With the increasing awareness of environmental protection and the in-depth implementation of sustainable development strategies, the commonly used liquid acid catalysts in traditional chemical production processes are facing the pressure of elimination or substitution due to their high corrosiveness, difficulty in recycling and potential environmental impact. Solid acids, renowned for their straightforward preparation, minimal ecological footprint, and exceptional catalytic prowess, have become the focus of scientific research and industrial attention. Currently, solid acid catalysts have been proven to be efficient in catalyzing diverse chemical reactions such as alkylation, isomerization, and esterification reactions. Nevertheless, their extensive industrial adoption is significantly hindered by the challenges of suboptimal stability and limited reusability. Developing advanced solid acid catalysts with high activity and stability is of great value and significance in both theoretical research and experimental exploration. A significant amount of notable fundamental research has been devoted to overcoming these limitations, and this review summarizes the scientific and technological work dedicated to preparing efficient solid acid catalysts. At the same time, we highlight the importance of rare earth elements for modification of solid acid catalysts due to their unique multi-electronic bonding and coordinated variability nature, which can have a positive effect on the structural evolution of acid catalysts, thereby improving the activity and stability of solid acid catalysts. This review initially presents concept, classification, synthesis methods and characterization of commonly used solid acid catalysts. Beyond that, we introduce the represented research progress of rare earth elements modified solid acid catalysts. The main emphasis of this review is investigating the contribution of acid properties to the catalytic performance (e.g., acid strength, acid content, type of acid sites, etc.), rather than the traditional physical and chemical properties (e.g., specific surface area, crystalline structure, morphology, etc.). Finally, we present the challenges of the existing catalytic systems and prospects of this field.

Nanozymes, characterized by their combination of the favorable catalytic activity of biological enzymes with the structural properties of nanomaterials, have emerged as effective substitutes for natural enzymes. They exhibit high stability, adjustable activity, and robust environmental tolerance, which makes them as ideal candidates for various applications. The exceptional catalytic properties have facilitated their widespread adoption in colorimetric sensing analysis, particularly when integrated with paper substrates. Paper, renowned for its low cost, high porosity, and biodegradability, serves as an excellent platform for developing simple and effective point-of-care testing (POCT) tools. In this paper, we first delve into the construction and operational principles of paper-based colorimetric sensors. These sensors leverage the unique characteristics of paper to create microfluidic channels and reaction zones, enabling the controlled flow and mixing of analytes with detection reagents. The colorimetric response, resulting from the catalytic reaction between the analyte and the nanozyme-based reagent, serves as the basis for qualitative and quantitative analysis. Subsequently, a comprehensive overview of the types of nanozymes and their catalytic reaction mechanisms is provided. Nanozymes encompass a wide range of materials, including metal oxides, metal sulfides, carbon-based nanomaterials, metal-organic frameworks, and single-atom nanozymes, etc., each exhibiting distinct catalytic properties tailored for specific sensing applications. The catalytic reactions involve the oxidation or reduction of analytes, leading to a color change that can be visually detected or analyzed using a smartphone or spectrophotometer. Furthermore, the significant applications of paper-based colorimetric sensors based on nanozymes for POCT are reviewed, focusing on key areas such as food safety analysis, environmental quality monitoring, and biomedical diagnosis. Despite lots of advantages, paper-based colorimetric sensors based on nanozymes face several challenges in the field of POCT. These include limitations in detection sensitivity, biosecurity, and integration with advanced technologies for real-time data analysis. In conclusion, the field of paper-based colorimetric sensors based on nanozymes for POCT is rapidly evolving. With ongoing research and technological advancements, it is anticipated that these sensors will overcome current challenges and offer even more accurate, rapid, and user-friendly solutions for POCT applications in various fields. Their potential to revolutionize healthcare, food safety, and environmental monitoring is immense, making them a promising area of research for the future.

Carbon dioxide (CO₂) is the primary contributor to the greenhouse effect, and its increasing concentration in the atmosphere has become a major driver of global climate change. However, CO₂ is also the most inexpensive and abundant carbon resource in nature. The hydrogenation of CO₂ to produce high-value-added chemicals such as light olefins not only enables the utilization of CO₂ as a resource but also reduces the reliance on non-renewable resources like petroleum for light olefins production. This has profound implications for global energy security and sustainable development. This article reviews the research progress and reaction mechanisms (CO₂-FTS pathway and CO₂-MeOH pathway) of iron-based catalysts for the hydrogenation of CO₂ to produce light olefins. This article comprehensively reviews recent advances in iron-based catalysts for CO₂ hydrogenation to light olefins, with particular emphasis on the CO₂-FTS and CO₂-MeOH pathways: the surface carbide mechanism, the surface enol mechanism, and the CO insertion mechanism. The active sites and structural evolution of Fe-based catalysts during the reaction process are discussed. Based on this, the main factor leading to the deactivation of Fe-based catalysts is identified as the irreversible oxidation of the active phase (Fe₅C₂) to the inactive phase (Fe₃O₄). The article emphasizes the effects of bimetallic active components (Fe-Co, Fe-Ni, Fe-Ru bimetallic catalysts), supports (oxides, metal-organic frameworks, carbon materials, zeolites), promoters (alkali and alkaline earth metals, transition metals and their oxides, rare earth metals, biological promoters), and catalyst preparation methods and conditions on the activity and selectivity of Fe-based catalysts in the CO₂-FTS pathway. The compositional and structural factors influencing the performance of Fe-based catalysts are analyzed. Additionally, representative bifunctional catalysts in both the CO₂-FTS and CO₂-MeOH pathways are introduced, with examples illustrating how bifunctional catalysts can accelerate the reaction process and reduce energy consumption. Finally, we provide an outlook on the research directions of iron-based catalysts for CO₂ hydrogenation to light olefins, proposing potential future research trends and challenges, aiming to offer references and insights for researchers in this field.

Exosomes are small extracellular vesicles derived from parent cells, carrying nucleic acids, proteins, and other biomolecules. Due to their ability to reflect the physiological and pathological states of parent cells in real time, exosomes have significant potential in biomedical applications, including drug delivery, disease diagnosis, and therapeutic interventions. A key step in their application is the efficient separation and purification of exosomes from biological fluids (such as blood, saliva) or cell culture supernatants, ensuring the removal of impurities. Numerous separation techniques, including ultracentrifugation, ultrafiltration, size exclusion chromatography, polymer precipitation, and immunoaffinity capture, have been developed based on the size, density, charge, and composition of exosomes. Although ultracentrifugation is widely regarded as the gold standard for exosome isolation, each method has its advantages and limitations in terms of purity, efficiency, processing capacity, complexity, and convenience. Recently, the combination of different separation methods has emerged as a promising strategy. Moreover, advances in interdisciplinary fields, such as chemistry, materials science, biology, medicine, engineering, and mechanics, have led to the development of innovative separation technologies, including microfluidics, fluid flow-based methods, thermophoresis, lipid-based recognition, and DNA aptamer-based affinity. These novel techniques have substantially improved the efficiency and purity of exosome isolation. In this review, we first offer a comprehensive overview of both traditional and emerging separation methods, the advantages and disadvantages of each method were discussed and summarized. We also illustrate the latest progress and representative work in the exosome separation field. Finally, we put forward our own insights on the future development, including balancing between purity and yield, isolation of specific subpopulations of exosomes, standardization and automation separation and exploration of new separation technologies. We believe that significant breakthroughs in exosome separation will be achieved in the near future, and will contribute to the development of the biomedical applications. We hope this review will be helpful in promoting the development of exosome separation field.

Covalent triazine frameworks (CTFs) represent a class of crystalline two-dimensional materials constructed by the interconnection of triazine rings. These materials are increasingly recognized for their potentials in photocatalysis due to their tunable functionality, adjustable bandgap, and structural stability. However, the inherent two-dimensional nature of these frameworks results in stacking through non-covalent interactions between layers, which means that the interlayer forces are relatively weak. This characteristic introduces the possibility of variations in stacking arrangements during both the framework formation process and its subsequent photocatalytic applications. Such variations in stacking can significantly impact the photocatalytic performance by altering its light absorption properties, exciton excitation, and migration characteristics, which, in turn, affect the photocatalytic dynamics of the material. Currently, the mechanisms underlying the formation of interlayer displacements in CTFs have not been extensively studied. Moreover, the influence of different displacement behaviors on the photocatalytic carrier dynamics within these frameworks remains underexplored and not well understood. To address this gap, this study employs density functional theory (DFT) to investigate the key factors influencing interlayer displacement behaviors in four types of CTFs: CTF-1, CTF-2, CTF-13, and CTF-133. The findings reveal that the process of interlayer displacement in these CTFs is a spontaneous process. Through analyses of electronic localization functions and charge density distributions, it was determined that the displacement is primarily caused by repulsive π-electron interactions on the nitrogen atoms within the triazine rings of adjacent layers. This repulsion creates a tendency for layer displacement, while the stacking of benzene ring units serves to stabilize the interlayer arrangement. Additionally, the study explores the photocatalytic carrier dynamics of CTF-1 frameworks with various stacking configurations. The results demonstrate that the CTF-1 frameworks with AA-stacking mode exhibits an optimal bandgap and carrier migration rate, positioning it as a promising candidate for use as a semiconductor photocatalyst. This study investigates the interlayer displacement behavior of triazine-based covalent organic framework materials from a microscopic perspective, and will provide theoretical insights and a basis for the design of novel catalysts based on CTFs.

