Latest ArticlesThe asymmetric catalytic synthesis of planar chiral ferrocene derivatives has received dramatic attention in recent years. Transition metal-catalyzed asymmetric cross-coupling reactions and CH functionalization reactions have played significant roles in the stereoselective construction of planar chiral ferrocene derivatives. Transition metals such as copper, palladium, rhodium, iridium, gold, and platinum have been adopted as the effective catalysts in combination with various chiral ligands to achieve satisfactory yields and stereoselectivity. Organic catalysts have also shown great potential in the synthesis of planar chiral ferrocenes. Chiral amines and N-heterocyclic carbenes (NHCs) have been the key catalysts for facile access to multi-functional ferrocene derivatives. Some of the planar chiral ferrocene molecules obtained from the above methods have demonstrated promising applications in the development of novel ligands for asymmetric synthesis and pesticides for plant protection. This review provides an overview on the key progresses in the catalytic synthesis of planar chiral ferrocene derivatives using transition metal catalysts and organic catalysts. The merits, challenges and potential directions in the future development within this highly active research field are also discussed at the end of this review.
Nanozymes are nanomaterials with enzyme-like catalytic activities that have rapidly advanced in the biomedical field in recent years due to their high stability, low cost, and catalytic versatility. As promising alternatives to natural enzymes, nanozymes have demonstrated unique advantages in infection control, cancer therapy, and tissue regeneration. This review systematically summarizes key advances in recent years in nanozyme-based catalytic therapeutics. We focus on their mechanisms and applications in combating bacterial, viral, and fungal infections via membrane lipid peroxidation, protein/genome damage, and biofilm disruption; in cancer treatment through chemodynamic therapy (CDT), tumor microenvironment modulation, and multimodal synergistic strategies; and in bone regeneration through antioxidant, anti-inflammatory, and osteoinductive functions. Moreover, we highlight the integration of nanozymes with hydrogels, scaffolds, and microrobotic systems to enhance therapeutic outcomes. Finally, current challenges such as targeting specificity, in vivo catalytic control, biosafety, and clinical translation are discussed to provide a comprehensive roadmap for future research and clinical development in catalytic nanomedicine.
Based on recently reported high-performance doubly concerted companion (DCC) dye XW96 constructed by covalently linking a porphyrin dye and an organic dye with hexyl chain protected phenothiazine and fluorenyl indoline donors, respectively, we herein employ a branched 2-ethylhexyl chain to realize better anti-charge-recombination and anti-aggregation abilities, achieving improved photovoltaic behavior. Thus, based on XW96, dye XW98 has been synthesized by introducing branched chains to the donors. As a result, the bulkier donors on both sub-dye units cause spatial repulsion, resulting in more severe twisting, decreased adsorption amount and lowered efficiency, compared to XW96. To reduce the steric hindrance, the linker between the two subdye units has been extended on the basis of XW98 (seven bonds) to give XW99 (eight bonds) and XW100 (nine bonds), affording considerably improved adsorption. Notably, XW99 affords an open-circuit voltage (VOC) of 784 mV, a short-circuit current density (JSC) of 22.08 mA/cm2, and a high power conversion efficiency (PCE) of 12.54%. Compared with XW99, dye XW100 exhibits a larger percentage of single anchoring despite its larger adsorption amount, leading to a lowered efficiency of 12.25%. This work indicates that combination of bulky branched chains on the donors with optimized linker length is essential for developing efficient DCC sensitizers.
Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.
The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.
Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr3+-doped Sr9Ga1-x(PO4)7 (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr9Ga0.5(PO4)7:0.5Cr3+ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr9Ga0.5(PO4)7:0.5Cr3+ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.
Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization
Benzo[b]furans are significant scaffolds in drug molecules and are prevalent structural components in natural products. Chemically encoded non-natural peptidomimetics have a substantial impact on pharmaceuticals by offering enhanced stability, improved cell permeability, and resistance to enzymatic degradation. Consequently, a strategy for the sustainable assembly of benzo[b]furan/benzopyran-functionalized peptides through the electrochemical late-stage modification of alkyne-modified tyrosine oligopeptides is proposed. This approach facilitates the multifunctional integration of non-native tyrosine-derived substrates, as well as their subsequent functionalization. Notably, the resulting peptides exhibit favorable properties regarding biocompatibility and cellular uptake.
Polymer surface modification constitutes a pivotal strategy for enhancing the efficacy of nanomedicine delivery, where intentional modifications (e.g., PEGylation, hyaluronic acid coating) are designed to optimize nanocarrier performance. However, conventional approaches remain constrained by the impermeable stratum corneum in transdermal applications. Dissolving microneedles (DMNs) circumvent this barrier by creating transient microchannels, thereby offering an innovative route for cutaneous nanocarriers administration. Nevertheless, the DMN polymeric matrix may unintentionally alter the physicochemical attributes of loaded nanocarriers via non-covalent interactions, giving rise to a distinct “polymer modification effect” (PME) that differs from purposeful surface engineering. Such unintended interfacial phenomena can modulate nanocarrier characteristics and, consequently, dictate their in vivo fate, including release kinetics, biodistribution, clearance, cellular uptake, and other interactions with the biological system. Herein, we review documented cases of DMN polymer-nanocarrier modifications, elucidate the underlying mechanisms and implications of PME, and propose rational strategies for its precise regulation. This conceptual framework is expected to guide the rational design of next-generation nanocarrier-loaded DMN delivery systems.
Developing passive cooling materials with dual functionality of high-performance thermal management and aesthetic appeal remains a critical challenge for sustainable development. Here, we present a hydrophobic force-driven assembly strategy to construct crack-free colloidal photonic crystals (CPCs) for colored passive daytime cooling (PDC) textiles. Monodispersed poly(styrene-hydroxypropyl acrylate-hexafluorobutyl methacrylate) (P(St-HPA-HFBMA)) colloidal particles with low surface energy (9 mN/m) and high monodispersity (PDI < 0.05) are synthesized via soap-free emulsion polymerization. The hexafluorobutyl terminal groups (C3F6) enable robust hydrophobicity (water contact angle: 124°), facilitating crack-free CPC assembly through hydrophobic driving force. By integrating the CPCs with SiO2 aerogel-embedded polyethylene oxide (PEO/SiO2 aerogel) fiber scaffold based on microfluidic spinning technology, a colored hybrid composite film is fabricated, achieving 0.76 solar reflectance and 0.84 thermal emissivity in the atmospheric window (8-13 µm). Outdoor evaluations demonstrate a sub-ambient cooling temperature of 4.1 ℃ under 732 W/m² solar intensity, reaching the desirable level of PDC materials. The hybrid composite film also exhibits angle-independent structural colors, mechanical robustness (tensile strength: 1.86 MPa), and scalable manufacturability. This work provides a paradigm for multifunctional PDC systems combining aesthetic versatility with sustainable cooling performance.
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