. However, their cycling lifespan is crucially affected by the electrode kinetics of lithium polysulfides. Herein, the polysulfide solvation structure is correlated with polysulfide electrode kinetics towards long‐cycling Li−S batteries. The solvation structure derived from strong solvating power electrolyte induces fast anode kinetics and rapid anode failure, while that derived from weak solvating power electrolyte causes sluggish cathode kinetics and rapid capacity loss. By contrast, the solvation structure derived from medium solvating power electrolyte balances cathode and anode kinetics and improves the cycling performance of Li−S batteries. Li−S coin cells with ultra‐thin Li anodes and high‐S‐loading cathodes deliver 146 cycles and a 338 Wh kg−1 pouch cell undergoes stable 30 cycles. This work clarifies the relationship between polysulfide solvation structure and electrode kinetics and inspires rational electrolyte design for long‐cycling Li−S batteries. [ABSTRACT FROM AUTHOR]

Viscosity is an extremely important property for ion transport and wettability of electrolytes. Easy access to viscosity values and a deep understanding of this property remain challenging yet critical to evaluating the electrolyte performance and tailoring electrolyte recipes with targeted properties. We proposed a screened overlapping method to efficiently compute the viscosity of lithium battery electrolytes by molecular dynamics simulations. The origin of electrolyte viscosity was further comprehensively probed. The viscosity of solvents exhibits a positive correlation with the binding energy between molecules, indicating viscosity is directly correlated to intermolecular interactions. Salts in electrolytes enlarge the viscosity significantly with increasing concentrations while diluents serve as the viscosity reducer, which is attributed to the varied binding strength from cation–anion and cation–solvent associations. This work develops an accurate and efficient method for computing the electrolyte viscosity and affords deep insight into viscosity at the molecular level, which exhibits the huge potential to accelerate advanced electrolyte design for next‐generation rechargeable batteries. [ABSTRACT FROM AUTHOR]

Nongenetic strategies that enable control over the cell‐cell interaction network would be highly desired, particularly in T cell‐based cancer immunotherapy. In this work, we developed an aptamer‐functionalized DNA circuit to modulate the interaction between T cells and cancer cells. This DNA circuit was composed of recognition‐then‐triggering and aggregation‐then‐activation modules. Upon recognizing target cancer cells, the triggering strand was released to induce aggregation of immune receptors on the T cell surface, leading to an enhancement of T cell activity for effective cancer eradication. Our results demonstrated the feasibility of this DNA circuit for promoting target cancer cell‐directed stimulation of T cells, which, consequently, enhanced their killing effect on cancer cells. This DNA circuit, as a modular strategy to modulate intercellular interactions, could lead to a new paradigm for the development of nongenetic T cell‐based immunotherapy. [ABSTRACT FROM AUTHOR]

The multiple metastable excited states provided by excited‐state intramolecular proton transfer (ESIPT) molecules are beneficial to bring temperature‐dependent and color‐tunable long persistent luminescence (LPL). Meanwhile, ESIPT molecules are intrinsically suitable to be modulated as D‐π‐A structure to obtain both one/two‐photon excitation and LPL emission simultaneously. Herein, we report the rational design of a dynamic CdII coordination polymer (LIFM‐106) from ESIPT ligand to achieve the above goals. By comparing LIFM‐106 with the counterparts, we established a temperature‐regulated competitive relationship between singlet excimer and triplet LPL emission. The optimization of ligand aggregation mode effectively boost the competitiveness of the latter. In result, LIFM‐106 shows outstanding one/two‐photon excited LPL performance with wide temperature range (100–380 K) and tunable color (green to red). The multichannel radiation process was further elucidated by transient absorption and theoretical calculations, benefiting for the application in anti‐counterfeiting systems. [ABSTRACT FROM AUTHOR]