The chemistry of main group elements with low oxidation states occupies an important position in main group chemistry. Research results in this field can not only enrich the theoretical connotation of chemical bonding, but also have great significance in organometallic chemistry and catalysis, small molecule activation and transformation, etc. Compared with the chemistry of low-oxidation-state p-block elements, the s-block alkaline earth metal elements with low electronegativity can easily lose two valence electrons to form stable ＋2 oxidation state compounds, but it is more difficult to form low-oxidation-state species with relatively low stability and strong reducing property. Therefore, the study on low-oxidation-state alkaline earth organometallic chemistry is full of challenges. This review outlines the development history of low-oxidation-state alkaline earth organometallic chemistry, briefly describes the relatively mature low-oxidation-state magnesium chemistry, comprehensively introduces the low-oxidation-state beryllium chemistry that has recently made significant progress, highlights the low-oxidation-state calcium, strontium, and barium chemistry that still needs urgent breakthrough.

Aqueous organic redox flow batteries (AORFBs), recognized as a promising large-scale energy storage technology due to their high efficiency, inherent safety, and tunable performance characteristics, have garnered significant research interest in recent years. This review systematically summarizes recent advances in positive redox-active materials for AORFBs, with a focused analysis of representative organic electroactive species, including ferrocene derivatives, ferrocyanides/iron-based complexes, nitroxide radicals, quinones, and phenothiazine-based compounds. Through molecular engineering strategies such as functional group modification, conjugation extension, and electronic structure modulation, critical properties of organic active materials, including redox potentials, solubility in aqueous electrolytes, and chemical and electrochemical stability, have been substantially enhanced, leading to marked improvements in battery performance metrics. Despite these advancements, the practical deployment of organic positive materials continues to face challenges related to long-term cycling stability under operational conditions, limited energy density, and cost-effectiveness in scalable synthesis and processing, requiring further research and solutions.

Novel ultra-thin lithium foils, present significant advantages over conventional lithium foils in terms of energy density, safety, and material cost reduction for lithium metal batteries. These benefits stem from the enhanced electrochemical performance and efficiency that ultra-thin foils can deliver. However, the industrial production of such foils is fraught with challenges. Key issues include the potential for creases and damage during the manufacturing process, as well as the complexity of the techniques required to produce them at scale. Thus, there is an urgent need to innovate existing manufacturing methods to meet the growing industrial demand for ultra-thin lithium foils. In addition to their manufacturing challenges, ultra-thin lithium foils play a crucial role in enhancing the initial coulomb efficiency (ICE) and extending the cycle life of lithium-ion batteries. They are commonly employed to replenish active lithium on the cathode side, compensating for the lithium consumed during the initial charging and discharging phases. However, excessive lithium metal can lead to side reactions with the electrolyte, negatively affecting battery life and safety. Therefore, careful management of lithium deposition is essential to optimize battery performance while ensuring safety. This review specifically addresses the challenges associated with conventional lithium foil manufacturing, providing a detailed analysis of the underlying issues and proposing targeted strategies to overcome them. Relevant examples from recent research will be presented to illustrate successful approaches. Furthermore, the review explores novel preparation methods for ultra-thin lithium foils, evaluating their feasibility for industrial applications. Additionally, the review will summarize the current use of lithium foils in pre-lithiation processes, emphasizing the trend toward integrating ultra-thin lithium foil manufacturing with these processes. This integration is expected to enhance the performance of lithium batteries while simultaneously addressing manufacturing challenges. Ultimately, this review aims to provide valuable insights and inspiration for researchers in the field, serving as a comprehensive resource to stimulate further innovation in lithium foil manufacturing and application.

In recent years, organic reactions involving mesylation have attracted the attention of organic chemists and have made great progress. The sources of methylsulfonyl group mainly include: (1) methylsulfonyl chloride; (2) methylsulfinate salts; (3) dimethyl sulfoxide; (4) dimethyl sulfite; (5) SO₂ and methyl sources in situ generating. Mesylation can be achieved by means of transition-metal-free catalysis, transition metal catalysis, photocatalysis, electrocatalysis, etc. In this review, the applications of mesylation in recent years are summarized. The photocatalysis or electrocatalysis of radical methylsulfonation are emphasized. Additionally, mesylation reactions have been aroused considerable interests both from methylsulfonyl structural standpoint and its application in drugs. Given the increasing application of methylsulfonyl group in the development of drugs and unarguable importance of methylsulfonyl compounds in medicinal chemistry and agrochemistry, it is no doubt that the methylsulfonyl skeleton is a bioactive molecule and is currently in the “emerging mesylation motifs”. Although the synthesis and application of structurally diverse methylsulfonyl compounds have been witnessed in the past decade, the most widely used methods for the preparation of these compounds include all kinds of modern techniques with various methylsulfonyl reagent, which can be generated from various kinds of precursors. For the transition metal-catalyzed synthesis of methylsulfonyl compounds, some common metal salts (such as copper, copper, palladium, iron, nickel) are used as catalysts. Moreover, the visible-light synergistic transition metal catalysis strategy is a simple and efficient method for the construction of methylsulfonyl compounds, and the asymmetric synthesis of methylsulfonyl compounds can be achieved in the presence of chiral ligands. In multi-component reactions, SO₂-insertion has some advantages that cannot be achieved by traditional mesylated reagents for the direct mesylation of alkenes or alkynes. Despite the remarkable achievements in the synthesis of methylsulfonyl compounds, there are still many issues that need to be addressed. For instance, multi-component mesylation reactions are rarely applied in electrocatalysis, asymmetric catalysis fields and flow chemistry. Hopefully, mesylation can gradually appear in photo- and electro-catalyzed radical chemistry, and the related asymmetric reactions will also get more attention and development in the near future.

Leucine zipper (LZ) is a unique protein structure characterized by the periodic insertion of a hydrophobic amino acid, typically leucine, every seven amino acids. In the human genome, 77 leucine zipper transcription factors (LZ TFs) with DNA-binding capabilities have been identified, including basic leucine zipper (bZIP) transcription factors and basic helix-loop-helix leucine zipper (bHLH-LZ) transcription factors. These transcription factors interact through their leucine zipper domains to form homodimers or heterodimers, constructing a complex and extensive network of transcription factor interactions and signal cascades. They exhibit diverse biological functions in various aspects such as growth and development, homeostasis maintenance, response to external stimuli, disease progression, and tumorigenesis. In this article, we will focus on the pivotal roles of leucine zipper transcription factors in cancer and summarize the small molecule inhibitors that directly target these transcription factors so far, to inform and reference the development of small molecule inhibitors of transcription factors and disease research.

Cancer is still a global health challenge and developing novel anticancer drugs with new skeletons is of great importance. Recently, peptide-based agents have become promising candidates for anticancer treatments, especially for the treatment of drug-resistant refractory malignancies. Peptide drug conjugates (PDCs) are novel targeted anticancer drugs with advantages including high permeability to cancer tissues, low production costs, and ease of structural optimization. PDCs could significantly enhance the selectivity and anticancer activity of cytotoxic drugs. Octreotide, which is a cyclic peptide inherently containing one pair of disulfide bonds, could specifically target the somatostatin receptor 2 (SSTR2) on the surface of cancer cells, leading to its widespread clinical applications. The reducible disulfide bonds serve as a commonly utilized cleavable linker in PDCs. However, traditional synthesis of octreotide-drug conjugates based on disulfide bond linkers generally used the “three-step” strategy, including complex synthetic procedure and inducing low isolation yields. To address this issue, we developed a “two-step” synthetic strategy. First, octreotide containing one disulfide bond and the free thiol group (OCT-SH) was synthesized by the straightforward solid-phase peptide synthesis (SPPS). Subsequently, the OCT-SH was conjugated to small molecule drugs through site-specific liquid-phase reaction. To achieve the efficient and economic synthesis of OCT-SH, various SPPS based strategies and peptide cleavage systems were explored. Considering the chromatographic purity and synthetic yield, the optimal synthetic route (SPPS-2) and peptide cleavage system were established. To further validate the robustness of SPPS-2, the influences of different solid resins and peptide cleavage time on synthetic efficiency were investigated. After the efficient manual synthesis of OCT-SH, the promising chemotherapeutic drug doxorubicin (DOX) was covalently coupled to OCT-SH through liquid-phase reaction, affording the octreotide-doxorubicin conjugate. In vitro anticancer studies indicated that the octreotide-doxorubicin conjugate exhibited potent anticancer activity, significantly reducing toxicity to normal cells while achieving selectivity towards cancer cells. The cellular uptake experiment indicated that the covalent conjugation of doxorubicin did not significantly impair the cellular uptake potency of octreotide by cancer cells. Collectively, this study established the “two-step” synthetic strategy, enabling efficient and straightforward preparation of octreotide-doxorubicin conjugates containing the disulfide bond linker. This work also provides valuable references for the SPPS based synthesis of PDCs containing multiple disulfide bonds and inspires the development of novel PDCs for cancer therapy.

