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Recycling waste biomass to pyrolytic carbon has become a development direction of sodium-ion batteries (SIBs) anodes. However, it remains a challenge to precisely control the composition and structure of biomass to modify the properties of derived carbon. Herein, a strategy of hydrolyzing cellulose in phellem with sulfuric acid is proposed, which can promote cellulose fracture, reduce the graphitization and increase the content of closed pores in hard carbon. Accordingly, after the regulation of closed pore structure, the reversible capacity increased from 207 to 330 mAh g -1 at 20 mA g -1 , realizing an increase of ≈130 mAh g -1 in the plateau region and the initial Coulombic efficiency (ICE) is enhanced from 78% to 90%. When applied in full cell with O3-Na[Ni 1/3 Fe 1/3 Mn 1/3 ]O 2 , it showed an energy density of 247 Wh kg -1 . This strategy has certain universality, and it provides the feasibility to use low-value cellulose-containing biomass to fabricate high-performance hard carbon materials., (© 2024 Wiley‐VCH GmbH.)

Nitrogen-heterocycles are privileged structures in both marketed drugs and natural products. On the other hand, C-H amination reactions furnish unconventional and straightforward approaches for the construction of C-N bonds. Yet, most of the known methods rely on precious metal catalysts. Herein we report a site-selective intermolecular C(sp 3 )-H amination of N-heterocycles, catalyzed by inexpensive FeCl 2, which allows the functionalization of a wide range of pharmaceutically relevant cyclic amines. The C-H amination occurs site-selectively in α-position to the nitrogen atom, even when weaker C-H bonds are present, and furnishes Troc-protected aminals or amidines. The method employs the N-heterocycle as limiting reagent and is applicable to the late-stage functionalization of complex molecules. Its synthetic potential was further illustrated through the derivatization of α-aminated products and the application to a concise total synthesis of the reported structure for senobtusin. Mechanistic studies allowed to propose a plausible reaction mechanism involving a turnover-limiting Fe-nitrene generation followed by fast H atom transfer and radical rebound., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Starting from N-acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N-O couplings to provide unprecedented 1,3,2,4-oxathiadiazole 3-oxides in good to excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol % in the presence of phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required in this solvent-free procedure. Under heat or blue light, the newly formed five-membered heterocycles function as nitrene precursors reacting with sulfoxides as exemplified by the imidation of dimethyl sulfoxide., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The oxidative formation of N-N bonds from primary amides has been recently reported and then retracted in the journal Nature Communications by Kathiravan, Nicholls, and co-authors, utilizing a hypervalent iodane reagent. Unfortunately, the authors failed to recognize the Curtius reaction taking place under the described reaction conditions. Thus, the claimed N-N coupling products were not formed. Instead, the Curtius rearrangement urea coupling products were obtained. We demonstrate this herein by means of NMR and x-ray analysis, as well as with the support of an alternative synthetic route., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Lithium (Li) metal anode (LMA) replacing graphite anode for developing Li metal batteries (LMB) with the higher energy density has attracted much attention. However, LMA faces many issues, e. g., Li dendrites, dead Li and the side reactions, which causes the safety hazards and low coulomb efficiency (CE) of battery, therefore, LMB still cannot replace the current Li ion battery for practical use. Among those issues, dead Li is one of the decisive factors affecting the CE of LMB. To better understand dead Li, we summarize the recent work about the generation of dead Li, its impact on batteries performance, and the strategies to reuse and eliminate dead Li. Finally, the prospect of the future LMA and resultant LMB is also put forward., (© 2024 Wiley-VCH GmbH.)

There is notable progress in the development of efficient oxygen reduction electrocatalysts, which are crucial components of fuel cells. However, these superior activities are limited by imbalanced mass transport and cannot be fully reflected in actual fuel cell applications. Herein, the design concepts and development tracks of platinum (Pt)-nanocarbon hybrid catalysts, aiming to enhance the performance of both cathodic electrocatalysts and fuel cells, are presented. This review commences with an introduction to Pt/C catalysts, highlighting the diverse architectures developed to date, with particular emphasis on heteroatom modification and microstructure construction of functionalized nanocarbons based on integrated design concepts. This discussion encompasses the structural evolution, property enhancement, and catalytic mechanisms of Pt/C-based catalysts, including rational preparation recipes, superior activity, strong stability, robust metal-support interactions, adsorption regulation, synergistic pathways, confinement strategies, ionomer optimization, mass transport permission, multidimensional construction, and reactor upgrading. Furthermore, this review explores the low-barrier or barrier-free mass exchange interfaces and channels achieved through the impressive multidimensional construction of Pt-nanocarbon integrated catalysts, with the goal of optimizing fuel cell efficiency. In conclusion, this review outlines the challenges associated with Pt-nanocarbon integrated catalysts and provides perspectives on the future development trends of fuel cells and beyond., (© 2024 Wiley‐VCH GmbH.)

Solid polymer electrolytes (SPEs) for lithium metal batteries have garnered considerable interests owing to their low cost, flexibility, lightweight, and favorable interfacial compatibility with battery electrodes. Their soft mechanical nature compared to solid inorganic electrolytes give them a large advantage to be used in low pressure solid-state lithium metal batteries, which can avoid the cost and weight of the pressure cages. However, the application of SPEs is hindered by their relatively low ionic conductivity. In addressing this limitation, enormous efforts are devoted to the experimental investigation and theoretical calculations/simulation of new polymer classes. Recently, metal-organic frameworks (MOFs) have been shown to be effective in enhancing ion transport in SPEs. However, the mechanisms in enhancing Li + conductivity have rarely been systematically and comprehensively analyzed. Therefore, this review provides an in-depth summary of the mechanisms of MOF-enhanced Li + transport in MOF-based solid polymer electrolytes (MSPEs) in terms of polymer, MOF, MOF/polymer interface, and solid electrolyte interface aspects, respectively. Moreover, the understanding of Li + conduction mechanisms through employing advanced characterization tools, theoretical calculations, and simulations are also reviewed in this review. Finally, the main challenges in developing MSPEs are deeply analyzed and the corresponding future research directions are also proposed., (© 2024 Wiley‐VCH GmbH.)