Rechargeable lithium batteries are one of the most appropriate energy storage systems in our electrified society, as virtually all portable electronic devices and electric vehicles today rely on the chemical energy stored in them. However, sub‐zero Celsius operation, especially below −20 °C, remains a huge challenge for lithium batteries and greatly limits their application in extreme environments. Slow Li+ diffusion and charge transfer kinetics have been identified as two main origins of the poor performance of RLBs under low‐temperature conditions, both strongly associated with the liquid electrolyte that governs bulk and interfacial ion transport. In this review, we first analyze the low‐temperature kinetic behavior and failure mechanism of lithium batteries from an electrolyte standpoint. We next trace the history of low‐temperature electrolytes in the past 40 years (1983–2022), followed by a comprehensive summary of the research progress as well as introducing the state‐of‐the‐art characterization and computational methods for revealing their underlying mechanisms. Finally, we provide some perspectives on future research of low‐temperature electrolytes with particular emphasis on mechanism analysis and practical application. [ABSTRACT FROM AUTHOR]

Practical lithium–sulfur (Li−S) batteries are severely plagued by the instability of solid electrolyte interphase (SEI) formed in routine ether electrolytes. Herein, an electrolyte with 1,3,5‐trioxane (TO) and 1,2‐dimethoxyethane (DME) as co‐solvents is proposed to construct a high‐mechanical‐stability SEI by enriching organic components in Li−S batteries. The high‐mechanical‐stability SEI works compatibly in Li−S batteries. TO with high polymerization capability can preferentially decompose and form organic‐rich SEI, strengthening mechanical stability of SEI, which mitigates crack and regeneration of SEI and reduces the consumption rate of active Li, Li polysulfides, and electrolytes. Meanwhile, DME ensures high specific capacity of S cathodes. Accordingly, the lifespan of Li−S batteries increases from 75 cycles in routine ether electrolyte to 216 cycles in TO‐based electrolyte. Furthermore, a 417 Wh kg−1 Li−S pouch cell undergoes 20 cycles. This work provides an emerging electrolyte design for practical Li−S batteries. [ABSTRACT FROM AUTHOR]

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

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO2), i.e. artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C2 compounds with a high CO2 conversion rate remains challenging for current AP technologies. We performed CO2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C2H5OH) selectivity of>99 % and a CO2 conversion rate of up to 17.1 mmol gcat−1 h−1 with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few‐layer graphene overlayer, which also favored an efficient CO2 to C2H5OH conversion pathway. [ABSTRACT FROM AUTHOR]

Extreme fast charging (XFC) of high‐energy Li‐ion batteries is a key enabler of electrified transportation. While previous studies mainly focused on improving Li ion mass transport in electrodes and electrolytes, the limitations of charge transfer across electrode–electrolyte interfaces remain underexplored. Herein we unravel how charge transfer kinetics dictates the fast rechargeability of Li‐ion cells. Li ion transfer across the cathode–electrolyte interface is found to be rate‐limiting during XFC, but the charge transfer energy barrier at both the cathode and anode have to be reduced simultaneously to prevent Li plating, which is achieved through electrolyte engineering. By unlocking charge transfer limitations, 184 Wh kg−1 pouch cells demonstrate stable XFC (10‐min charge to 80 %) which is otherwise unachievable, and the lifetime of 245 Wh kg−1 21700 cells is quintupled during fast charging (25‐min charge to 80 %). [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) battery is strongly considered as one of the most promising energy storage systems due to its high theoretical energy density and low cost. However, the sluggish reduction kinetics from Li2S4 to Li2S during discharge hinders the practical application of Li–S batteries. Although various electrocatalysts have been proposed to improve the reaction kinetics, the electrocatalytic mechanism is unclear due to the complexity of sulfur reduction reactions (SRR). It is crucial to understand the electrocatalytic mechanism thoroughly for designing advanced electrocatalysts. Herein an electrocatalytic model is constructed to reveal the chemical mechanism of the SRR in Li–S batteries based on systematical density functional theory calculations, taking heteroatoms‐doped carbon materials as an example. The adsorption energy of LiSy⋅ (y=1, 2, or 3) radicals is used as a key descriptor to predict the reaction pathway, rate‐determining step, and overpotential. A diagram for designing advanced electrocatalysts is accordingly constructed. This work establishes a theoretical model, which is an intelligent integration for probing the complicated SRR mechanisms and designing advanced electrocatalysts for high‐performance Li–S batteries. [ABSTRACT FROM AUTHOR]