Polymer materials play a crucial role in modern industry and technology due to their versatile properties and broad range of applications. However, conventional industrial modification strategies often suffer from an inherent inability to finely tune the balance between strength and toughness, thereby constraining their utility in high-performance applications. To address this challenge, researchers have focused on optimizing the internal structure of polymers as a means to regulate their macroscopic mechanical behavior. Among various strategies, network structure design has emerged as a particularly effective approach. This review takes network structure as a central theme and categorizes the mechanisms of polymer modification based on their energy dissipation pathways. Six major mechanisms are discussed: hydrogen bonding, coordination interactions, host-guest interactions, force-sensitive groups, mechanically interlocked structures, and other reinforcing effects. For each category, we provide overview of recent representative and innovative studies. Through detailed structural analysis and performance evaluation, we highlight how different pathways contribute to the enhancement of mechanical properties. These special structures markedly enhance the material's ability to dissipate energy upon external force. This improvement arises primarily through three synergistic pathways: (1) the reversible breaking and reformation of sacrificial bonds, which serve to absorb and redistribute applied stress; (2) energy dissipation via molecular mobility and chain segmental friction; and (3) multiscale mechanisms of stress transfer and dispersion, which effectively mitigate stress concentration and delay failure. Finally, based on the current research, we identify key unresolved questions and major challenges that must be addressed to further advance the mechanical performance of polymer materials. Looking ahead, the development of next-generation high-performance polymers is expected to converge on several critical directions: achieving sustainability in material sourcing and processing, the combination of high elasticity and high toughness, reducing economic costs, and deepening the multiscale understanding of structure-property relationships. These avenues will be pivotal in guiding the rational design of polymer systems for future technological demands.

The growing demand for rare earth elements (REEs) has posed significant challenges to their exploitation. Traditional chemical extraction methods of ion-adsorption type rare earth ores (IAREOs), which constitute the primary supply chain for medium and heavy rare earth resources, have caused severe ecological damage. Bioleaching technology has emerged as a promising solution to address the pollution issues in rare earth mining processes. This review comprehensively examines the occurrence states of REEs in IAREOs, the evolution of REEs leaching theory, and focuses on the bioleaching process. Initially, it introduces the genesis and characteristics of different REEs occurrence states in IAREOs and describes the development of leaching theories for IAREOs. The review then systematically explores bioleaching modes, key parameters, influencing factors, and mechanisms. Different bioleaching modes have their specific advantages. In contact bioleaching, microbial activity and metabolic processes may be inhibited by the metal ions leached and the toxic compounds present in the minerals or materials. On the other hand, non-contact bioleaching could avoid this issue while it requires additional facilities and results in a high cost. The choice of bioleaching mode needs to consider factors such as the type of minerals, the types of microorganisms, and operational costs, seeking a balance among these multiple factors. The efficiency of bioleaching is jointly influenced by microbial species and their metabolic products, cultivation conditions, and mineral types. To improve the performance of the bioleaching process, it is essential to consider several physicochemical and microbial factors that affect the bioleaching efficiency of REEs. Fundamentally, improving bioleaching efficiency involves enhancing microbial activity and metabolite concentration while minimizing, or eliminating the inhibitory effects of toxic substances on microbial activity and metabolic processes. The bioleaching mechanisms of IAREOs primarily comprise acid dissolution and subsequent ion exchange mechanisms, complexation-promoted dissolution mechanisms, and intracellular uptake mechanisms. The dominant mechanisms of bioleaching change with different environmental conditions. Bioleaching is often a synergistic process involving acid dissolution and complexation, with the predominance of either process depending on the pH value of solution, the acid dissociation constants (pK_a) of the functional groups, and the stability of the formed complexes. In terms of biological uptake, the overall effectiveness is determined by the dynamic balance of multiple factors, which also influences the final rare earth recovery rate obtained through cell recovery. The ecological impact of bioleaching on mining areas is thoroughly examined. Through microbial metabolism and chemical speciation transformation, bioleaching technology significantly reduces the toxicity and mobility of heavy metals in residues, thereby minimizing potential environmental hazards and laying the foundation for rapid ecological restoration. Compared to pyrometallurgical or hydrometallurgical methods, bioleaching demonstrates superior environmental and economic advantages, reducing environmental pollution and ecological risks associated with mineral extraction, while enabling rapid recovery of ecology. Finally, this review addresses current challenges in bioleaching technology and analyzes potential solutions. The summary and analysis of the bioleaching process presented in this review can provide support for the green bio-extraction of IAREOs and the development of microbial extraction technologies for REEs.

Hydrogen peroxide (H₂O₂), a green oxidizing agent, is extensively utilized across diverse industries, including wastewater treatment and disinfection. The direct electrochemical synthesis of H₂O₂ via the two-electron oxygen reduction reaction (2e⁻-ORR) presents a sustainable and environmentally friendly alternative to the conventional anthraquinone process, which suffers from high energy consumption and complex multi-step reactions. In this study, sulfur-doped carbon nanotube materials (S-CNTs) were successfully synthesized by utilizing sublimed sulfur as the sulfur source and carbon nanotubes as the carbon carrier, heated at 750 ℃ in an H₂/Ar atmosphere for sulfurization and annealing. For comparison, oxygen-doped carbon nanotubes (O-CNTs) and pure carbon nanotubes (CNTs) were also prepared. The results demonstrate that S-CNTs catalysts exhibit outstanding 2e⁻-ORR performance in both alkaline and neutral environments. In alkaline conditions, the selectivity for H₂O₂ exceeds 80%, with a peak value of 93% over a wide potential range of 0.20~0.60 V (vs. RHE), while in neutral conditions, the selectivity is 87%, within a potential range of 0.20~0.50 V (vs. RHE). Furthermore, in a flow-cell configuration utilizing commercial RuIr@Ti as the anode, the H₂O₂ yield reached 6.16 mmol•cm^-2•h^-1 with a cumulative concentration of 30.8 mmol•L^-1 under alkaline conditions, while under neutral conditions, the yield was 5.82 mmol•cm^-2•h^-1 with over 80% Faradaic efficiency. The incorporation of sulfur into the carbon nanotube catalysts effectively modulated the coordination environment and electronic structure, while the introduction of defect sites provided an ideal active center and robust structural foundation. The electronic structure modulation of the carbon substrate and the enhancement of water dissociation via sulfur-doped carbon nanotube catalysts not only significantly reduced the reaction overpotential across a wide pH range but also facilitated the production of high-concentration hydrogen peroxide, thereby improving synthesis efficiency. This study offers a novel and cost-effective approach for the development of efficient non-metal-doped carbon materials as electrocatalysts for the two-electron reduction of O₂ to H₂O₂ and suggests promising applications in the field of energy and environmental technologies.

The amide moiety is unarguable importance due to its widespread presence in numerous biologically active molecules, including agrochemicals, insecticides, pharmaceutical agents, peptides, proteins, polysaccharides and nucleic acids. The condensation of a carboxylic acid and an amine using a coupling reagent or metal/boronic catalyst represents the most common approach in amide synthesis and is frequently employed in producing modern pharmaceuticals. However, the use of stoichiometric amounts of coupling agents, oxidants, or catalytic amounts of metal catalysts often involves challenges such as toxicity and high cost. In connection with our studies on photoredox acylations, we herein report an efficient photoredox dealkylative acylation of tertiary amines with acid anhydrides using a commercially available and inexpensive acridine salt-based photocatalyst, which enables the preparation of a wide range of amides from tertiary amines under mild reaction conditions. To an oven dried Schlenk-tube, benzoic anhydride (45.2 mg, 0.20 mmol), triethylamine (60.7 mg, 0.60 mmol), $\mathrm{Mes}-\mathrm{Acr}^{+} \mathrm{ClO}_{4}^{-}$ (1.6 mg, 0.004 mmol) and MeCN (2 mL) were added under argon atmosphere. The reaction mixture was stirred under the irradiation of 20 W Blue LED (450 nm) at room temperature. After completion of the reaction, the reaction mixture was concentrated by vacuum, purified by silica gel chromatography, and eluted by petroleum ether/ethyl acetate to obtain products. With the optimized reaction conditions in hand, we investigated the scope of anhydrides and tertiary amines in the present dealkylative acylation. In general, all tested substrates were suitable for yielding amidation products, all of the aliphatic, aromatic anhydrides and tertiary amines are suitable reactants for the transformations to afford the corresponding amides in moderate to excellent yields. The successful gram-scale reaction and late-stage functionalization of drug molecule in mild conditions under room temperature have qualified the protocol to be practical, cost-effective, and environmentally friendly. The mechanistic studies have verified the single-electron oxidation of tertiary amine by the photosensitiser and the generation of an acyl radical via single electron reduction of anhydride.