A carbonyl-assisted asymmetric 1,2-migratory allylation through in situ generation of vicinal tetrasubstituted stereocenters is reported to access enantiopure α-amino ketones and amino alcohols with excellent yields and diastereoselectivities. In a remarkable divergence, despite higher steric hindrance, the allylation exclusively occurs on ketones over imines in the first step, followed by a face-selective 1,2-allyl transfer, thus highlighting an exciting interplay between two distinct electrophiles. The methodology distinguishes itself through its adaptability to gram-scale synthesis, showcasing broad functional-group tolerance and stereodivergence. Density functional theory (DFT) analysis led to a deeper understanding of its selectivity and mechanistic framework. Highlighting its transformative potential, the method was applied to the total synthesis of hapalindole alkaloids., (© 2024 Wiley-VCH GmbH.)

A highly efficient and chemoselective approach for the divergent assembling of unsymmetrical hydrazines through an unprecedented intermolecular desulfurdioxidative N-N coupling is developed. This metal free protocol employs readily accessible N-arylhydroxylamines and N-sulfinylanilines to provide highly valuable hydrazine products with good reaction yields and excellent functional group tolerance under simple conditions. Computational studies suggest that the in situ generated O-sulfenylated arylhydroxylamine intermediate undergoes a retro-[2π+2σ] cycloaddition via a stepwise diradical mechanism to form the N-N bond and release SO 2 ., (© 2024 Wiley-VCH GmbH.)

The electrolyte chemistry is crucially important for promoting the practical application of lithium metal batteries (LMBs). Here, we demonstrate for the first time that 1,3-dimethylimidazolium dimethyl phosphate (DIDP) and trimethylsilyl trifluoroacetate (TMSF) can undergo in situ transesterification in carbonate electrolyte to generate dimethyl trimethylsilyl phosphate (DTMSP) and 1,3-dimethylimidazolium trifluoroacetate (DITFA) as multifunctional additives for LMBs. H 2 O and HF can be removed by the Si-O group in DTMSP to improve the moisture resistance of electrolyte and the stability of cathode. Furthermore, the dissolution of lithium nitrate (LiNO 3 ) in carbonate electrolyte can be promoted by the trifluoroacetate anion (TFA - ) in DITFA, thereby optimizing the solvation structure and transport kinetics of Li + . More importantly, both DTMSP and DITFA tend to preferential redox decomposition due to the low lowest unoccupied molecular orbital (LUMO) and high highest occupied molecular orbital (HOMO). Consequently, a thin and robust layer rich in P/N/Si on the cathode and an inorganic-rich layer (e.g. Li 3 N/Li 3 P) on the anode can be constructed and superior electrochemical performances are achieved. This artificial transesterification strategy to introduce favorable additives paves an efficient and ingenious route to high-performance electrolyte for LMBs., (© 2024 Wiley-VCH GmbH.)

New methods and strategies for the direct oxidation of benzylic C-H bonds are highly desirable, owing to the importance of ketone motifs in significant organic transformations and the synthesis of valuable molecules, including pharmaceuticals, pesticides, and fine chemicals. Herein, we describe an electrochemical benzylic C-H oxidation strategy for the synthesis of ketones using MeOH as an oxygen source. Inexpensive and safe KBr serves as both an electrolyte and a bromide radical precursor in the reaction. This transformation also offers several advantages such as mild conditions, broad functional group tolerance, and operational simplicity. Mechanistic investigations by control experiments, radical scavenging experiments, electron paramagnetic resonance (EPR), kinetic studies, cyclic voltammetry (CV), and in-situ Fourier transform infrared (FTIR) spectroscopy support a pathway involving the formation and transformation of benzyl methyl ether via hydrogen atom transfer (HAT) and single-electron transfer (SET). The practical application of our strategy is highlighted by the successful synthesis of five pharmaceuticals, namely lenperone, melperone, diphenhydramine, cinnarizine, and flunarizine., (© 2024 Wiley-VCH GmbH.)

Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )-H functionalization, among which the Os(II)/Salox species is found to be the most efficient for precise stereocontrol in realizing the asymmetric C(sp 3 )-H amidation. As exemplified by the enantioenriched pyrrolidinone synthesis, such tailored Os(II)/Salox catalyst efficiently enables an intramolecular site-/enantioselective C(sp 3 )-H amidation in the γ-position of dioxazolone substrates, in which benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording the corresponding chiral γ-lactam products with good er values (up to 99 : 1) and diverse functionality (>35 examples). The unique performance advantage of the developed chiral Os(II)/Salox system in terms of the catalytic energy profile and the chiral induction has been further clarified by integrated experimental and computational studies., (© 2024 Wiley-VCH GmbH.)

Hydroxytrifluoroethyl and trifluoroacetyl groups are of utmost importance in biologically active compounds, but methods to tether these motifs to organic architectures have been limited. Typically, the preparation of these compounds relied on the use of strong bases or multistep routes. The renaissance of radical chemistry in photocatalytic, transition metal mediated, and hydrogen atom transfer (HAT) processes have allowed the installation of these medicinally relevant fluorinated motifs. This review provides an overview of the methods available for the direct synthesis of hydroxytrifluoroethyl- and trifluoroacetyl-derived compounds governed by single-electron transfer processes., (© 2024 Wiley‐VCH GmbH.)

