The Royal Society of Chemistry最新文献

Organic–inorganic hybrid materials have significant potential in the photocatalytic degradation of Rhodamine B (RhB). In this study, five hybrid materials were successfully synthesized by modifying silicotungstic acid (H₄SiW₁₂O₄₀, abbreviated SiW₁₂O₄₀) with diverse MnL [L = Salen(L¹), 5-Br-Salen(L²), 5-Cl-Salen(L³), 3-Me-Salen(L⁴), di-tBu-Salen(L⁵)] complexes, specifically derivatives featuring various substituents. All the compounds are characterized by IR spectra, elemental analyses and thermogravimetric analyses (TGA). The band gaps of 1.33–1.52 eV and energy bands are obtained through the measurement of UV-Vis DRS and Mott–Schottky. Photocatalytic experiments of (MnL¹)₄SiW₁₂O₄₀ (compound 1), (MnL²)₄SiW₁₂O₄₀ (compound 2), (MnL³)₄SiW₁₂O₄₀ (compound 3), (MnL⁴)₄SiW₁₂O₄₀ (compound 4) and (MnL⁵)₄SiW₁₂O₄₀ (compound 5) indicate that compound 2 catalyst exhibits the best photocatalytic properties (RhB degrades to 6% during 70 min) while all of them possess catalytic activity for photodegradation of RhB under UV irradiation. Free radical trapping experiments show that the addition of PBQ (·O₂⁻ trapping agents) makes the RhB residual ratio increase from 6% to 60% and indicates that ·O₂⁻ is playing a pivotal role. A possible mechanism of RhB photodegradation in the presence of compound 2 is proposed based on free radical trapping experiments and the energy bands. Future work could focus on fine-tuning the molecular architecture through strategic modification of the organic ligands and precise control of the metal-to-POM ratio, potentially leading to optimized electronic structures and enhanced charge transfer kinetics for superior photocatalytic performance in environmental applications.

This study developed a nano-foam gold modified boron-doped diamond (NFG/BDD-Apt) electrochemical aptasensor through a synergistic electrodeposition-dealloying strategy combined with aptamer functionalization for detecting 17β-estradiol (E2) in aquatic environments. The NFG/BDD-Apt sensor was systematically characterized using SEM, Raman, and EIS to elucidate its surface morphology, molecular structure, and electrochemical properties. SEM analysis revealed the successful formation of a homogeneous three-dimensional porous NFG structure on the BDD surface, which significantly enhanced the specific surface area (1.9-fold increase vs. bare BDD) and electron transfer efficiency. Electrochemical performance evaluation through CV and DPV demonstrated superior E2 detection capabilities. Under optimized conditions, the sensor exhibited a wide linear response range from 1.0 × 10⁻¹⁴ to 1.0 × 10⁻⁸ mol L⁻¹ (R² = 0.997) with an ultralow detection limit of 1.8 × 10⁻¹⁵ mol L⁻¹ (S/N = 3). NFG/BDD-Apt demonstrated exceptional selectivity (>92% specificity against common interferents) and long-term stability. This work provides a novel sensing platform combining diamond electrode advantages with nanostructured amplification effects, offering significant potential for rapid and reliable monitoring of endocrine disruptors in environmental water systems.

Our understanding of the formation pathways of interstellar mineral dust is still evolving. This study investigated the formation of astrophysical mineral dust, such as olivine, by shock processing. Low-velocity (∼1.8 km s⁻¹) interstellar shock conditions were simulated using high-intensity shock tubes. These conditions enabled the examination of various cosmic mineral dust precursors such as the mixtures of Mg, Fe and SiO₂ under a shock strength of approximately 5.6 M and temperatures around 7300 K. Analysis of the processed samples revealed the presence of Mg-rich olivine, forsterite, MgO quantum dots (QD), and magnetite. These results indicate that shockwaves can rapidly induce dust formation in interstellar space. Furthermore, we demonstrated that shock processing of mineral dust precursors could contribute to the formation of crystalline silicate dust observed in comets and the creation of chondrules, which are observed in chondritic meteorites.

The application of metal organic frameworks (MOFs) in targeted drug delivery for ischemic stroke therapy has emerged as a hot issue recently. Although significant progress has been made in immobilizing neuroprotective agents on MOFs, environmentally friendly large-scale preparation of nano-drug-loaded MOFs with controlled size, morphology, purity and therapeutic effect remains challenging. PEGylation of MIL-101(Cr) nanoparticles with dual ligands that have the 2,2-dimethylthiazolidine (DMTD) structure was developed in this work to mitigate nervous system injury induced by ischemia/reperfusion (IR) during a stroke. A green ultrasound-assisted continuous-flow system was established for efficient production of the versatile MOF nanoparticles. Unified nanoparticles (diameter: ∼250–350 nm) were obtained with both high quality and high space-time yield (5664 kg m⁻³ d⁻¹). The MOF exhibited protective activity in SH-SY5Y cells against oxygen and glucose deprivation and H₂O₂ insults, and prevented reactive oxygen species accumulation. The cellular uptake of the PEGylated MOFs by brain capillary endothelial cells was investigated, showing targeting capability in vitro, which proposes the biomaterial as a promising therapeutic candidate for reducing IR-induced nervous system injury.