Nuclear energy, recognized as an efficient and stable power source, is poised to play an increasingly significant role in the global energy mix. The reprocessing of spent nuclear fuel is crucial in assessing whether nuclear energy can be deemed a sustainable form of energy. Among the various technologies involved, partitioning-transmutation technology not only reduces the long-term hazards associated with radioactive waste but also mitigates the environmental risks linked to the treatment of nuclear waste. The transuranic elements in high-level liquid waste (HLLW) possess relatively high toxicity and long half-lives. Therefore, the effective separation of transuranic elements from HLLW is a necessary condition and a key technology for separation-transmutation. Among the methods for the separation of actinides, solvent extraction has been widely applied due to its simplicity and low cost. However, this method also presents several challenges, such as the use of toxic or flammable solvents, the formation of emulsions, and the generation of large amounts of secondary organic hazardous waste. In contrast, solid-phase adsorption does not require organic solvents, thereby reducing the volume of solvents and the risk of secondary pollution. Moreover, the adsorption process can be conducted at ambient temperature and pressure, making it simple, low-cost, environmentally friendly, and regenerable. These advantages have contributed to its increasing popularity and research interest in recent years. However, the harsh conditions in HLLW present significant challenges in the development of solid-phase adsorbents. Despite many obstacles, advancements in solid-phase adsorbent materials for transuranic element separation have demonstrated considerable potential within the nuclear energy sector. This article provides a comprehensive analysis of the benefits, challenges, and prospective applications of solid-phase adsorbents. It offers a systematic review of research progress in various solid adsorbents, including inorganic porous materials, carbon-based porous materials, polymer resins, metal-organic frameworks (MOFs), and covalent organic frameworks (COFs), specifically in the context of transuranic element separation. The review investigates their strengths in terms of adsorption performance, selectivity, stability, and regenerability. Additionally, it highlights research challenges such as the complexity of preparation, economic viability, and the scalability of production processes. This thorough analysis is instrumental in the development of more efficient and eco-friendly transuranic element adsorbent materials and in facilitating their integration into practical nuclear energy processing applications.

Bismuth ferrite-based compounds, such as BiFeO₃ and Bi₂Fe₄O₉, have attracted significant attention as photocatalytic materials due to their favorable structural properties and stability. In this study, Ag-doped BiFeO₃ and Bi₂Fe₄O₉ powders were synthesized using the sol-gel method, and their photocatalytic properties were evaluated through the degradation of Rhodamine B (RhB) under ultraviolet (UV) light. The results showed that Ag doping notably enhanced the photocatalytic properties of Bi₂Fe₄O₉. Specifically, 3 mol% Ag-doped Bi₂Fe₄O₉ exhibited an impressive RhB degradation rate of 96%, indicating its high efficiency for photocatalytic applications. In contrast, Ag doping in BiFeO₃ led to the formation of mixed phases, including Bi₂Fe₄O₉ and Bi₂₅FeO₄₀, and resulted in only a modest improvement in photocatalytic performance, with a RhB degradation rate of 50%. These findings highlight the superior photocatalytic activity of Bi₂Fe₄O₉ compared to BiFeO₃, emphasizing the importance of material composition and doping concentration in optimizing photocatalytic efficiency. Moreover, UV-Vis diffuse reflectance spectroscopy was used to investigate the electronic properties of the materials. The analysis revealed that Bi₂Fe₄O₉ exhibits a dual-bandgap feature with values of 1.28 eV and 1.36 eV, which enhances the material's ability to absorb visible light and improves its photocatalytic performance under ambient light conditions. To explore the mechanisms behind these improvements, density functional theory (DFT) calculations were conducted. The results indicate that the Ag 4d orbitals introduce defect energy levels near the valence band maximum of Bi₂Fe₄O₉, effectively narrowing the bandgap. This facilitates more efficient charge separation, which is crucial for enhancing photocatalytic properties. Fluorescence spectroscopy further confirmed that Ag doping effectively inhibits the recombination of photogenerated electron-hole pairs, further boosting the photocatalytic efficiency of Bi₂Fe₄O₉. This study provides valuable insights into the potential of Ag-doped bismuth ferrite-based compounds for advanced photocatalysis, and pave the way for the development of efficient photocatalysts for environmental and energy-related applications, such as water purification and solar energy conversion.

The national transition toward sustainable energy solutions necessitates the development of advanced materials and technologies for efficient energy conversion and storage. Addressing this demand requires innovative approaches to overcome existing limitations in energy systems, including the need for high-capacity storage, rapid charge transfer, and long term stability. In this context, research on innovative energy storage carriers and mass/charge transfer mechanisms has become a pivotal focus at the forefront of materials science and energy technology. Porous organic cages (POCs), a unique class of low crystalline density porous materials, have attracted significant interest due to their well-defined molecular structures, discrete nanopore cavities and high porosity. These properties make them highly effective for applications in gas adsorption/separation and catalysis. Unlike traditional extended framework materials such as metal organic frameworks (MOFs) or covalent organic frameworks (COFs), POCs are discrete and solution-processable molecules that offer superior solubility and structural tunability, which can be easily designed as various functional composites, broadening their applicability in emerging energy technologies. A particularly promising avenue for POCs lies in energy conversion and storage. Recent studies have demonstrated that functionalized POCs can serve as efficient charge transport materials, facilitating electron and ion movement in energy storage applications. Despite their immense potential, several challenges must be addressed before POCs can be widely adopted in commercial energy technologies. Key challenges include improving the scalability of POC synthesis, optimizing their stability under operational conditions, and enhancing their conductivity for broader energy applications. Furthermore, fundamental research is needed to better understand the charge transport mechanisms within POC-based materials, which will be crucial for advancing their practical implementation. This review provides a comprehensive overview of the design and synthesis strategies of POCs, summarizes recent advancements in their energy-related applications, and discusses the challenges and future research directions in the field. By offering theoretical insights into the strategic development of POCs for energy conversion and storage, this work aims to drive further innovation in sustainable energy technologies, contributing to the ongoing efforts to address global energy challenges.

Oxime is a widely used organic compound with numerous applications in chemistry, biology, environmental science, medicine, pesticides, materials, and related industrial production. Among the various synthetic methods, directly converting carbon-hydrogen bonds in hydrocarbon compounds into oximes is the most straightforward and practical approach for synthesizing oximes. The oximinylations of reactive methylene and methyl C(sp³)—H bonds often involve oximinylating reagents such as nitrous acid, nitrosyl halides, nitrite, and nitrosyl esters, with the nitrosyl cation as a crucial intermediate. In contrast, radical-mediated oximinylations have a broader substrate scope and can even be applied to substrates containing only unactivated C(sp³)—H bonds. Mechanistically, the reactions involve the homolytic cleavage of a nitroso compound via light irradiation or heating, generating a heteroatom-centered radical and a nitric oxide radical. The heteroatom-centered radical subsequently abstracts a hydrogen atom from the substrate to form an alkyl radical, which then undergoes subsequent radical reactions and finally couples with the nitric oxide radical. This coupling produces a nitroso intermediate, which isomerizes to oxime. This paper reviews the oximinylations of saturated C(sp³)—H bonds from the early 20th century to the present. It categorizes the reactions based on their mechanisms, including the oximinylations of reactive methylene and methyl C(sp³)—H bonds, radical-mediated oximinylations of C(sp³)—H bonds, and metal-mediated oximinylations of C(sp³)—H bonds. Additionally, this paper not only elucidates the development of the C(sp³)—H oximinylation reaction but also discusses the challenges in this field and offers future perspectives with the aim of providing insights for innovative applications in synthetic chemistry and industrial processes.

There are still many challenges in the transformation of supercapacitors from laboratory research to industrial application, especially the low-mass load electrodes used in laboratories cannot meet the needs of commercial applications. Herein, we present a highly loaded nickel-cobalt double hydroxide-based (NiCo-LDH) supercapacitor. Three-dimensional ZnO@C nanorod scaffolds with high conductivity were introduced, and ZnO@C@NiCo-LDH heterostructure materials on carbon cloth were prepared by solvothermal, high-temperature annealing, electrochemical deposition and other methods, achieving loading up to 11.0 mg•cm⁻². The typical synthesis process is as follows. Firstly, the neatly arranged ZnO nanorods were grown on the carbon cloth fiber by seed growth method. Then, ZIF-8 nanoparticle coatings were grown in situ on zinc oxide nanorods through etching and recombination in a solution containing 2-methylimidazole. Subsequently, we obtained ZIF-8-derived carbon-coated ZnO nanorods by carbonizing ZnO@ZIF-8 heteronanostructures in nitrogen. During the carbonization process, the ZIF-8 shell is transformed into a carbon layer containing zinc oxide nanoparticles. Finally, NiCo-LDH nanosheets were deposited on the ZnO@C framework by electrochemical cyclic voltammetry. The conductive ZnO@C nanorods can avoid the agglomeration of NiCo-LDH nanosheets and promote the transport of electrons. The outer NiCo-LDH nanosheets with high capacity can continue to improve the electrolyte ion contact points on the electrode surface, further improving the specific capacity of the material. This heterostructure electrode utilizes the synergistic effect of the two to greatly improve the charge storage capacity and exhibits excellent electrochemical performance. The results show that the assembled asymmetric supercapacitor ZnO@C@NiCo-LDH//AC achieves a high energy density of 0.93 mWh•cm⁻² at a power density of 15 mW•cm⁻². After 5000 cycles at a current density of 10 mA•cm⁻², the capacity retention rate is still 93.6%, demonstrating excellent stability. This work provides a new idea for developing new high-mass load electrodes.