Advanced electrolyte design is essential for building high‐energy‐density lithium (Li) batteries, and introducing anions into the Li+ solvation sheaths has been widely demonstrated as a promising strategy. However, a fundamental understanding of the critical role of anions in such electrolytes is very lacking. Herein, the anionic chemistry in regulating the electrolyte structure and stability is probed by combining computational and experimental approaches. Based on a comprehensive analysis of the lowest unoccupied molecular orbitals, the solvents and anions in Li+ solvation sheaths exhibit enhanced and decreased reductive stability compared with free counterparts, respectively, which agrees with both calculated and experimental results of reduction potentials. Accordingly, new strategies are proposed to build stable electrolytes based on the established anionic chemistry. This work unveils the mysterious anionic chemistry in regulating the structure–function relationship of electrolytes and contributes to a rational design of advanced electrolytes for practical Li metal batteries. [ABSTRACT FROM AUTHOR]

Serious safety risks caused by the high reactivity of lithium metal against electrolytes severely hamper the practicability of lithium metal batteries. By introducing unique polymerization site and more fluoride substitution, we built an in situ formed polymer‐rich solid electrolyte interphase upon lithium anode to improve battery safety. The fluorine‐rich and hydrogen‐free polymer exhibits high thermal stability, which effectively reduces the continuous exothermic reaction between electrolyte and anode/cathode. As a result, the critical temperature for thermal safety of 1.0 Ah lithium‐LiNi0.5Co0.2Mn0.3O2 pouch cell can be increased from 143.2 °C to 174.2 °C. The more dangerous "ignition" point of lithium metal batteries, the starting temperature of battery thermal runaway, has been dramatically raised from 240.0 °C to 338.0 °C. This work affords novel strategies upon electrolyte design, aiming to pave the way for high‐energy‐density and thermally safe lithium metal batteries. [ABSTRACT FROM AUTHOR]

Axially chiral molecules bearing multiple stereogenic axes are of great importance in the field of organic chemistry. However, the efficient construction of atropisomers featuring two different types of stereogenic axes has rarely been explored. Herein, we report the novel atroposelective synthesis of configurationally stable axially chiral B,N‐heterocycles. By using stepwise asymmetric allylic substitution‐isomerization (AASI) strategy, diaxially chiral B,N‐heterocycles bearing B−C and C−N axes that are related to the moieties of axially chiral enamines and arylborons were also obtained. In this case, all four stereoisomers of diaxially chiral B,N‐heterocycles were stereodivergently afforded in high enantioselectivities. Density functional theory (DFT) studies demonstrated that the NH⋅⋅⋅π interactions played a unique role in the promotion of stereospecific isomerization, thereby leading to the highly efficient central‐to‐axial chirality transfer. [ABSTRACT FROM AUTHOR]

The development of emerging rechargeable batteries is often hindered by limited chemical understanding composing of entangled patterns in an enormous space. Herein, we propose an interpretable hybrid machine learning framework to untangle intractable degradation chemistries of conversion‐type batteries. Rather than being a black box, this framework not only demonstrates an ability to accurately forecast lithium‐sulfur batteries (with a test mean absolute error of 8.9 % for the end‐of‐life prediction) but also generate useful physical understandings that illuminate future battery design and optimization. The framework also enables the discovery of a previously unknown performance indicator, the ratio of electrolyte amount to high‐voltage‐region capacity at the first discharge, for lithium‐sulfur batteries complying practical merits. The present data‐driven approach is readily applicable to other energy storage systems due to its versatility and flexibility in modules and inputs. [ABSTRACT FROM AUTHOR]