A modular platform for facile access to 1,2,3,9-tetrahydro-4H-carbazol-4-ones (H 4 -carbazolones) and 3,4-dihydrocyclopenta[b]indol-1(2H)-ones (H 2 -indolones) is described. The requisite 6- and 5-membered 2-arylcycloalkane-1,3-dione precursors were readily obtained through a Cu-catalyzed arylation of 1,3-cyclohexanediones or by a ring expansion of aryl succinoin derivatives. Enolization of one carbonyl group in the diones, conversion to a leaving group, and subsequent azidation gave 2-aryl-3-azidocycloalk-2-en-1-ones. This two-step, one-pot azidation is highly regioselective with unsymmetrically substituted 2-arylcyclohexane-1,3-diones. The regioselectivity, which is important for access to single isomers of 3,3-disubstituted carbazolones, was analyzed mechanistically and computationally. Finally, a Rh-catalyzed nitrene/nitrenoid insertion into the ortho C-H bond of the aryl moiety gave the H 4 -carbazolones and H 2 -indolones. One carbazolone was elaborated to an intermediate reported in the total synthesis of N-decarbomethoxychanofruticosinate, (-)-aspidospermidine, (+)-kopsihainanine A. With 2-phenylcycloheptane-1,3-dione, prepared from cyclohexanone and benzaldehyde, the azidation reaction was readily accomplished. However, the Rh-catalyzed reaction unexpectedly led to a labile but characterizable azirine rather than the indole derivative. Computations were performed to understand the differences in reactivities of the 5- and 6-membered 2-aryl-3-azidocycloalk-2-en-1-ones in comparison to the 7-membered analogue, and to support the structural assignment of the azirine., (© 2023 Wiley-VCH GmbH.)

Dendrimers are a family of polymers with highly branched structure, well-defined composition, and extensive functional groups, which have attracted great attention in biomedical applications. Micelles formed by dendrimers are ideal nanocarriers for delivering anticancer agents due to the explicit study of their characteristics of particle size, charge, and biological properties such as toxicity, blood circulation time, biodistribution, and cellular internalization. Here, the classification, preparation, and structure of dendrimer micelles are reviewed, and the specific functional groups modified on the surface of dendrimers for tumor active targeting, stimuli-responsive drug release, reduced toxicity, and prolonged blood circulation time are discussed. In addition, their applications are summarized as various platforms for biomedical applications related to cancer therapy including drug delivery, gene transfection, nano-contrast for imaging, and combined therapy. Other applications such as tissue engineering and biosensor are also involved. Finally, the possible challenges and perspectives of dendrimer micelles for their further applications are discussed., (© 2023 Wiley-VCH GmbH.)

To cater to the swift advance of flexible wearable electronics, there is growing demand for flexible energy storage system (ESS). Aqueous zinc ion energy storage systems (AZIESSs), characterizing safety and low cost, are competitive candidates for flexible energy storage. Hydrogels, as quasi-solid substances, are the appropriate and burgeoning electrolytes that enable high-performance flexible AZIESSs. However, challenges still remain in designing suitable and comprehensive hydrogel electrolyte, which provides flexible AZIESSs with high reversibility and versatility. Hence, the application of hydrogel electrolyte-based AZIESSs in wearable electronics is restricted. A thorough review is required for hydrogel electrolyte design to pave the way for high-performance flexible AZIESSs. This review delves into the engineering of desirable hydrogel electrolytes for flexible AZIESSs from the perspective of electrolyte designers. Detailed descriptions of hydrogel electrolytes in basic characteristics, Zn anode, and cathode stabilization effects as well as their functional properties are provided. Moreover, the application of hydrogel electrolyte-based flexible AZIESSs in wearable electronics is discussed, expecting to accelerate their strides toward lives. Finally, the corresponding challenges and future development trends are also presented, with the hope of inspiring readers., (© 2023 Wiley-VCH GmbH.)

Sodium-ion (Na-ion) battery is one of the research focuses because of high theoretical capacity and low cost. However, seeking for ideal anodes remains a big challenge. Here, a Co 3 S 4 @NiS 2 /C synthesized by in situ growing NiS 2 on CoS spheres then converting to Co 3 S 4 @NiS 2 heterostructures encapsulated by carbon matrix, is developed as a promising anode. Co 3 S 4 @NiS 2 /C as anode displays a high capacity of 654.1 mAh g -1 after 100 cycles. Even over 2000 cycles at a high rate of 10 A g -1 , capacity exceeds 143.2 mAh g -1 . Heterostructures between Co 3 S 4 and NiS 2 improve electron transfer as verified by density functional theory (DFT) calculations. In addition, when cycling at a high temperature of 50 °C, the Co 3 S 4 @NiS 2 /C anode displays 525.2 mAh g -1 , while it remains 340 mAh g -1 at -15 °C, indicating all-climate potential for using under different temperatures., (© 2023 Wiley-VCH GmbH.)

Herein, small-sized fluorescent carbon nanoparticles (CNs) with tunable shapes ranging from spheres to various rods with aspect ratios (ARs) of 1.00, 1.51, 1.89, and 2.85 are prepared using a simple anion-directed strategy for the first time. Based on comprehensive morphological and structural characteristics of CNs, along with theoretical calculations of density functional theory and molecular dynamics simulations, their shape-control mechanism is attributed to interionic interactions-induced self-assembly, followed by carbonization. The endoplasmic reticulum-targeting accuracy of CNs is gradually enhanced as their shape changes from spherical to higher-AR rods, accompanied by a Pearson's correlation coefficient up to 0.90. This work presents a facile approach to control the shape of CNs and reveals the relationship between the shape and organelle-targeting abilities of CNs, thereby providing a novel idea to synthesize CNs that serve as precise organelle-targeted fluorescent probes., (© 2023 Wiley-VCH GmbH.)