Circularly polarized room-temperature phosphorescence (CP-RTP) materials have garnered significant attention due to their exceptional optical sensitivity and spatial resolution, making them highly promising for a wide array of applications, such as three-dimensional displays, anti-counterfeiting, and information storage. Generally, the polarization magnitude is quantified by the luminescence dissymmetry factor (g_lum), which has a value between －2 and 2. However, while chiral organic RTP materials often demonstrate higher luminous efficiency, they typically display remarkably low g_lum values, generally in the order of 10^-5 to 10^-3, owing to their inherently weak magnetic transition dipole moment. This limitation significantly hinders the practical application of high-performance CP-RTP materials. Therefore, enhancing the g_lum values of CP-RTP materials remains a substantial challenge. With the rapid advancement of chiral supramolecular assembly, researchers have discovered that this system can construct long-range ordered helical nanostructures by precisely regulating intermolecular interactions, such as π-π stacking and hydrogen bonding. This approach facilitates the attainment of a high g_lum value while maintaining favorable luminous efficiency. Meanwhile, the processes of chiral self-assembly or co-assembly frequently involve chiral transfer, chiral induction, and intermolecular Förster resonance energy transfer. These processes are advantageous for inducing achiral dyes to achieve CP-RTP. This dramatically simplifies the synthesis of CP-RTP materials, circumventing the often-complex and costly preparation of intrinsically chiral RTP chromophores. Consequently, chiral supramolecular assembly systems have emerged as a highly effective strategy for the development of CP-RTP materials exhibiting substantially improved g_lum values. This review comprehensively examines the influence of helical structures on the photophysical properties of chiral supramolecular assembly systems, summarizing recent progress in the design, synthesis, and application of chiral supramolecular RTP materials, with a particular focus on their exploitation in advanced information encryption and anti-counterfeiting technologies. We delve into the underlying mechanisms driving enhanced circular polarization and discuss future directions for this rapidly evolving field.

Bacteria are widespread in nature and play an important role in human health. However, bacterial infections have long posed a serious threat to human life. The discovery of antibiotics has improved infection control, but their misuse has led to the problem of bacterial resistance. Therefore, the development of new antibacterial materials has become a hot research topic. Among them, the natural polymer chitosan has attracted much attention due to its excellent biocompatibility, biodegradability and antibacterial properties. This review introduces the structure and properties of chitosan, including its antimicrobial activity, solubility, etc., and points out that chitosan with different degrees of deacetylation and molecular weights exhibits different antimicrobial effects and solubility. The modification strategies of chitosan, including physical doping and chemical modification, such as Schiff base reaction, esterification reaction, quaternization reaction and graft copolymerization, are elaborated in detail, which are aimed at improving the solubility of chitosan and expanding its application range. The optimized chitosan can be prepared into nanofibers by various advanced fabrication processes such as electrostatic spinning, centrifugal spinning, solution blow spinning and wet spinning. These nanofibers have the advantages of high specific surface area, adjustable porosity, excellent mechanical strength and antimicrobial properties. This review discusses the potential applications of chitosan-based antimicrobial fiber materials in the fields of wound dressings, tissue engineering, drug delivery carriers, food packaging, living textiles, and environmental treatment. This review also points out that chitosan-based antimicrobial fiber materials need to solve some problems if they are going to be marketed, such as in-depth exploration of the relationship between chitosan molecular structure and performance, development of a more efficient preparation process, and focusing on resource conservation and environmental protection in the production and application process. This review provides useful references and lessons for the development and innovation of chitosan-based antimicrobial fiber materials.

Photoluminescent copper nanoclusters have broad application prospects in lighting and display. However, the difficulty of photoluminescence wavelength regulation greatly limits its practical application. Now, more and more studies show that the photoluminescence of metal nanoclusters cannot be simply attributed to the quantum confinement effect of the metal core, metal-metal, metal-ligand and ligand-ligand interactions play a pivotal role in the emission process. Achieving the effective regulation of these weak interactions in metal nanoclusters is the current research focus in this field. Self-assembly is an effective strategy to regulate these weak interactions in metal nanoclusters. The variation of the spatial assembly structure of metal nanoclusters will affect the charge and energy transfer process, and then affect the photoelectric properties of metal nanoclusters. Although many strategies have been proposed to regulate the assembly structure of metal nanoclusters, most of the proposed strategies need to be carried out under heating conditions, which is not conducive to the large-scale production of metal nanocluster assemblies and limits its practical application. In this paper, copper nanocluster assemblies with yellow and blue emission have been successfully synthesized by a solvent-regulated strategy at room temperature. Different solvent environments lead to different assembly modes of copper nanoclusters, and finally two typical assembly structures of nanosheet and nanorod are formed. In a high boiling solvent, such as dibenzyl ether, the solubility and fluidity of copper clusters are poor, which is conducive to the formation of loose nanosheet assembly structure. In contrast, in a low boiling solvent, such as n-hexane, the solubility and fluidity of copper clusters are better and the clusters tend to form a dense nanorod assembly structure. The spacing of clusters in the assembly plays a pivotal role in its photoluminescence performance. Compared with the single-layer nanosheet structure, the nanorod structure adds the additional interlayer interaction. This results in additional Cu(I)…Cu(I) interaction and the increasing of spacing between adjacent sulfhydryl ligands on the cluster surface. Finally, the emission wavelength of copper nanoclusters blue shifted from ca. 550 nm to ca. 490 nm. This solvent-regulated synthesis strategy is simple, easy to operate and short in time consuming, which is conducive to the large-scale synthesis of copper nanoclusters. In addition, light-emitting diodes (LEDs) with different emission colors based on the synthesized metal nanocluster assemblies were successfully prepared.

Carbenes (R₂C:) represent a unique class of neutral divalent carbon species that formally possess six valence electrons at the central carbon atom, thereby deviating from the octet rule. These species have long occupied a central role in organic, organometallic, and materials chemistry owing to their rich electronic structures and versatile reactivity. The vast majority of isolated stable carbenes adopt a singlet ground-state electronic configuration described as σ²π⁰, wherein a lone pair occupies an in-plane σ orbital and the out-of-plane π orbital remains unoccupied. This configuration underpins the pronounced nucleophilicity observed in classical N-heterocyclic carbenes and their analogs. A limited number of carbenes with a σ¹π¹ open-shell ground state have been spectroscopically characterized, often exhibiting radical-like behavior and enhanced reactivity. In sharp contrast, carbenes with an inverted electronic configuration—σ⁰π²—remain extraordinarily rare and conceptually intriguing. These carbenes possess two electrons fully occupying the out-of-plane π orbital, leaving the in-plane σ orbital vacant. Such a configuration inverts the typical orbital occupancy pattern, potentially leading to electrophilic or ambiphilic reactivity profiles. To date, four principal design strategies have been proposed to stabilize σ⁰π² carbenes: (1) cyclic di(imino)carbenes; (2) di(boryl)carbene; (3) metal-coordinated cyclic di(phosphino)carbenes; and (4) dicationic carbones. However, despite extensive conceptual exploration, only one stable and isolable σ⁰π² carbene has been structurally authenticated to date. This species features a rigid RhP₂C four-membered metallacycle, wherein the carbene carbon exhibits an unprecedented ¹³C NMR chemical shift below －30 parts per million, representing the most upfield resonance recorded for a carbene center. This carbene demonstrates divergent reactivity patterns uncharacteristic of classical σ²π⁰ congeners. It reacts with both Lewis acids and Lewis bases to yield coordination adducts and π-complexes, respectively, and participates in bond-forming processes such as ketenimine generation from isocyanides. Its demonstrated ambiphilicity offers promise for the activation of inert small molecules, including dinitrogen (N₂)—a long-standing goal in main group chemistry. This perspective provides a systematic overview of the emerging chemistry of σ⁰π² carbenes, critically analyzing structural parameters, stabilization frameworks, and reactivity paradigms. We further highlight the prospective roles of such carbenes in bond activation and novel ligand design, envisioning their integration into next-generation main-group and transition-metal cooperative systems.

With the intensification of environmental challenges and the ever-growing global energy demand, conventional materials are increasingly unable to satisfy the stringent requirements in energy and environmental fields. Metal-organic frameworks (MOFs), as a class of crystalline porous materials composed of metal nodes and organic ligands, have emerged as promising candidates due to their tunable pore structures, exceptionally high surface areas, and versatile functionalities. These features enable MOFs to play a significant role in applications such as adsorption and electrochemical energy storage. However, the poor intrinsic electrical conductivity and limited structural stability of pristine MOFs restrict their practical implementation. To address these limitations, MOF-based composites have been developed by integrating MOFs with a variety of guest materials including inorganic carbonaceous materials (e.g., graphene, carbon nanotubes), metal oxides, and conductive polymers. These composites not only retain the inherent advantages of MOFs but also enhance conductivity, mechanical robustness, and chemical stability through synergistic interactions. Importantly, the integration strategies often involve the construction of heterostructures, interface engineering, and the introduction of chemically bonded interfaces, thereby promoting efficient charge transfer and long-term cycling stability. Herein, a comprehensive summary of MOF composites and their emerging applications in electrochemical energy storage systems, such as supercapacitors, lithium-ion batteries, lithium-sulfur batteries and aqueous zinc ion batteries, as well as in environmental adsorption processes targeting heavy metals and CO₂ capture, is offered. The discussion also emphasizes dimensional design from zero-dimensional (0D) nanoparticles to three-dimensional (3D) frameworks, each exhibiting unique advantages in terms of electron transport, ion diffusion, and active site accessibility. The relationships of these composites are analyzed, highlighting how different combinations and morphologies (e.g., core-shell architectures, layered hybrids, and flexible films) influence their functional performance. MOF composites represent a promising frontier for the development of next-generation functional materials. Their tunable dimensionality, enhanced chemical properties and multifunctional adaptability open up new avenues for solving urgent global issues in energy sustainability and environmental remediation.