The performance of rechargeable lithium (Li) batteries is highly correlated with the structure of solid electrolyte interphase (SEI). The properties of a working anode are vital factors in determining the structure of SEI; however, the correspondingly poor understanding hinders the rational regulation of SEI. Herein, the electrode potential and anode material, two critical properties of an anode, in dictating the structural evolution of SEI were investigated theoretically and experimentally. The anode potential is identified as a crucial role in dictating the SEI structure. The anode potential determines the reduction products in the electrolyte, ultimately giving rise to the mosaic and bilayer SEI structure at high and low potential, respectively. In contrast, the anode material does not cause a significant change in the SEI structure. This work discloses the crucial role of electrode potential in dictating SEI structure and provides rational guidance to regulate SEI structure. [ABSTRACT FROM AUTHOR]

The access to full performance of state‐of‐the‐art Li‐ion batteries (LIBs) is hindered by the mysterious lithium plating behavior. A rapid quantified lithium plating determination method compatible with actual working conditions is an urgent necessity for safe working LIBs. In this contribution, the relationship between electrical double layer (EDL) capacitance and electrochemical active surface area (ECSA) of graphite anodes during the Li‐ion intercalation and Li plating processes is unveiled. We propose an operando lithium plating determination method based on the dynamic capacitance measurement (DCM) test. Reasonable selection of alternating current (AC) frequency protects the anodic responses from the interference of cathodic responses, which allows DCM to be applied in practical LIBs. The onset of lithium plating can be quantitatively traced, demonstrating the promise for real‐time operando determination for lithium plating in a working battery. [ABSTRACT FROM AUTHOR]

Lithium‐metal batteries (LMBs) capable of operating stably at high temperature application scenarios are highly desirable. Conventional lithium‐ion batteries could only work stably under 60 °C because of the thermal instability of electrolyte at elevated temperature. Here we design and develop a thermal stable electrolyte based on stable solvation structure using multiple ion–dipole interactions. The strong coordination in solvated structure of electrolyte defines the Li deposition behaviour and the evolution of solid electrolyte interphase at high temperature, which is important to achieve high Li Coulombic efficiency and avoid Li dendritic growth. For high mass loading LiFePO4‐Li cells, the cells at 60 °C with conventional electrolyte easily run into failures, but the cells with our electrolyte at 90 °C and 100 °C could cycle more than 120 and 50 cycles respectively. This work provides new insight into electrolyte design and contributes to the development of high temperature LMBs. [ABSTRACT FROM AUTHOR]

Aqueous zinc–air batteries possess inherent safety and are especially commendable facing high‐temperature working conditions. However, their working feasibility at high temperatures has seldom been investigated. Herein, the working feasibility of high‐temperature zinc–air batteries is systemically investigated. The effects of temperature on air cathode, zinc anode, and aqueous electrolyte are decoupled to identify the favorable and unfavorable factors. Specifically, parasitic hydrogen evolution reaction strengthens at high temperatures and leads to declined anode Faraday efficiency, which is identified as the main bottleneck. Moreover, zinc–air batteries demonstrate cycling feasibility at 80 °C. This work reveals the potential of zinc–air batteries to satisfy energy storage at high temperatures and guides further development of advanced batteries towards harsh working conditions. [ABSTRACT FROM AUTHOR]

Contact prelithiation is an important strategy to compensate the initial capacity loss of lithium‐ion batteries. However, the dead Li generated from inadequate Li conversion reduces the cycling stability of rechargeable batteries. Herein a mono‐solvent dimethyl carbonate (DMC) electrolyte was employed in contact prelithiation for the first time. We discover that the low‐organic‐content raw electrolyte interphase (REI) induced by this electrolyte on Li source and anode is a mixed ion/electron conductor. Therefore, electron channels can be maintained even when the Li source has been completely wrapped by the DMC‐derived REI. As a result, an outstanding Li source utilization of 92.8 % and a negligible dead Li yield can be realized. This strategy renders batteries with a very high initial Coulombic efficiency (90.0 %) and an excellent capacity retention (94.9 %) over 210 cycles, highlighting the significance of REI for effective contact prelithiation. [ABSTRACT FROM AUTHOR]