Luminescent materials possessing a "hot-exciton" mechanism and aggregation-induced emission (AIE) qualities are well-suited for use as emitting materials in nondoped organic light-emitting diodes (OLEDs), particularly in deep-red regions where their ground state and singlet excited state surfaces are in proximity, leading to the formation of multiple nonradiative channels. However, designing molecules that artificially combine the hot-exciton mechanism and AIE attributes remains a formidable task. In this study, a versatile strategy is presented to achieve hot-exciton fluorescence with AIE property by increasing the first singlet excited (S 1 ) state through modulation of the conjugation length of the newly created acceptor unit, matching the energy level of high-lying triplet (T n ) states, and enhancing exciton utilization efficiency by employing suitable donor moieties. This approach reduces the aggregation-caused quenching (ACQ) in the aggregate state, resulting in the proof-of-concept emitter DT-IPD, which produces an unprecedented external quantum efficiency (EQE) of 12.2% and Commission Internationale de I'Eclairage (CIE) coordinates of (0.69, 0.30) in a deep-red non-doped OLED at 685 nm, representing the highest performance among all deep-red OLEDs based on materials with hot-exciton mechanisms. This work provides novel insights into the design of more efficient hot-exciton emitters with AIE properties., (© 2023 Wiley-VCH GmbH.)

Inflammatory disease (ID) is a general term that covers all diseases in which chronic inflammation performs as the major manifestation of pathogenesis. Traditional therapies based on the anti-inflammatory and immunosuppressive drugs are palliative with the short-term remission. The emergence of nanodrugs has been reported to solve the potential causes and prevent recurrences, thus holding great potential for the treatment of IDs. Among various nanomaterial systems, transition metal-based smart nanosystems (TMSNs) with unique electronic structures possess therapeutic advantages owing to their large surface area to volume ratio, high photothermal conversion efficiency, X-ray absorption capacity, and multiple catalytic enzyme activities. In this review, the rationale, design principle, and therapeutic mechanisms of TMSNs for treatments of various IDs are summarized. Specifically, TMSNs can not only be designed to scavenge danger signals, such as reactive oxygen and nitrogen species and cell-free DNA, but also can be engineered to block the mechanism of initiating inflammatory responses. In addition, TMSNs can be further applied as nanocarriers to deliver anti-inflammatory drugs. Finally, the opportunities and challenges of TMSNs are discussed, and the future directions of TMSN-based ID treatment for clinical applications are emphasized., (© 2023 Wiley-VCH GmbH.)

As a type of room temperature phosphorescence (RTP) material, carbon dots (CDs) always show short lifetime and low phosphorescence efficiency. To counter these disadvantages, several strategies, such as embedding in rigid matrix, introducing of heteroatom, crosslink-enhanced emission, etc., are well developed. Consequently, lots of CDs-based RTP materials are obtained. Doping of CDs into various matrix is the dominant method for preparation of long-lived CDs-based RTP materials so far. The desired CDs@matrix composites always display outstanding RTP performances. Meanwhile, matrix-free CDs and carbonized polymer dots-based RTP materials are also widely developed. Amounts of CDs possessing ultra-long lived, multiple colored, and dynamic RTP emission are successfully obtained. Herein, the recent progress achieved in CDs-based RTP materials as well as the corresponding efficient strategies and emission mechanisms are summarized and reviewed in detail. Due to CDs-based RTP materials possess excellent chemical stability, photostability and low biological toxicity, they exhibit great application potential in the fields of anti-counterfeiting, data encryption, and biological monitoring. The application of the CDs-based RTP materials is also introduced in this review. As a promising functional material, development of long wavelength RTP emitting CDs with long lifetime is still challengeable, especially for the red and near-infrared emitting RTP materials., (© 2023 Wiley-VCH GmbH.)

Carbon dots (CDs), fluorescent carbon nanoparticles with particle sizes < 10 nm, are constantly being developed for potential large-scale applications. Recently, methods allow CD synthesis to be carried out on large-scale preparation in a controlled fashion are potentially important for multiple disciplines, including bottom-up strategy, top-down method. In this review, the recent progresses in the research of the methods for large-scale production of CDs and their functionalization are summarized. Especially, the methods of CD synthesis, such as large-scale preparation, hydrothermal/solvothermal, microwave-assisted, magnetic hyperthermia microfluidic and other methods, along with functionalization of CDs, are summarized in detail. By promising applications of CDs, there are three aspects have been already reported, such as enhancing mechanical properties, flame retardancy, and energy storage. Also, future development of CDs is prospected., (© 2022 Wiley-VCH GmbH.)

Quantum materials are usually heterogeneous, with structural defects, impurities, surfaces, edges, interfaces, and disorder. These heterogeneities are sometimes viewed as liabilities within conventional systems; however, their electronic and magnetic structures often define and affect the quantum phenomena such as coherence, interaction, entanglement, and topological effects in the host system. Therefore, a critical need is to understand the roles of heterogeneities in order to endow materials with new quantum functions for energy and quantum information science applications. In this article, several representative examples are reviewed on the recent progress in connecting the heterogeneities to the quantum behaviors of real materials. Specifically, three intertwined topic areas are assessed: i) Reveal the structural, electronic, magnetic, vibrational, and optical degrees of freedom of heterogeneities. ii) Understand the effect of heterogeneities on the behaviors of quantum states in host material systems. iii) Control heterogeneities for new quantum functions. This progress is achieved by establishing the atomistic-level structure-property relationships associated with heterogeneities in quantum materials. The understanding of the interactions between electronic, magnetic, photonic, and vibrational states of heterogeneities enables the design of new quantum materials, including topological matter and quantum light emitters based on heterogenous 2D materials., (© 2022 Wiley-VCH GmbH.)

In the past decades, great efforts have been made to develop novel visible-light photocatalysts to achieve high photocatalytic efficiency by utilizing visible light, the largest proportion of solar energy. As a new type of photocatalyst materials, all-inorganic lead-free halide double perovskites have begun to attract widespread interest. Herein, double perovskite Cs 2 AgBiCl 6 was developed into a visible-light photocatalyst for degrading organic dyes. Cs 2 AgBiCl 6 was prepared by the hydrochloric acid precipitation and anti-solvent recrystallization methods, respectively, and was used to degrade organic dyes under visible light. Samples prepared by the anti-solvent recrystallization method are smaller than those prepared by the hydrochloric acid precipitation method, which can degrade 95.7 % of Sudan III in 10 min and show excellent photocatalytic activity. The cyclic experiments demonstrate that Cs 2 AgBiCl 6 has a good cycle stability. Moreover, Cs 2 AgBiCl 6 -AS also exhibits good photocatalytic degradation ability for Methyl red and Malachite green. These distinctive results indicate that Cs 2 AgBiCl 6 may be a promising material for developing novel, high-efficient and stable visible-light photocatalysts., (© 2023 Wiley-VCH GmbH.)

