Latest ArticlesLight-energy-driven semiconductor catalysis offers attractive ways to address environmental and energy crises. TiO2 is the most promising catalyst for photocatalysis, but the lack of charge-carrier separation efficiency severely limits its catalytic performance. In this study, we carried out crystal phase engineering to prepare in situ Z-scheme hetero-phase homojunction of anatase-rutile and clarified the structure-performance relationship. The efficiency of sulfamerazine removal by hetero-phase homojunction TiO2 nanotube arrays in a single-compartment photocatalytic fuel cell system was improved by 1.93 times compared to conventional anatase TiO2 nanotube arrays and the degradation pathways were revealed by the Fukui function combined with HP-LCMS. The successful construction of Z-scheme hetero-phase homojunction was confirmed by Raman, X-ray diffraction (XRD), and electron spin resonance (ESR), which combined with density functional theory (DFT) calculations revealed the key role of crystal phase engineering in the construction of hetero-phase homojunction. This work provides a novel strategy for the scientific design of titanium dioxide photocatalysts.
The preparation of a novel nanoscale imazalil (IMZ)-based coordination polymer [Zn(HBTC)(IMZ)2]n (PDCP1) (H3BTC = 1,3,5-benzenetricarboxylic acid), and its antifungal application within a sustainable delivery system was reported. The intermolecular interactions presented in the structure, and their contributions to crystal packing were studied by Hirshfeld, Fingerprint plot and Mayer bond order. The obtained PDCP1 had a relatively high loading rate of IMZ (68.5%). PDCP1 exhibited notable antifungal activities against Colletotrichum gloeosporioides, Magnaporthe Oryzae, and Alternaria Nees strains, with EC50 values of 0.72, 0.92, and 0.56 µg/mL, respectively. The key benefits of the application of PDCP1 as a control release pesticide include high fungicide loading and offer nearly complete release, pH-responsive release, enhanced UV stability, exhibits favorable biosafety profiles. The remarkable inhibition of C. gloeosporioides growth by PDCP1 underscores a promising strategy for agrochemical material development, high loading of active ingredients and readily delivery fosters more efficient pesticides utilization in agricultural processes.
Polyethylene oxide (PEO)-based solid polymer electrolytes (SPEs) have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes. Here, we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions, which self-assemble into flower-like spherulites with radially aligned lamellar crystals. This unique structure creates continuous Li+ transport highways through densely packed crystalline domains, achieving a record-high ionic conductivity of 1.70 × 10–4 S/cm at 25 ℃ for pristine PEO-based systems. Strategic incorporation of lithium montmorillonite (MMTli, 10 wt%) further optimizes the composite electrolyte, balancing high ionic conductivity (1.47 × 10–4 S/cm) with enhanced electrochemical stability (4.99 V vs. Li+/Li), elevated Li+ transference number (0.62), and mechanical robustness. The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO4||Li solid-state batteries with 82% capacity retention after 200 cycles at 0.2 C under ambient conditions. This work pioneers a scalable processing paradigm for crystalline polymer electrolytes, offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
Albumin, owing to its high abundance and excellent biocompatibility, is widely used as a drug carrier to enhance delivery efficiency and reduce systemic toxicity. The Michael addition between albumin thiols and maleimide-functionalized prodrugs is a common in situ macromolecular prodrug strategy. However, the resulting reversible adducts are susceptible to retro-Michael reactions in vivo, leading to premature drug release and off-target effects. To address this limitation, a gemcitabine prodrug (GAB) bearing a chloroacetamide group was designed to form irreversible covalent bonds with albumin via nucleophilic substitution. A maleimide-based prodrug (GAM) was synthesized as a control. Compared to GAM, GAB showed faster and stronger albumin binding in plasma, enhanced blood circulation time, improved tumor accumulation, and superior in vivo antitumor efficacy. Moreover, GAB exhibited a better safety profile, with reduced cytotoxicity in normal tissues and no observable systemic toxicity. These advantages are attributed to the stable albumin-drug conjugate formed by GAB, which improves drug retention and targeted delivery. This study presents an effective and generalizable albumin-hitchhiking strategy for constructing irreversible prodrugs, offering a promising approach to enhance the therapeutic index of chemotherapeutic agents.
Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals. The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development. While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio (SCF3−) group on a stereogenic carbon, the synthesis of trifluoromethylthiolated alkanes featuring a SCF3-substituted stereogenic carbon at non-activated site remains understudied. Herein, we report a Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes. Important to the process is the regio- and enantioselective Cu-H insertion to SCF3-substituted alkene to form chiral α-SCF3 alkyl copper intermediates, outcompeting unproductive insertion to the coupling partner, and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.
The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction (HER) at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries. In this work, we propose sorbitan oleate (Span 80) as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO4, demonstrating multifunctional performance. The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface, forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions. Simultaneously, carbon chains can enhance the desolvation effect of [Zn(H2O)6]2+, leading to improve rate performance. Additionally, the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode, promoting uniform Zn2+ deposition and suppressing dendrite growth. The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability, sustaining reversible plating/stripping for 570 h at 50 mA/cm2 and the Zn||V2O5 full cell retains exceptional stability over 2000 cycles at 1 A/g. Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants. This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
The demand for 238Pu (nuclear battery heat source) drives the separation of its precursor, 237Np, from spent nuclear fuel (SNF). However, the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np. N-Butyraldehyde (n-C3H7CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ). Herein, we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory. Based on the results of the potential energy profiles, the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO are thermodynamically feasible, whereas only the former is kinetically achievable. It uncovers that n-C3H7CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction. The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer, whereas that for the second one involves outer-sphere electron transfer. Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ). This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by n-C3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
Hard carbon is a vital anode material for sodium-ion batteries; however, the nonuniform growth of solid electrolyte interphase (SEI) film substantially diminishes its initial coulombic efficiency (ICE) and cycle life. The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions. In this study, we have tuned orbital hybridization states forming an interface enriched with sp2 hybridized carbon (sp2–C), which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation. Benefiting from successfully constructed inorganic-rich SEI, the ICE increased to 91% and sodium storage capacity reached 346 mAh/g. Besides, the capacity retention rate was 90.7% after 700 cycles at 1 A/g higher than pristine electrode (83.8%).
One-dimensional (1D) organic-inorganic halide perovskites have produced significant research interest due to their unique structure and superior tunable luminescence properties. Here, we successfully achieved a unique color-tunable phenomenon of Mn-doped 1D post-perovskite (TDMP)PbBr4 (TDMP = trans-2,5-dimethylpiperazine) (TPBM-14) under high pressure. Which exhibited tunable photoluminescence (PL) emission from red to yellow orange. Meanwhile, the band gap continued to decrease below 20.0 GPa, accompanied by piezochromism, which was associated the shrinkage and distortion of inorganic, which enhances the crystal field splitting energy and reduces the energy gap of the 4T1 to 6A1 transition. The unique octahedral corner- and edge-sharing structure of (TDMP)PbBr4, the synergistic effect of Mn doping and pressure induces local lattice distortion in TPBM-14, leading to a significant enhancement of the STE emission at 8.1 GPa. Our research explores the intrinsic connection between the band structure and optical properties of TPBM-14 under high pressure and offers valuable insights for performance optimization.
The Smiles rearrangement is an exceptionally versatile method in organic synthesis, providing a broad canvas for designing cascade reactions that construct new Csp2-Y (Y = C, O, N, S, CO, etc.) bonds. Among the various types of Smiles rearrangement, the radical-type variant has emerged as a more powerful, mild, efficient, and modern synthetic technique compared to its traditional ionic counterpart. This approach excels in generating new (hetero)aromatic migration products, enabling significant advancements in recent years. This tutorial review focuses on the recent progress, since 2016, in the development and application of radical Smiles rearrangement in organic chemistry. Special attention is paid to novel transformations achieved through photochemical, electrochemical, and transition metal catalysis methods.
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