The lifespan of practical lithium (Li)‐metal batteries is severely hindered by the instability of Li‐metal anodes. Fluorinated solid electrolyte interphase (SEI) emerges as a promising strategy to improve the stability of Li‐metal anodes. The rational design of fluorinated molecules is pivotal to construct fluorinated SEI. Herein, design principles of fluorinated molecules are proposed. Fluoroalkyl (−CF2CF2−) is selected as an enriched F reservoir and the defluorination of the C−F bond is driven by leaving groups on β‐sites. An activated fluoroalkyl molecule (AFA), 2,2,3,3‐tetrafluorobutane‐1,4‐diol dinitrate is unprecedentedly proposed to render fast and complete defluorination and generate uniform fluorinated SEI on Li‐metal anodes. In Li–sulfur (Li−S) batteries under practical conditions, the fluorinated SEI constructed by AFA undergoes 183 cycles, which is three times the SEI formed by LiNO3. Furthermore, a Li−S pouch cell of 360 Wh kg−1 delivers 25 cycles with AFA. This work demonstrates rational molecular design principles of fluorinated molecules to construct fluorinated SEI for practical Li‐metal batteries. [ABSTRACT FROM AUTHOR]

This article, published in Angewandte Chemie, explores the solvation structure of lithium polysulfides (Li2Sn) in electrolytes used in lithium-sulfur batteries. The authors, Bo-Quan Li, Qiang Zhang, and their team, investigate how LiPSs interact with other electrolyte components and form specific ion-solvent complexes. They find that Li salt anions are favored to enter the first solvation sheath of cationic LiPSs and form contact ion pairs, which updates our understanding of ion-solvent interaction in Li-S batteries. This research provides valuable insights for the development of more efficient and stable lithium-sulfur batteries. [Extracted from the article]

We report on a paper device capable of carrying out target-induced rolling circle amplification (RCA) to produce massive DNA amplicons that can be easily visualized. Interestingly, we observed that RCA was more proficient on paper than in solution, which we attribute to a significantly higher localized concentration of immobilized DNA. Furthermore, we have successfully engineered a fully functional paper device for sensitive DNA or microRNA detection via printing of all RCA-enabling molecules within a polymeric sugar film formed from pullulan, which was integrated with the paper device. This encapsulation not only stabilizes the entrapped reagents at room temperature but also enables colorimetric bioassays with minimal steps. [ABSTRACT FROM AUTHOR]

ϕ29 DNA polymerase (ϕ29DP) is able to carry out repetitive rounds of DNA synthesis using a circular DNA template by rolling circle amplification (RCA). It also has the ability to execute 3′-5′ digestion of single-stranded but not double-stranded DNA. A biosensor engineering strategy is presented that takes advantage of these two properties of ϕ29DP coupled with structure-switching DNA aptamers. The design employs a DNA assembly made of a circular DNA template, a DNA aptamer, and a pre-primer. The DNA assembly is unable to undergo RCA in the absence of cognate target owing to the formation of duplex structures. The presence of the target, however, triggers a structure-switching event that causes nucleolytic conversion of the pre-primer by ϕ29DP into a mature primer to facilitate RCA. This method relays target detection by the aptamer to the production of massive DNA amplicons, giving rise to dramatically enhanced detection sensitivity. [ABSTRACT FROM AUTHOR]

The lifespan of high‐energy‐density lithium metal batteries (LMBs) is hindered by heterogeneous solid electrolyte interphase (SEI). The rational design of electrolytes is strongly considered to obtain uniform SEI in working batteries. Herein, a modification of nitrate ion (NO3−) is proposed and validated to improve the homogeneity of the SEI in practical LMBs. NO3− is connected to an ether‐based moiety to form isosorbide dinitrate (ISDN) to break the resonance structure of NO3− and improve the reducibility. The decomposition of non‐resonant −NO3 in ISDN enriches SEI with abundant LiNxOy and induces uniform lithium deposition. Lithium–sulfur batteries with ISDN additives deliver a capacity retention of 83.7 % for 100 cycles compared with rapid decay with LiNO3 after 55 cycles. Moreover, lithium–sulfur pouch cells with ISDN additives provide a specific energy of 319 Wh kg−1 and undergo 20 cycles. This work provides a realistic reference in designing additives to modify the SEI for stabilizing LMBs. [ABSTRACT FROM AUTHOR]