Circularly polarized electroluminescence (CP-EL) is generally produced in organic light-emitting diodes (OLEDs) based on special CP luminescent (CPL) materials, while common achiral luminescent materials are rarely considered to be capable of direct producing CP-EL. Herein, near ultraviolet CPL materials with high photoluminescence quantum yields and good CPL dissymmetry factors are developed, which can induce blue to red CPL for various achiral luminescent materials. Strong near ultraviolet CP-EL with the best external quantum efficiencies (η ext s) of 9.0 % and small efficiency roll-offs are achieved by using them as emitters for CP-OLEDs. By adopting them as hosts or sensitizers, commercially available yellow-orange achiral phosphorescence, thermally activated delayed fluorescence (TADF) and multi-resonance (MR) TADF materials can generate intense CP-EL, with high dissymmetry factors and outstanding η ext s (30.8 %), demonstrating a simple and universal avenue towards efficient CP-EL., (© 2023 Wiley-VCH GmbH.)

Energy band structure of inorganic nano-sonosensitizers is usually optimized by surface decoration with noble metals or metal oxide semiconductors, aiming to enhance interfacial charge transfer, augment spin-flip and promote radical generation. To avoid potential biohazards of metallic elements, herein, metal-free graphitic carbon nitride quantum dots (g-C 3 N 4 QDs) are anchored onto hollow mesoporous TiO 2 nanostructure to formulate TiO 2 @g-C 3 N 4 heterojunction. The direct Z-scheme charge transfer significantly improves the separation/recombination dynamics of electron/hole (e - /h + ) pairs upon ultrasound (US) stimulation, which promotes the yield of singlet oxygen ( 1 O 2 ) and hydroxyl radicals (·OH). The conjugated g-C 3 N 4 QDs with peroxidase-mimic activity further react with the elevated endogenous H 2 O 2 and aggravate oxidative stress. After loading prodrug romidepsin (RMD) in TiO 2 @g-C 3 N 4 , stimulus-responsive drug delivery can be realized by US irradiation. The disulfide bridge of the released RMD tends to be reduced by glutathione (GSH) into a monocyclic dithiol, which arrests cell cycle in G2/M phase and evokes apoptosis through enhanced histone acetylation. Importantly, reactive oxygen species accumulation accompanied by GSH depletion is devoted to deleterious redox dyshomeostasis, leading to augmented systemic oncotherapy by eliciting antitumor immunity. Collectively, this paradigm provides useful insights in optimizing the performance of TiO 2 -based nano-sonosensitizers for tackling critical diseases., (© 2023 Wiley-VCH GmbH.)

Circularly polarized luminescence (CPL) has attracted much interest due to its potential applications on chiral photonic techniques and optoelectronic materials science. As known, dissymmetry factor (g em ) of CPL is one essential factor for evaluating the features of CPL-active materials. Much attention has focused on how to increase the g em value, which is one of the most important issues for CPL practical applications. Recently, more and more works have demonstrated that chiral supramolecular could provide the significant strategy to improve the g em value through the orderly helical superstructure of chiral building blocks. Normally, this kind of chiral supramolecular assembly process can be accompanied by chirality transfer and induction mechanism, which can promote the amplification effect on the induced CPL of achiral dyes. In this review, we fully summarized recent advances on the induced CPL-active materials of chiral supramolecular co-assemblies, their applications in circularly polarized organic light-emitting diodes (CP-OLEDs) and current challenges., (© 2023 Wiley-VCH GmbH.)

The 3D supramolecular framework (3D-SF) is constructed in this work through the hydrogen bond assisted self-assembly of spherical dendritic nanopolymer to regulate the flexibility, stability, and resistive switching (RS) performance of perovskite resistive random-access memory (RRAM). Herein, the 3D-SF network acts as the perovskite crystallization template to regulate the perovskite crystallization process due to its coordination interaction of functional groups with the perovskite grains, presenting the uniform, pinhole-free, and compact perovskite morphology for stable flexible RRAM. The 3D-SF network in situ stays at the perovskite intergranular boundaries to crosslink the perovskite grains. The RS performance of 3D-SF-modified perovskite RRAM device is evidently improved to the ON/OFF ratio of 10 5 , the cycle number of 500 times, and the data retention time of 10 4 s. The 50-days exposure of unencapsulated RRAM device at ambient environment still makes the ON/OFF ratio to be kept at ≈10 4 , indicating the potential of long-term stable multilevel storage in the high-density data storage. The bending action under different radius also does not change the RS performance due to the excellent bending-resistant ability of 3D-SF-modified perovskite film. This work explores a novel polymer additive strategy to construct the 3D supramolecular framework for stable flexible perovskite optoelectronic devices., (© 2022 Wiley-VCH GmbH.)

The sodium (Na)-metal anode with high theoretical capacity and low cost is promising for construction of high-energy-density metal batteries. However, the unsatisfactory interface between Na and the liquid electrolyte induces tardy ion transfer kinetics and dendritic Na growth, especially at ultralow temperature (-40 °C). Herein, an artificial heterogeneous interphase consisting of disodium selenide (Na 2 Se) and metal vanadium (V) is produced on the surface of Na (Na@Na 2 Se/V) via an in situ spontaneous chemical reaction. Such interphase layer possesses high sodiophilicity, excellent ionic conductivity, and high Young's modulus, which can promote Na-ion adsorption and transport, realizing homogenous Na deposition without dendrites. The symmetric Na@Na 2 Se/V cell exhibits outstanding cycling life span of over 1790 h (0.5 mA cm -2 /1 mAh cm -2 ) in carbonate-based electrolyte. More remarkably, ab initio molecular dynamics simulations reveal that the artificial Na 2 Se/V hybrid interphase can accelerate the desolvation of solvated Na + at -40 °C. The Na@Na 2 Se/V electrode thus exhibits exceptional electrochemical performance in symmetric cell (over 1500 h at 0.5 mA cm -2 /0.5 mAh cm -2 ) and full cell (over 700 cycles at 0.5 C) at -40 °C. This work provides an avenue to design artificial heterogeneous interphase layers for superior high-energy-density metal batteries at ambient and ultralow temperatures., (© 2023 Wiley-VCH GmbH.)