Using mild photoelectrocatalytic technology to co-reduce CO₂ from the atmosphere and $NO_{2}^{-}$ from water pollutants into high-value-added chemical urea is an effective approach to achieving pollution reduction and carbon reduction goals. However, this reaction involves a 12-electron co-reduction with dual-substrate molecules, making it highly challenging with a complex pathway and high demands on the catalyst. So, there are few reports on this reaction currently. In this study, Ru, Cu, and Zn atom-modified TiO₂ catalytic materials (Ru, Cu, and Zn-TiO₂) were prepared via a hydrothermal method combined with photodeposition method. The specific synthesis processes are as follows: titanium butoxide was dropwise added into a H₂O/HCl mixed solution. Then the solution and fluorine-doped tin oxide (FTO) substrate were transferred and sealed in a Teflon-lined stainless-steel autoclave and heated to 150 ℃ for 20 h. The obtained TiO₂ photoelectrode was annealed in a muffle furnace at 350 ℃ for 2 h. The TiO₂ with different metal atom surface modifications were prepared by adding metal salt solution and methanol in a beaker, placing the TiO₂ photoelectrode in the solution and irradiating it with a 300 W xenon lamp for 1 h. We conducted catalytic urea synthesis experiments by using three-electrode configuration in a H-type quartz cell equipped with pretreated Nafion 117 membrane. The as-prepared semiconductor, Ag/AgCl electrode and Pt foil were utilized as the photocathode, reference and counter electrodes, respectively. 0.1 mol•L⁻¹ KNO₂ was used as the electrolyte in both the cathode and anode compartments. CO₂ gas was injected into the cathode chamber during the photoelectrocatalytic test. The experimental results showed that Ru-TiO₂ modified with 5% (w) Ru achieved a urea yield of 50.58 μmol•g⁻¹•h⁻¹ and a Faradaic efficiency (FE) of 16.66% under 2 h light irradiation at －0.1 V (vs. RHE). The 5% (w) Ru-TiO₂ catalyst exhibits a FE 1.65 times than that of TiO₂ under identical conditions. UV-Vis diffuse reflectance spectra (DRS) and electrochemical impedance spectra (EIS) indicate that Ru atoms can effectively enhance the light absorption, charge separation and transfer of TiO₂. Photogenerated electrons transfer from TiO₂ to Ru atomic sites, participating in the C—N coupling reaction. This work provides theoretical guidance for designing and synthesizing efficient catalysts for photoelectrocatalytic urea synthesis, offering novel idea and pathway for synergetic control of environmental pollution and carbon emissions.

With the gradual depletion of traditional energy sources, hydrogen energy as a clean energy source has gradually attracted people's attention. Among various hydrogen-production methods, semiconductor photocatalytic water splitting stands out as a promising approach due to its numerous advantages, including low-cost operation and environmental friendliness. The efficiency of photocatalytic hydrogen production is intricately linked to the electronic properties of photocatalysts. One of the key factors is the recombination of electrons and holes, which can significantly reduce the utilization of photo-generated carriers. Therefore, precisely and rationally regulating the transfer of photoelectrons has emerged as a crucial strategy to enhance hydrogen production efficiency. In this paper, the electronic structure, optical properties, interfacial properties, and carrier transport after illumination of the MoSi₂N₄/ZrS₂(HfS₂) heterojunction were studied by using first-principles and nonadiabatic molecular dynamics. The results show that the MoSi₂N₄/ZrS₂(HfS₂) heterojunction exhibits stronger light absorption capability in the visible region, the carrier mobility in the heterojunction is significantly higher than that in the single phase, and the electron-hole separation efficiency is also effectively improved. Additionally, the interfacial properties, which play a vital role in carrier transfer between different materials, and the carrier transport behavior after illumination are studied in detail. The research findings reveal that within the visible-light region, the MoSi₂N₄/ZrS₂(HfS₂) heterojunctions demonstrate enhanced light-absorption capabilities. Moreover, the carrier mobility within these heterojunctions is remarkably higher compared to their single-phase counterparts. This higher mobility promotes the rapid movement of electrons and holes, effectively improving the efficiency of electron-hole separation. As a result, more electrons can participate in the hydrogen production reaction, simultaneously, the heterojunctions exhibit a higher hydrogen evolution efficiency. The ΔG_H* value in the hydrogen evolution reaction is lower than that of their single-component materials. A lower ΔG_H* indicates that the reaction requires less energy input, which can effectively enhance the performance of photocatalytic water splitting for hydrogen production. Based on these experimental results, the paper elaborates on the corresponding mechanisms in detail, aiming to provide in-depth insights into the underlying principles. This study offers a solid theoretical foundation for the further development of highly efficient two-dimensional heterojunction photocatalysts.

Vitamin E is one of the most widely used antioxidants, extensively applied in the medical and food industries. However, its susceptibility to oxidation poses significant challenges during production, storage, and transportation. In recent years, a derivative of Vitamin E—Vitamin E succinate (VES) has garnered increasing attention. VES not only retains the biological functions of Vitamin E but also exhibits excellent stability and unique anti-tumor properties. The main methods for preparing VES include chemical synthesis and enzymatic synthesis. Enzymatic synthesis has become a popular research topic due to its environmental friendliness and high efficiency. Nevertheless, the high cost and poor reusability of free enzymes severely limit the industrial application of this method. Designing enzyme-friendly solvents and immobilized enzyme technologies has proven to be effective strategies to overcome these limitations. In this study, the synthesis of VES was employed as a model reaction to integrate immobilization and solvent design strategies. The lipase was immobilized in a dual-functional macroporous resin, combined with a novel deep eutectic solvent, significantly enhancing the performance of lipase. Under the optimal conditions, the experimental results revealed a VES yield of 99.3%. When scaled up tenfold, the system achieved a 99.1% esterification yield, with the catalytic activity remaining above 80.0% even after five reuse cycles. Notably, molecular dynamics simulation results indicated that the deep eutectic solvent has excellent biocompatibility, which enhances the stability and reusability of lipase. Furthermore, this solvent improves the affinity of lipase for the substrate, thereby increasing the yield of VES. The synthetic strategy developed in this study is environmentally friendly, catalytically efficient, and offers broad applications in the field of biosynthesis.

DNA-encoded library (DEL) technology has emerged as an important platform for drug development. It has attracted widespread attention from industry and academia due to its advantages such as short synthesis cycle, simple operation, high throughput and low cost. However, the advancement of DEL technology still faces challenges, such as the lack of DNA-compatible chemical reactions for constructing drug-like privileged scaffolds in DELs. Thiohydantoin is an important nitrogen-containing heterocycle widely present in natural products, bioactive molecules, and marketed drugs (e.g., enzalutamide and apalutamide). Among thiohydantoin compounds, the 5-arylidene thiohydantoin derivatives, which have demonstrated a wide range of biological effects, have attracted much attention. Additionally, aldehydes, as widely available building blocks, offer new synthetic approaches for expanding the chemical space of such thiohydantoin-focused DELs. Based on this, we aimed to develop a method for the efficient synthesis of 5-arylidene thiohydantoin DELs under DNA-compatible conditions. The method involves the Knoevenagel reaction between DNA-conjugated thiohydantoins and aldehydes. First, we optimized the reaction conditions and identified the optimal parameters: DNA-conjugated thiohydantoin (200 pmol, 100 µmol/L in water), aldehyde (2500 nmol, 500 mmol/L in dimethyl sulfoxide (DMSO)), pyrrolidine (400 nmol, 200 mmol/L in DMSO), total reaction volume of 20 μL, organic-to-aqueous phase volume ratio of 1∶1, reaction temperature of 60 ℃, and reaction time of 1 h. Subsequently, we evaluated the substrate scope using different aldehydes and DNA-conjugated thiohydantoins. The results demonstrated a broad substrate tolerance, with most reactions achieving moderate to excellent conversions (50%~98%). This study supports the practical construction of DELs focused on the drug-like 5-arylidene thiohydantoin scaffold and expands the accessible chemical space of DELs.

Alcohols are one of the most widespread existent in nature, and one of promising chemical feedstocks, due to their cheap and easy availability. Half a century ago, the Barton-McCombie deoxygenation was discovered, and continued to be improved by organic synthetic chemists, becoming an important and rather broad fields in modern organic chemistry. In the last decade, visible-light-driven photoredox catalysis is a powerful tool in organic synthesis, and can realize a good deal of chemical transformations, because of its milder reaction condition, functional group tolerance, high efficiency and environmental-friendly characteristics. It has been reported direct deoxygenation of alcohol in the previous literatures, including the photochemical reactions and metal-transition catalytic systems. Herein, we summarized and discussed some significant advances since in 2014, about the deoxygenative functionalization of alcohol derivatives in photochemical synthetic reactions. And oxygen-containing derivatives of alcohol mainly includes carboxylic esters, oxalic esters, thiocarbonates and their derivatives, ethers and others. In this minireview, in terms of their structural properties, we went to classify and introduce the catalytic modes and mechanisms of deoxygenation, reaction universalities, advantages and shortcomings. In these advances, the oxygen-containing derivatives of alcohol could proceed single electron oxidation and reduction processes, hydrogen atom transfer (HAT), as well as radical addition process, as to assist the C—O bond cleavage to yield the key alkyl radical intermediates, subsequent functionalization to construct the newly C—C, C—N, C—O, C—S, C—X (halo) and C—B bonds. In addition, we also outlooked the challenges and opportunities in the field of deoxygenation of alcohols, and the application prospects of some compounds containing the hydroxy group in the future was discussed as well.