Precise monitoring of the subtle pH fluctuation during biological events remains a big challenge. Previously, we reported an ultra‐pH‐sensitive (UPS) nanoprobe library with a sharp pH response using co‐polymerization of two tertiary amine‐containing monomers with distinct pKa. Currently, we have generalized the UPS nanoparticle library with tunable pH transitions (pHt) by copolymerization of a tertiary amine‐containing monomer with a series of non‐ionizable monomers. The pHt of nanoparticles is fine‐tuned by the non‐ionizable monomers with different hydrophobicity. Each non‐ionizable monomer presents a constant contribution to pH tunability regardless of tertiary amine‐containing monomers. Based on this strategy, we produced two libraries of nanoprobes with continuous pHt covering the entire physiological pH range (5.0–7.4) for fluorescent imaging of endosome maturation and cancers. This generalized strategy provides a powerful toolkit for biological studies and cancer theranostics. [ABSTRACT FROM AUTHOR]

Lithium–sulfur (Li–S) batteries are deemed as future energy storage devices due to ultrahigh theoretical energy density. Cathodic polysulfide electrocatalysts have been widely investigated to promote sluggish sulfur redox kinetics. Probing the surface structure of electrocatalysts is vital to understanding the mechanism of polysulfide electrocatalysis. In this work, we for the first time identify surface gelation on disulfide electrocatalysts. Concretely, the Lewis acid sites on disulfides trigger the ring‐opening polymerization of the dioxolane solvent to generate a surface gel layer, covering disulfides and reducing the electrocatalytic activity. Accordingly, a Lewis base triethylamine (TEA) is introduced as a competitive inhibitor. Consequently, Li–S batteries with disulfide electrocatalysts and TEA afford high specific capacity and improved rate responses. This work affords new insights on the actual surface structure of electrocatalysts in Li–S batteries. [ABSTRACT FROM AUTHOR]

Emerging machine learning (ML) methods are widely applied in chemistry and materials science studies and have led to a focus on data‐driven research. This Minireview summarizes the application of ML to rechargeable batteries, from the microscale to the macroscale. Specifically, ML offers a strategy to explore new functionals for density functional theory calculations and new potentials for molecular dynamics simulations, which are expected to significantly enhance the challenging descriptions of interfaces and amorphous structures. ML also possesses a great potential to mine and unveil valuable information from both experimental and theoretical datasets. A quantitative "structure–function" correlation can thus be established, which can be used to predict the ionic conductivity of solids as well as the battery lifespan. ML also exhibits great advantages in strategy optimization, such as fast‐charge procedures. The future combination of multiscale simulations, experiments, and ML is also discussed and the role of humans in data‐driven research is highlighted. [ABSTRACT FROM AUTHOR]

High‐energy‐density lithium (Li) metal batteries suffer from a short lifespan owing to apparently ceaseless inactive Li accumulation, which is accompanied by the consumption of electrolyte and active Li reservoir, seriously deteriorating the cyclability of batteries. Herein, a triiodide/iodide (I3−/I−) redox couple initiated by stannic iodide (SnI4) is demonstrated to reclaim inactive Li. The reduction of I3− converts inactive Li into soluble LiI, which then diffuses to the cathode side. The oxidation of LiI by the delithiated cathode transforms cathode into the lithiation state and regenerates I3−, reclaiming Li ion from inactive Li. The regenerated I3− engages the further redox reactions. Furthermore, the formation of Sn mitigates the corrosion of I3− on active Li reservoir sacrificially. In working Li | LiNi0.5Co0.2Mn0.3O2 batteries, the accumulated inactive Li is significantly reclaimed by the reversible I3−/I− redox couple, improving the lifespan of batteries by twice. This work initiates a creative solution to reclaim inactive Li for prolonging the lifespan of practical Li metal batteries. [ABSTRACT FROM AUTHOR]