How to control the stability of oil-in-water (O/W) emulsions is one of the main topics for scientists working in colloidal systems. Recently, carbon dots (CDs) have received great interest as smart materials because of their excellent physicochemical properties and versatile applications. Herein, for the first time, advanced and switchable O/W emulsions are presented that are stabilized by the synergistic effect of cationic surfactant cetyltrimethylammonium bromide CTAB (emulsifier) and similarly charged CDs (stabilizer). In the formulated emulsion, the cationic surfactant molecules are adsorbed at the oil and water interface to decrease the interfacial tension and enrich the drops with a positive charge to ensure intensive electrostatic repulsions among them. On the contrary, cationic CDs are distributed in the water phase among the droplets to reduce the water secretion and prevent flocculation and droplet coalescence. The stabilizing effect is found to be universal for emulsions of a range of oil phases. Furthermore, the formulated emulsion is found to be switchable between "stable" and "unstable" modes by adding an equivalent of anionic surfactant sodium dodecyl benzene sulphonate (SDBS). The stabilized and switchable O/W emulsions are believed to have wide practical applications in water purification, pharmaceuticals, protein recognition, as well as catalysis., (© 2022 Wiley-VCH GmbH.)

It is essential to create organic compounds that exhibit circularly polarized luminescence (CPL) in the near-infrared (NIR) range. Helicene-type emitters possess appealing chiroptical features, however, such NIR molecules are scarce due to a paucity of synthetic strategies. Herein, we developed a series of helical β-isoindigo-based B-O-B bridged aza-BODIPY analogs that were synthesized conveniently. The reaction of diimino-β-isoindigo with a heteroaromatic amine produced a restricted ligand cavity, which triggered off the generation of a B-O-B bridge. The B-O-B bridge led to distorted conformations that satisfy the helical requirements, resulting in excellent spectroscopic and chiroptical properties. Tunable CPL with the highest luminescence dissymmetry factor (g lum ) of 1.3×10 -3 and a CPL brightness (B CPL =11.5 M -1  cm -1 ) in the NIR region was achieved. This synthetic approach is expected to offer a new opportunity to chiral chemistry and increase flexibility for chiroptical tuning., (© 2022 Wiley-VCH GmbH.)

As a critical action plan formulated for peaking carbon dioxide emissions, polymeric electromagnetic interference (EMI) shielding materials based on CO 2 foaming technology have recently been attracting widespread attention in both research and industry, attributable to their efficient use of CO 2 , high specific strength, corrosion resistance and low-cost characteristics. In the past decade, the emergence of novel design concepts and preparation techniques for CO 2 foaming technology has led to the development of new high-performance EMI shielding materials in this field. This review summarizes the research progress made to date on the fabrication of EMI shielding composite foams by supercritical carbon dioxide (scCO 2 ) foaming. We also explore the structure-activity relationships between the component/distribution and EMI shielding properties. Additionally, the application prospects and development challenges of new EMI shielding composite foams are described., (© 2022 Wiley-VCH GmbH.)

White circularly polarized organic light-emitting diodes (CP-WOLEDs) are of great significance in potential lighting sources and full-color 3D displays. However, High-performance white CP-EL sources are almost unexplored. We have constructed full-color CP-EL devices based on chiral co-assemblies by using three achiral conjugated pyrene-based dyes (BP, w-WP and c-WP) doped with chiral binaphthyl-based enantiomers (S-/R-M) as the EMLs through an intermolecular chirality induction mechanism. (S-/R-M) 0.2 -(c-WP) 0.8 films exhibit regular helix nanofibers under annealing treatment and emit strong white CPL. Significantly, remarkable CP-WOLEDs based on (S-/R-M) 0.2 -(c-WP) 0.8 were achieved with |g EL | values as high as 6.2×10 -2 and an excellent CRI of 98 at the CIE coordinates of (0.33, 0.33). These are the highest g EL and CRI values of reported CP-WOLEDs to date. This is the first achievement of CP-WOLEDs based on chiral co-assembled helix nanofiber emitters, and provides a valuable strategy with which to develop white CP-EL for future practical applications., (© 2022 Wiley-VCH GmbH.)

Rechargeable aqueous zinc-ion batteries are of great potential as one of the next-generation energy-storage devices due to their low cost and high safety. However, the development of long-term stable electrodes and electrolytes still suffers from great challenges. Herein, a self-separation strategy is developed for an interface layer design to optimize both electrodes and electrolytes simultaneously. Specifically, the coating with an organometallics (sodium tricyanomethanide) evolves into an electrically responsive shield layer composed of nitrogen, carbon-enriched polymer network, and sodium ions, which not only modulates the zinc-ion migration pathways to inhibit interface side reactions but also adsorbs onto Zn perturbations to induce planar zinc deposition. Additionally, the separated ions from the coating can diffuse to the electrolyte to affect the Zn 2+ solvation structure and maintain the cathode structural stability by forming a stable cathode-electrolyte interface and sodium ions' equilibrium, confirmed by in situ spectroscopy and electrochemical analysis. Due to these unique advantages, the symmetric zinc batteries exhibit an extralong cycling lifespan of 3000 h and rate performance at 20 mA cm -2 at wide temperatures. The efficiency of the self-separation strategy is further demonstrated in practical full batteries with an ultralong lifespan over 10 000 cycles from -35 to 60 °C., (© 2022 Wiley-VCH GmbH.)