Square-planar complexes were synthesized by the reaction of 2′,6′-di(thiazol-2-yl)-2,4′-bipyridine with either Na₂[PdCl₄] or K₂[PtCl₄], and these were thoroughly structurally characterized using some analytical and spectroscopic techniques. Density functional theory computations, including natural bond orbital analysis, were used to complement the experimental work to gain insight into the natural charge and electronic arrangement of the metal ion, as well as the strength of the metal–ligand bonds. The Pd(II) complex exhibited exceptional cytotoxicity against the A549 and HCT-116 cell lines with IC₅₀ values of 60.1 ± 3.45 and 23.8 ± 1.48 μM, respectively. Unfortunately, the Pd(II) complex was harmful to the Vero normal cell line with an IC₅₀ value of 24.5 ± 2.13 μM. The Pt(II) complex is unstable and has a high likelihood of exchanging the chlorido ligand for solvent molecules such as DMSO. The fluorescent-stain photos of the treated HCT-116 cells with the Pd(II) complex showed increased apoptotic bodies, indicating both early (18%) and late apoptosis (32%), as well as a necrosis ratio of about 10%. Flow cytometric analysis demonstrated that a cell arrest was induced by the Pd(II) complex on HCT-116 cells in the G₂/M phase.

An efficient iodine-catalyzed thio-arylation reaction of aniline was developed under electrochemical conditions. A variety of diaryl sulfide compounds can be obtained under metal-free and chemical oxidant-free conditions. The reaction features a broad substrate scope, regulation of product distribution, and scalable preparation.

Photocatalytic CO₂ reduction offers a promising pathway for achieving sustainable development. However, the effectiveness of this method faces challenges related to imbalanced charge transfer/utilization. To address these issues, this paper reports on cobalt-doped zinc oxide nanoparticles (Co-ZnO NPs). The cobalt doping not only increases light absorption but also improves charge transfer/separation kinetics and modulates the reduction reaction dynamics. Notably, photocatalytic tests show that cobalt-doped zinc oxide (Co-ZnO) achieves a CO yield of 143.90 μmol g⁻¹ h⁻¹, which is 15.73 times higher than that of undoped ZnO, and exhibits excellent stability. This study emphasizes the importance of polarization states induced by doping for achieving efficient charge separation, providing a new approach to enhance the efficiency of photoredox catalysis.

Soil contamination by heavy metals presents a substantial environmental challenge. Remediation strategies employing biochar and apatite offer promise for restoring compromised sites. However, the efficacy of apatite and biochar derived from various biomass sources remains an under-investigated area. Taro stem-derived biochar produced at 300 and 500 °C (TSB300 and TSB500) and apatite amendments were incubated in contaminated soil for one month at various ratios (biochar 3%, 6%, 10%, mixture of biochar/apatite 3 : 3%, and 6 : 6% w/w) to investigate their potential to immobilize Pb and Zn. The initial concentrations of Pb and Zn in the contaminated soil were 4165.1 ± 19.6 mg kg⁻¹ and 3424.9 ± 20.4 mg kg⁻¹, respectively. Soil samples were subjected to Tessier's sequential extraction for analysis of Pb and Zn in five chemical fractions (F1: exchangeable fraction; F2: carbonate fraction; F3: Fe/Mn oxide fraction; F4: organic carbon fraction and F5: residual fraction). The results indicated that one-month biochar and/or apatite amendment significantly increased soil pH, organic carbon (OC), and electrical conductivity (EC) compared to the control (p < 0.05). Amendments also notably reduced exchangeable fractions of Pb and Zn (F1) up to 71.8% and 61.5%, respectively, while enhancing their presence in more stable fractions (F4 and F5). This immobilization effect peaked at the 10% biochar application and 6 : 6% biochar–apatite combination. These findings suggest that TSB300, TSB500, and their blends with apatite hold promise for immobilizing Pb and Zn in heavily contaminated soil, potentially mitigating environmental risks.

Photocatalytic nitrogen fixation is a forward-looking technology for zero-carbon nitrogen fixation, which is crucial for alleviating the energy crisis and achieving carbon neutrality. Based on research into the structural regulation of nitrogen-fixing photocatalysts, this review summarizes the latest progress and challenges in photocatalytic ammonia synthesis from three dimensions: active sites, crystal structures, and composite structures. In terms of active site construction, common types of active sites, including metal sites, non-metal sites, vacancies, and single atoms, are discussed. Their characteristics and methods for improving photocatalytic nitrogen fixation performance are analyzed. Furthermore, starting from the mechanism of nitrogen activation, a general strategy for active sites to promote the electron exchange process and thereby enhance nitrogen activation efficiency is explored. In terms of crystal structure construction, the design of nitrogen-fixing photocatalysts is described from three perspectives: crystal form, crystal facet, and morphology control. In terms of composite structure construction, this review discusses the key role of structures such as semiconductor–metal composites and semiconductor–semiconductor composites in promoting carrier separation. It is hoped that this review can provide new insights for the design and preparation of efficient nitrogen-fixing photocatalysts and inspire practical applications of photocatalytic nitrogen fixation.

The development of environmentally friendly oil-absorbing fibrous materials is crucial, as conventional separation materials contribute to secondary pollution due to their nondegradability. In this study, highly hydrophobic and superoleophilic porous polylactic acid (PLA) fibers were fabricated via centrifugal spinning combined with nonsolvent-induced phase separation. The fiber porosity was controlled by adjusting the ratio of good solvents to nonsolvent in the spinning solution. The morphology and physical properties of the PLA fibers were systematically analyzed. Among the prepared samples, PLA fibrous membranes spun from a chloroform/dimethylformamide (80/20 w/w) solution exhibited a high water contact angle and superior oil absorption capacity. These results demonstrate the potential of porous PLA fibers as sustainable materials for environmental applications.