The rapid development of aerospace and other fields has driven a revolution in electronic packaging materials, and in the development of integrated circuits, it is critical to develop electronic packaging materials with high reliability and performance to withstand more extreme operating environments. To this end, a new benzoxazine hyperbranched silicone resin based on the high designability characteristics of hyperbranched silicone structure was designed in this paper, and its rapid moulding characteristics can fill in the gaps of conventional silicone resins in this application. The combination of benzoxazine group and hyperbranched silicone resin can provide the advantages of both, and the introduction of silicon-oxygen bond with high bond energy can improve the oxidation- and ablation-resistance of traditional organic resin materials. The benzoxazine ring can effectively improve the processing performance and mechanical properties of silicone resin materials, thus solving the problems of traditional organic resin materials (e.g., poor oxidation- and ablation-resistance) and the organic silicon material (e.g., difficult to process and poor mechanical properties). Due to the low entanglement and the high intramolecular free volume of hyperbranched polysiloxane chain segments, the prepared benzoxazine hyperbranched polysiloxane resin has the characteristics of low viscosity. At the same time, its initial curing temperature was only 163 ℃, and the activation energy of curing was 93.25 kJ•mol⁻¹, so the curing activity was significantly improved, and the processing performance was greatly enhanced. Moreover, the introduction of silicon-oxygen bond and high cross-linked structure gives benzoxazine hyperbranched polysiloxane cured products excellent temperature-resistance and ablation-resistance performance. Its glass-transition temperature was more than 270 ℃, its 5% decomposition temperature was higher than 410 ℃, the residual carbon rate was more than 78% in 1000 ℃ nitrogen and more than 35% in oxygen, demonstrating significant improvement compared with the existing electronic packaging moulding compound substrates. In addition, it also shows good fire-resistance (not burning in open flame), water-resistance (water absorption rate<1%) and electrical insulation. This study provides a new idea for the development of new temperature-resistant rapid moulding materials and high-performance packaging materials.

Lithium-rich layered oxides (LLOs) has attracted the attention of scientists due to its theoretical specific capacity exceeding 250 mAh•g⁻¹. It is considered the most promising new generation of lithium-ion battery cathode materials. However, the aggregation of Li₂MnO₃ domains and the release of lattice oxygen in LLOs can lead to severe capacity/voltage degradation, hindering their commercial applications. This work adopts a manganese-based lithium-rich layered Li_1.17Ni_0.165Co_0.165Mn_0.5O₂ (Li-Ni-Co-Mn-O) model with C2/m symmetry. Select a 2×2×1 supercell with a total of 96 atoms, namely Li₂₈Ni₄Co₄Mn₁₂O₄₈. Construct two systems, one with Co permeation into Li₂MnO₃ domain (LNCMO-P) and the other without (LNCMO-nP), to investigate the effect of Co permeation on the redox process and delithiation structure stability of Li₂MnO₃ domain and O. The spin-polarized generalized gradient approximation (GGA) method with PBE (Perdew Burke Ernzerhof) exchange-correlation function is adopted, and the projected augmented wave (PAW) potential function is selected to describe the interaction between ions and electrons to complete all calculations. The research results indicate that by regulating the concentration of oxygen vacancies, Co can penetrate Li₂MnO₃ domains. The permeation of Co alleviates the stress distortion between Li₂MnO₃ and LiTMO₂ phases and suppresses the lattice strain caused by uneven electrochemical activity and structural evolution. The study on the geometry and electronic structure of the Li_1.17Ni_0.165Co_0.165Mn_0.5O₂ system found that Co-Ni aggregation caused the appearance of high-spin Co electronic states, which alleviated the volume expansion caused by charging. The permeation of Co activates more interfacial oxygen, and oxygen at the interface participates in charge compensation and disperses oxygen oxidation, thereby sharing the oxidation pressure of oxygen in the Li-O-Li configuration, which is beneficial for suppressing the release of lattice oxygen and improving the problem of irreversible oxygen evolution caused by lattice oxygen reactions. This study provides a theoretical basis for designing lithium-rich cathode materials with high-performance structural stability.

The N-alkylation of alcohols over solid catalysts represents an environmentally benign approach for the synthesis of amine compounds. In this study, niobium oxide synthesized via a hydrothermal method was employed for the N-alkylation of benzyl alcohol with aniline. Compared to various metal oxides and conventional aluminum trichloride catalysts, niobium oxide demonstrated superior catalytic activity, achieving complete conversion of benzyl alcohol (100%) and a 65.2% yield of N-benzylaniline under optimized conditions (180 ℃, 1 MPa N₂, 4 h). To elucidate the reaction pathway and mechanism of benzyl alcohol N-alkylation over niobium oxide, comprehensive investigations were conducted, including reaction kinetics, solvent polarity effects, steric hindrance studies, and carbocation-trapping experiments. Kinetic analysis revealed a reaction order of 1.04 for benzyl alcohol and 0.008 for aniline, indicating a first-order overall reaction predominantly governed by the alcohol. Solvent polarity significantly influenced the reaction outcome: in toluene (a polar solvent), the yield remained stable at 65.0%, while in nonpolar solvents (cyclohexane and dodecane), the yields drastically decreased to 3.2% and 4.4%, respectively. This highlights the critical role of polar media in stabilizing carbocation intermediates. Steric effects were evaluated using diphenylmethanol as a bulky substrate, which surprisingly yielded 77% of the target product, suggesting minimal steric hindrance under the S_N1 mechanism. Definitive evidence for carbocation intermediate was obtained through experiments with 1-phenylcyclopropylmethanol, where only products derived from rearranged carbocations were detected. These results demonstrated that the reaction proceeds via the S_N1 mechanism involving carbocations generated from benzyl alcohol. Furthermore, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis of benzyl alcohol and aniline revealed that niobium oxide activates the C—O bond of benzyl alcohol and the N—H bond of aniline, facilitating the formation of carbocations and the cleavage of the N—H bond of aniline, thereby exhibiting good catalytic activity for benzyl alcohol N-alkylation. The niobium oxide catalyst also exhibited exceptional stability, maintaining its activity even after six cycles. This study not only provides a comprehensive mechanistic understanding of Nb₂O₅-catalyzed N-alkylation but also establishes a green and practical strategy for sustainable amine synthesis.

Organic light-emitting diode (OLED) technology has been widely applied in the fields of full-color flexible displays and solid-state lighting. As one of the three primary colors, blue light plays a crucial role in OLED technology, making blue-emitting materials a focal point of research in this domain. To achieve blue light emission with high color purity, blue-emitting materials need to emit light within a narrow wavelength range. However, this narrow-band emission often comes at the cost of reduced luminescence efficiency, as precise regulation of molecular energy levels to realize narrow-band emission is highly challenging in practical material design. Considering this, this work proposes an innovative molecular design strategy. Through the Suzuki-Miyaura coupling reaction of pyridine units with corresponding boronate esters, three bipyridine derivatives with different substitution sites were successfully synthesized. Subsequently, 3,6-di-tert-butylcarbazole groups were introduced to the ortho, meta, and para positions of the pyridine nitrogen atoms in the bipyridine core via C—N coupling reactions, yielding three target compounds with distinct twisted structures. In these materials, the 3,6-di-tert-butyl- carbazole unit acts as the donor and the pyridine unit as the acceptor. A significant dihedral angle exists between the carbazole substituents and the bipyridine core. This steric-induced twisted structure effectively restricts the extension of the molecular conjugated system and suppresses the energy loss due to intramolecular vibrations, thereby ensuring high color purity of blue light. Thermogravimetric analysis indicates that all three materials exhibit excellent thermal stability, with decomposition temperatures exceeding 310 ℃. Photophysical tests reveal that 2,2'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzOBPy) and 4,4'-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,3'-bipyridine (2TCzPBPy) show deep blue light emission at 440 nm and 422 nm, respectively, in doped films. OLED devices fabricated with these two compounds as the emissive layers have CIE coordinates of (0.152, 0.063) and (0.172, 0.098), respectively, with y values of the color coordinates both less than 0.1, indicating deep blue light emission with high color purity. Additionally, devices based on 3,3'-bis(3,6-di-tert-butyl- 9H-carbazol-9-yl)-4,4'-bipyridine (2TCzMBPy) exhibit blue-green light emission, achieving a maximum external quantum efficiency (EQE) of 3.6% and a maximum brightness of 5423 cd•m⁻².