Halide perovskite semiconductors with extraordinary optoelectronic properties have been fascinatedly studied. Halide perovskite nanocrystals, single crystals, and thin films have been prepared for various fields, such as light emission, light detection, and light harvesting. High-performance devices rely on high crystal quality determined by the nucleation and crystal growth process. Here, the fundamental understanding of the crystallization process driven by supersaturation of the solution is discussed and the methods for halide perovskite crystals are summarized. Supersaturation determines the proportion and the average Gibbs free energy changes for surface and volume molecular units involved in the spontaneous aggregation, which could be stable in the solution and induce homogeneous nucleation only when the solution exceeds a required minimum critical concentration (C min ). Crystal growth and heterogeneous nucleation are thermodynamically easier than homogeneous nucleation due to the existent surfaces. Nanocrystals are mainly prepared via the nucleation-dominated process by rapidly increasing the concentration over C min , single crystals are mainly prepared via the growth-dominated process by keeping the concentration between solubility and C min , while thin films are mainly prepared by compromising the nucleation and growth processes to ensure compactness and grain sizes. Typical strategies for preparing these three forms of halide perovskites are also reviewed., (© 2022 Wiley-VCH GmbH.)

An aerobic phosphorylation of N-aryltetrahydroisoquinolines was realized by SbCl 3 initiated sp 3 C-H bond functionalization, providing a series of α-aminophosphonates in high yields. This work reveals that SbCl 3 /O 2 is an efficient and facile catalyst system to enable the aerobic C-H functionalization, and antimony containing reagents might be potentially applied to more general transformations., (© 2022 Wiley-VCH GmbH.)

The knowledge of mechanics of materials has been extensively implemented in developing functional materials, giving rise to recent advances in soft actuators, flexible electronics, mechanical metamaterials, tunable mechanochromics, regenerative mechanomedicine, etc. While conventional mechanics of materials offers passive access to mechanical properties of materials in existing forms, a paradigm shift is emerging toward proactive programming of materials' functionality by leveraging the force-geometry-property relationships. Here, such a rising field is coined as "mechanomaterials". To profile the concept, the design principles in this field at four scales is first outlined, namely the atomic scale, the molecular scale, the manipulation of nanoscale materials, and the microscale design of structural materials. A variety of techniques have been recruited to deliver the multiscale programming of functional mechanomaterials, such as strain engineering, capillary assembly, topological interlocking, kirigami, origami, to name a few. Engineering optical and biological functionalities have also been achieved by implementing the fundamentals of mechanochemistry and mechanobiology. Nonetheless, the field of mechanomaterials is still in its infancy, with many open challenges and opportunities that need to be addressed. The authors hope this review can serve as a modest spur to attract more researchers to further advance this field., (© 2021 Wiley-VCH GmbH.)

Multibridge channel field-effect transistors (MBCFETs) enable improved gate control and flow of a large drive current and they are regarded as promising candidates for next-generation transistor architecture. However, in achieving a larger drive current with a thinner channel, limitations arise from the decrease in mobility when the thickness of the Si nanosheet is less than 5 nm. In addition, an increase in the leakage current is unavoidable when a large number of channels are stacked. Here, a 2D ultrathin MBCFET is demonstrate, constructed based on 2 nm/2 nm MoS 2 channels. The normalized drive current (23.11 µA*µm µm -1 ) in each level channel of this MBCFET exceeds that of the latest seven-level-stacked Si MBCFET, while the leakage current is only 0.4% of this value, with the subthreshold swing reaching 60 mV dec -1 and an on/off ratio reaching up to 4 × 10 8 at room temperature. Furthermore, the drive current of this 2D ultrathin MBCFET can be further increased by regulating the polarity of the operation voltage to reduce the injection barrier. The combination of 2D materials and an MBC structure has the potential for use in high-performance and low-power-consumption electronics., (© 2021 Wiley-VCH GmbH.)

The limited effectiveness of current therapeutics against malignant brain gliomas has led to an urgent need for development of new formulations against these tumors. Chelator Dp44mT (di-2-pyridylketone-4,4-dimethyl-3-thiosemicarbazone) presents a promising candidate to defeat gliomas due to its exceptional anti-tumor activity and its unique ability to overcome multidrug resistance. The goal of this study is to develop a targeted nano-carrier for Dp44mT delivery to glioma tumors and to assess its therapeutic efficacy in vitro and in vivo. Dp44mT is loaded into poly(ethylene glycol) (PEG)ylated poly(lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) decorated with glioma-targeting ligand Interlukin 13 (IL13). IL13-conjugation enhanced the NP uptake by glioma cells and also improved their transport across an in vitro blood-brain-barrier (BBB) model. This targeted formulation showed an outstanding toxicity towards glioma cell lines and patient-derived stem cells in vitro, with IC 50 values less than 125 nM, and caused no significant death in healthy brain microvascular endothelial cells. In vivo, when tested on a xenograft mouse model, IL13-conjugated Dp44mT-NPs reduced the glioma tumor growth by ≈62% while their untargeted counterparts reduced the tumor growth by only ≈16%. Notably, this formulation does not cause any significant weight loss or kidney/liver toxicity in mice, demonstrating its great therapeutic potential., (© 2020 Wiley-VCH GmbH.)

Developing hydrogen evolution reaction (HER) electrocatalysts with high activity, durability and moderate price is essential for sustainable hydrogen energy utilization. Here, the facile coupling of carbon dots (CDs, 0D carbon materials) and carbon fibres (CFs, 1D carbon materials) for enhanced electrochemical hydrogen production was demonstrated. Electrochemical tests revealed that the CD/CF catalysts showed outstanding catalytic activity with a small overpotential of 280 mV at the current density of 10 mA cm -2 , a small Tafel slope of 87 mV dec -1 and prominent durability. Percolation theory was for the first time introduced to interpret the catalytic mechanism of the CD/CF catalysts. The special morphology assembled by the 0D carbons constituted the percolating clusters and promoted electron transport throughout the 1D carbons. The strategy and theory can be adapted to general electrocatalytic applications for achieving and interpreting precise tuning on highly efficient electron transfer in electrocatalysts., (© 2020 Wiley-VCH GmbH.)

