Science China Chemistry最新文献

Metabolic adaptation of cancer cells is a key tactic for maintaining their tumorigenicity and viability in the tumor immune microenvironment (TIME). Concurrent modulation on the metabolic pathway and immune system could change the living condition of cancer cells and potentiate the efficacy of anticancer drugs. A copper complex (DDCu) was designed to influence the energy metabolism of cancer cells and reshape the TIME. DDCu restrained the production and transportation of lactate by inhibiting the expression of lactate dehydrogenase and monocarboxylate transporter 4, thereby altering the metabolic pathway of cancer cells and improving the acidic tumor microenvironment. Meantime, DDCu was reduced to Cu⁺ by cellular glutathione to react with lipoylated proteins of the tricarboxylic acid cycle and destabilize the Fe–S cluster proteins, leading to the aggregation of dihydrolipoamide S-acetyltransferase and cuproptosis in cancer cells. Furthermore, DDCu promoted the polarization of macrophages from the M2 to M1 phenotype, activated CD4⁺ and CD8⁺ T cells, and reversed the immunosuppression. As a result, DDCu inhibited the tumor growth through a synergy between metabolic regulation and immunomodulation.

Achieving green ammonia (NH₃) synthesis requires developing effective catalysts under mild conditions. However, the competitive adsorption of N₂ and H₂, as well as the strong binding of N-containing intermediates on the catalyst, greatly inhibits the active sites for efficient NH₃ synthesis. Here, we constructed a series of ZrH₂-modified Fe catalysts with dual active sites to address these issues and realized efficient NH₃ synthesis under mild conditions. Our study shows that ZrH₂ can not only provide active sites for H₂ activation but also transfer electrons to Fe sites for accelerating N₂ activation. The interaction between Fe and ZrH₂ over 40ZrH₂-Fe leads to a decrease in work function and a downward shift of the d-band center, which is conducive to N₂ activation and NH₃ desorption, respectively. The utilization of distinct sites for activating different reactants can avoid the competitive adsorption of N₂ and H₂, leading to excellent NH₃ synthesis activity of the 40 wt.% ZrH₂-mediated Fe catalyst. As a result, 40ZrH₂-Fe exhibits a high NH₃ synthesis rate of 23.3 mmol g_cat⁻¹ h⁻¹ at 400 °C and 1 MPa and robust stability during 100 h time-on-stream.

Metal-organic frameworks (MOFs) refer to novel crystalline porous materials constructed by linking metal nodes and organic linkers through coordination bonds. Featuring predictable and designable long-range ordered structures, high surface areas, guest-accessible voids, and easily functionalized channels by pre- or post-modifications, MOFs have attracted much attention in the past two decades. In this review, we discussed the design strategies, synthesis methods, and structural characteristics of MOFs and MOF-derived/composite materials. Meanwhile, the challenges facing MOF research were also discussed.

Tetra-coordinated fluoroboron compounds have garnered significant attention in organic light-emitting diodes (OLEDs) due to their remarkable optoelectronic properties and high chemical stability. However, the design of novel tetra-coordinated fluoroboron-based blue thermally activated delayed fluorescence (TADF) materials with excellent external quantum efficiency (EQE) remains crucial. In this study, a novel tetra-coordinated difluoroboron-based blue TADF material with 3,6-diphenylcarbazole donor and 2-(4-phenylpyridin-2-yl)phenolate difluoroboron acceptor molecular skeleton has been designed and synthesized. Benefiting from the larger dihedral angle (68.0°) between the donor and acceptor moieties, the compound m-PhCz-BF2 exhibited a smaller singlet-triplet energy splitting (ΔE_ST) value of 0.043 eV. As a result, a sky-blue emission with peak wavelengths of 491 and 487 nm and photoluminescence quantum yields (PLQY) of 93% and 99% were obtained in solution and doped film, respectively. Additionally, the m-PhCz-BF2 doped OLED demonstrated sky-blue electroluminescence (Commission Internationale de l’Éclairage, CIE_y ⩽ 0.33) and a high peak EQE of 27.4% with maximum brightness of 17,493 cd/m². Notably, these devices also achieved a high current efficiency of 62.5 cd/A and a power efficiency of 49.4 lm/W. These remarkable performances indicate that the m-PhCz-BF2 has the potential to function as a highly efficient TADF dopant for the fabrication of sky-blue OLEDs.

Phototherapy has emerged as a promising modality in modern medicine, attracting significant attention due to its non-invasiveness, exceptional spatiotemporal controllability, and reduced side effects. Advanced technologies have been developed in phototherapy, encompassing three main approaches: photodynamic therapy, photothermal therapy, and photoactivatable prodrug-based therapy. In this review, we present photosensitizers, photothermal agents, and photoactivatable prodrugs, along with photo-responsive carriers used in therapy. Subsequently, we discuss the advantages of phototherapy in combating cancer, infections, and other diseases. Additionally, we highlight the benefits of combining phototherapy with other treatments, as single-mode therapeutic modalities often fail to achieve satisfactory efficiency. Finally, we address the current challenges in developing effective phototherapy agents, particularly regarding their clinical applications. We believe that advancements in phototherapy will promote non-invasive theranostic techniques for clinical studies.