Calixarene derivatives are widely used in the fields of supramolecular chemistry, coordination chemistry, self-assembly chemistry, optoelectronic materials, and so on. The extensive development of calixarene studies has fostered growing interest in exploring the chemistry of heterocalixarenes, particularly while the aryl units of calixarenes are replaced by heterocycles. Calixfurans, also known as tetraoxaporphyrinogens, represent a significant class of heterocalixarenes. Here, we present a novel class of calixfuran macrocycles and study their interactions with acid compounds. Under catalysis by sulfuric acid, furan and tetrahydro-2H-pyran-4-one were condensed to obtain calix[4]furan macrocyclic compound C4TP and calix[6]furan macrocyclic compound C6TP. The macrocycles were characterized by ¹H nuclear magnetic resonance (¹H NMR), ¹³C nuclear magnetic resonance (¹³C NMR), and mass spectrometry, specifically, the structure of C4TP and C6TP were determined by single-crystal X-ray diffraction analysis. The crystal of C4TP was cuboidal, colorless with smooth surface, good light transmittance, and triclinic system, space group name was P-1. According to the single crystal structure, the molecular skeleton showed a tetragonal cup structure with mirror symmetry. The four furan rings were enclosed like four walls, and tetrahydropyranes were located at the four corners through spiral-conjugate interactions. It was found that the solvents of macrocycle C4TP could change color after interacting with acid compounds. The interactions between the macrocycle host C4TP and a series of acid guests were systematically studied by ultraviolet-visible absorption spectroscopy. The results indicated that the solvents of macrocycle C4TP and different acids presented new absorption bands in the visible light region, exhibiting different colors. Particularly, when macrocycle C4TP was mixed with methanesulfonic acid (MSA), it appeared a wide range absorption over 300~700 nm and displayed green color. Subsequently, we investigated the effects of interaction time and different equivalents of MSA on the ultraviolet-visible absorption spectra. The results figured out that the interaction between the macrocycle C4TP and MSA essentially reached a stable state after 48 h, and achieved a high intensity at a molar ratio of 1∶2000. This study provides a new model and insight into the research of host-guest interactions of calixfuran macrocycles with acid.

Seeking efficient direct Z-scheme heterojunction photocatalysts for water splitting and hydrogen production is an effective way to solve energy crises and environmental problems. Here, we used first-principles calculations based on density functional theory (DFT) to systematically study the electronic structure, optical properties, and photocatalytic performance of the constructed two-dimensional Hittorf’s violet phosphorene (HP)/SnS₂ heterojunction. To achieve more accurate results, the Heyd-Scuseria-Ernzerhof (HSE06) calculations are performed to verify the results, especially for the calculations of the electronic structure and the optical properties. The hybrid functional computational results showed that the HP/SnS₂ heterojunction is a direct bandgap semiconductor with a bandgap value of 1.30 eV. The staggered band structure and the built-in electric field induced by interlayer charge transfer result in a direct Z-scheme carrier migration mechanism, giving it a stronger oxidation-reduction ability to trigger water-splitting reactions. Under illumination conditions, the external voltage provided by the photogenerated electrons on the HP side and the photogenerated holes on the SnS₂ side can significantly reduce the Gibbs free energy of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which is substantially lower than Gibbs free energy required for single-layer HP and two-dimensional SnS₂ to catalyze the same reaction, resulting in excellent hydrogen evolution activity and oxygen evolution activity. In addition, theoretical calculations showed that biaxial strain can effectively regulate the photocatalytic ability and light absorption characteristics of HP/SnS₂ heterojunction. We found that at a strain of –10%, the HP/SnS₂ heterojunction exhibits the strongest light absorption ability under visible light, with a light absorption coefficient of up to 1.71×10⁶ cm^-1. By comparing the oxidation-reduction potentials of water, it was found that HP/SnS₂ heterojunction can meet the conditions for photocatalytic overall water splitting when the strain ranges from –10% to 8%. Its solar to hydrogen (STH) conversion efficiency can reach up to 54.90%, far exceeding the commercial requirement of 10%. In summary, HP/SnS₂ heterojunction is an excellent candidate material for overall photocatalytic water splitting under visible light.

The iteration of intelligent electronic products has promoted the rapid development of flexible transparent electronics, greatly stimulating the demand of matched energy storage units. Flexible transparent zinc-ion hybrid supercapacitors (ZHSCs) not only combine the advantages of high energy density and high power density, but also exhibit excellent transparency, leading a new revolution in flexible electronic technology. Transparent conductive electrode is the most critical component of ZHSCs, which determines the energy storage characteristics of the whole device. Therefore, it is very important to develop advanced electrode materials with high specific capacitance and high optical transmittance. Transition metal carbides/nitrides (MXenes) are considered ideal materials for fabricating ZHSCs due to their high electrical conductivity and large specific surface area. However, it still faces challenges of small flake size and limited electrochemical performance, as well as low synthesis yield, high cost, and difficulty in large-scale application. To address these issues, this work reports a simple and effective method to fabricate high-yield large-sized Ti₃C₂T_x, through in-situ etching approach to prepare multilayer Ti₃C₂T_x (MXene) and mechanical shaking strategy. Using Ti₃C₂T_x electrode as the positive electrode, zinc electro-deposited indium tin oxide/polyethylene terephthalate (ITO/PET) as the negative electrode, and zinc trifluoromethanesulfonate as the electrolyte, an asymmetric ZHSC device was assembled. Experimental results show that when the shaking time is 1.5 h, the Ti₃C₂T_x flake size reaches 5.2 μm with a high yield of 32.4%. The resulting ZHSCs exhibit a voltage window of 1.2 V, a large areal capacitance of 7.79 mF•cm^-2, high power density of 60.0 µW•cm^-2, high energy density of 1.56 µWh•cm^-2, and high transparency of 62.1%. After bending and folding at 180°, the device retains 94.1% of its capacitance. Moreover, the ZHSC-30 device maintains a capacitance retention rate of 82.3% after 1000 cycles at a current density of 600 µA•cm^-2, demonstrating its stable cycling performance. This work provides a powerful method for the fabrication of large-sized MXenes for application in flexible transparent ZHSCs.

Energy storage technology is particularly important for stabilizing smart grids for the future. All-solid-state energy storage remains a critical challenge for advancing energy storage systems. Carbon nitride conjugated polymers have the greatest development potential due to their special direct photogenerated charge storage behavior. We successfully fabricated an electrolyte-free, all-solid-state photo-supercapacitor based on carbon-rich carbon nitride, comprising a C-rich carbon nitride conjugated polymer (CPCN), TiO₂ nanocrystals, and fluorine-doped tin oxide (FTO) conductive glass. The device structure follows the configuration FTO//TiO₂//CPCN//TiO₂//FTO, where CPCN functions as the light-absorbing layer for photogenerated carrier generation and charge storage, while TiO₂ serves as both charge stabilization and transport material. Material morphology was characterized by scanning electron microscopy (SEM), and the composition was analyzed by element distribution map equipped with SEM. Photoelectrochemical performance and charge storage behavior were systematically evaluated using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) measurements, and electrochemical impedance spectroscopy (EIS). The optimal CPCN aging time, TiO₂ mesoporous film thickness and TiO₂/CPCN electrode area were found to make the photogenerated charge storage capacity of the single cell reach 380.1 C•g^-1. It was also found that the specific capacity of the battery was stable at a constant level between 350.7 C•g^-1 and 340.3 C•g^-1 when the electrode area exceeded 9 cm^-2. The energy management concept of the photo-supercapacitor to store photogenerated electrons first and then release them can avoid the problem of photoelectric conversion performance degradation caused by the increase in size like photovoltaic cells. In parallel mode, the photoelectric synergistic effect of CPCN can further reduce electron loss, and the photo charge storage capacity is significantly improved to 412.8 C•g^-1, and the performance does not decay with the increase in battery size. C-rich carbon nitride-based all-solid-state photo-supercapacitors use solar energy to achieve efficient, stable, safe, easy-to-control, low-carbon and environmentally friendly all-solid-state energy storage. The device has broad application prospects in the fields of solar energy management, visual energy storage equipment and self-powered sensors in smart grids.

The gemini cationic surfactant is a type of surfactant that simultaneously connects at least two hydrophobic hydrocarbon chains and two polar head groups through one intermediate group. Multiple hydrophobic chain segments and hydrophilic groups act concurrently in the system, enabling more effective reduction of the surface tension within the system. However, within the research realm of alternatives to fluorinated surfactants, the potential of the gemini cationic surfactant structure as a substitute has received relatively little attention. In this study, we synthesized tertiary amines using CF₃OCF(CF₃)CF₂OCF(CF₃)- (C72), CF₃(OCF₂)₃- (OC3), CF₃(OCF₂)₄- (OC4) and C₅F₁₁- (C6) methyl esters in methanol solvent at room temperature. Subsequently, a series of gemini cationic surfactants were obtained through the quaternization of the tertiary amine with one benzylbromide and three dibromide compounds in acetonitrile solvent. The reaction conditions for most samples were mild. After purification, the purity of the samples could nearly reach 95%, which rendered the surface activity characterization results more accurate and persuasive. The sample named C72(Et)-o-phenyl-C72, which features diethyl substitution, requires the optimization of reaction conditions. Subsequent purification through column chromatography is necessary to obtain products of high purity. 1% (w), 0.1% (w), 0.01% (w) and 0.001% (w) solutions were prepared for each compound, and the surface tension was measured by the Wilhelmy plate method. The properties of the samples were compared, and the rule between the properties of fluorine-containing gemini cationic surfactants and the degree of incorporation of oxygen atoms on the hydrophobic chain, as well as their different isomers, was preliminarily explored. The results suggest that the characterization results of OC3 and OC4 series samples, of which hydrophobic chain segment featured repetitive -OCF₂O- units, are the most favorable, and the sample properties are minimally affected by the structure. The sample surface activity of C72 series samples, whose hydrophobic chain segment contains only two oxygen atoms, are relatively low, while the sample characterization results of C6 samples, which has no oxygen atoms, are the least outstanding. The results manifest the uniqueness and feasibility of the fluoroether chain segment gemini cationic surfactants, and the structure has potential to serve as a substitute for long-chain fluorocarbon surfactants.