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co-doped carbon dots (F,N-doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N-doped CDs increases with UV light irradiation (5 s-30 min), accompanied with a blue-shift of the fluorescence emission from 586 nm to 550 nm. F,N-doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N-doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure-triggered aggregation-induced emission in the range 1.0 atm-0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high-pressure conditions and enhances their anti-photobleaching., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon dots (CDs), with excellent optical property and cytocompatibility, are an ideal class of nanomaterials applied in the field of biomedicine. However, the weak response of CDs in the near-infrared (NIR) region impedes their practical applications. Here, UV-vis-NIR full-range responsive fluorine and nitrogen doped CDs (N-CDs-F) are designed and synthesized that own a favorable donor-π-acceptor (D-π-A) configuration and exhibit excellent two-photon (λ ex = 1060 nm), three-photon (λ ex = 1600 nm), and four-photon (λ ex = 2000 nm) excitation upconversion fluorescence. D-π-A-conjugated CDs prepared by solvothermal synthesis under the assistance of ammonia fluoride are reported and are endowed with larger multiphoton absorption (MPA) cross sections (3PA: 9.55 × 10 -80 cm 6 s 2 photon -2 , 4PA: 6.32 × 10 -80 cm 8 s 3 photon -3 ) than conventional organic compounds. Furthermore, the N-CDs-F show bright deep-red to NIR fluorescence both in vitro and in vivo, and can even stain the nucleoli of tumor cells. A plausible mechanism is proposed on the basis of the strong inter-dot and intra-dot hydrogen bonds through NH···F that can facilitate the expanding of conjugated sp 2 domains, and thus not only result in lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy level but also larger MPA cross sections than those of undoped CDs., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Bone tissue engineering (BTE) has received significant attention due to its enormous potential in treating critical-sized bone defects and related diseases. Traditional materials such as metals, ceramics, and polymers have been widely applied as BTE scaffolds; however, their clinical applications have been rather limited due to various considerations. Recently, carbon-based nanomaterials attract significant interests for their applications as BTE scaffolds due to their superior properties, including excellent mechanical strength, large surface area, tunable surface functionalities, high biocompatibility as well as abundant and inexpensive nature. In this article, recent studies and advancements on the use of carbon-based nanomaterials with different dimensions such as graphene and its derivatives, carbon nanotubes, and carbon dots, for BTE are reviewed. Current challenges of carbon-based nanomaterials for BTE and future trends in BTE scaffolds development are also highlighted and discussed., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Carbon dots (CDs) have attracted increasing attention in disease therapy owing to their low toxicity and good biocompatibility. Their therapeutic effect strongly depends on the CDs structure (e.g., size or functional groups). However, the impact of CDs chirality on maltase and blood glucose level has not yet been fully emphasized and studied. Moreover, in previous reports, chiral CDs with targeted optical activity have to be synthesized from precursors of corresponding optical rotation, severely limiting chiral CDs design. Here, chiral CDs with optical rotation opposite to that of the precursor are facilely prepared through electrochemical polymerization. Interestingly, their chirality can be regulated by simply adjusting reaction time. At last, the resultant (+)-DCDs (700 µg mL -1 ) are employed to modify maltase in an effort to regulate the hydrolytic rate of maltose, showing an excellent inhibition ratio to maltase of 54.7%, significantly higher than that of (-)-LCDs (15.5%) in the same reaction conditions. The superior performance may be attributed to the preferable combination of DCDs with maltase. This study provides an electrochemical method to facilely regulate CDs chirality, and explore new applications of chiral CDs as antihyperglycemic therapy for controlling blood glucose levels., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The vascular endothelial growth factor (VEGF) induces pathological angiogenetic ocular diseases. It is a scientific challenge to develop carriers for the controlled release of inhibitors for VEGF present in the back of the eye domain. Carbon dots (C-dots) functionalized with the VEGF aptamer are introduced and the hybrid nanoparticles are used for ocular nanomedicine. The C-dots are applied as effective carriers of the anti-VEGF aptamer across the cornea, yielding therapeutic levels upon topical administration. The hybrids show no toxicity for both in vitro and in vivo murine animal model, and further enable noninvasive intraocular concentration monitoring through the C-dots inherent fluorescence. In addition, the hybrid C-dots effectively inhibit VEGF-stimulated angiogenesis in choroidal blood vessels. This inhibition is comparable to two commercially available anti-VEGF drugs, bevacizumab and aflibercept. The hybrid aptamer-modified C-dots provide a versatile nanomaterial to treat age-related macular degeneration and diabetic retinopathy., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scope: The aim of this article is to conduct an umbrella review to study the strength and validity of associations between tea consumption and diverse health outcomes., Methods and Results: Meta-analyses of observational studies examining associations between tea consumption and health outcomes in all human populations and settings are screened. The umbrella review identifies 96 meta-analyses with 40 unique health outcomes. Tea consumption shows greater benefits than harm to health in this review. Dose-response analyses of tea consumption indicates reduced risks of total mortality, cardiac death, coronary artery disease, stroke, and type 2 diabetes mellitus with increment of two to three cups per day. Beneficial associations are also found for several cancers, skeletal, cognitive, and maternal outcomes. Harmful associations are found for esophageal and gastric cancer when the temperature of intake is more than 55-60 °C., Conclusion: Tea consumption, except for very hot tea, seems generally safe at usual levels of intake, with summary estimates indicating the largest reduction for diverse health outcomes at two to three cups per day. Generally, tea consumption seems more beneficial than harmful in this umbrella review. Randomized controlled trials are further needed to understand whether the observed associations are causal., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)