New Journal of Chemistry最新文献

Developing a rapid and accurate method for determining baicalin (Bn) content is of great significance for the quality control, pharmacological research, and clinical application of Scutellaria baicalensis. Herein, we fabricated a novel electrochemical sensor based on a composite material of a V-substituted Dawson-type polyoxometalate (POM, P₂W₁₅V₃) and carbon nanotubes (CNTs) for the sensitive detection of Bn. The P₂W₁₅V₃@CNTs composite was successfully prepared and characterized by transmission electron microscopy (TEM), infrared spectroscopy (IR), powder X-ray diffraction (PXRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical techniques. Benefiting from the synergistic effect between P₂W₁₅V₃ and CNTs, the P₂W₁₅V₃@CNTs/GCE exhibited excellent analytical performance for Bn detection. Within the concentration range of 2.6–8.2 µM, the proposed electrode achieved a sensitivity of 2.843 µA µM⁻¹ and a detection limit of 26.4 nM (S/N = 3), coupled with favorable selectivity, reproducibility and stability. Moreover, we employed the P₂W₁₅V₃@CNTs-based sensor to detect Bn content in Scutellaria baicalensis samples, and the recoveries ranged from 101.2% to 106.3%, revealing its suitability for practical applications. This study presented a novel strategy for constructing a POM-based electrochemical sensing platform to monitor Bn.

The novel porous material MOF@COF, due to its controllability, porosity and stability, has outstanding capabilities in the field of adsorption. In this study, a Ni-MOF was successfully combined with a 2DPA-1 COF to prepare a hybrid material with mesopores and multilayer structures. The Ni-MOF@2DPA-1 COF exhibits an excellent adsorption effect on dyes through electrostatic and π–π interactions. Experiments show that when pH = 7, it exhibits the best adsorption effect on methylene blue (MB), methyl orange (MO) and crystal violet (CV), and the maximum adsorption capacities are 103.4 mg g⁻¹, 95.7 mg g⁻¹ and 84.6 mg g⁻¹ respectively. Meanwhile, the high adsorption efficiency was maintained after five cycles, indicating that the Ni-MOF@2DPA-1 COF is a promising recyclable wastewater treatment material.

A base-catalyzed strategy for the diastereodivergent synthesis of complex spirocyclic oxindoles and linear Michael's adducts are disclosed. Isoxazole–styrene derivatives display dual reactivity: 3-methyl-4-nitro-5-isatylidenyl-isoxazole undergoes a domino vinylogous 1,4-Michael addition/intramolecular cyclization with vinyl malononitriles to afford spiro[indoline-3,2′-naphthalene]-4′-carbonitriles in good to excellent yields. Remarkably, solvent control enables exclusive access to two specific diastereomers. These scalable and operationally simple protocols deliver two distinct classes of valuable isoxazole-derived products, underscoring the unique reactivity of this scaffold.

The ring-opening copolymerization (ROCOP) of propylene oxide (PO) and CO₂ offers a practical and sustainable approach for producing poly(propylene carbonate) (PPC). However, when this copolymerization is mediated by heavy-metal catalysts, the process often suffers from limited CO₂ incorporation, undesirable formation of polyether linkages, and poor selectivity toward PPC. To overcome these limitations, we introduce a potassium phenyl thiolate/triethylborane (PhSK/Et₃B) catalytic system that enables highly selective production of strictly alternating PPC while completely suppressing polyether formation. Mechanistic studies supported by density functional theory (DFT) reveal that the catalyst operates through a cooperative pathway: PhSK initially captures CO₂ to generate a phenyl carbonate nucleophile, which subsequently attacks Et₃B-activated PO. This synergistic polarization significantly lowers the kinetic barriers for both PO ring-opening and CO₂ insertion, thereby facilitating efficient alternating copolymerization. A systematic investigation further highlights the strong interplay among CO₂ pressure, temperature, and catalyst loading in governing polymer growth. Under optimized conditions, this approach yields high average molecular weight PPC (M_n = 40.33 kg mol⁻¹) with narrow dispersity (Đ = 1.04), excellent selectivity (99%), and complete suppression of polyether linkages. Overall, the PhSK/Et₃B system provides a scalable and environmentally benign platform for CO₂ utilization, advancing the development of high-performance polycarbonate materials.

The synthesis of a new class of dyes based on Rhodamine-ChalcogenoAmino-Thymidine derivatives (RhoCAT) is described. The respective compounds were obtained in moderate to excellent yields using a straightforward protocol, employing Rhodamine-B (RhB) and Aryl-chalcogenoamine-thymidine, via an amidation reaction. The photophysical evaluation showed typical behaviour of rhodamine derivatives with bands centered in the visible region, emission peaks between 450–580 nm and lifetimes ranging from 3.00 to 24 ns, in the solvents studied. The electrochemical behaviour of the derivatives showed processes related to the inserted chalcogen atom and the reactive oxygen species (ROS) generation data indicate the preferential formation of singlet oxygen species and superoxide radicals, depending on the chalcogen atom as well as the aryl substituent. The In silico calculations show the characteristic differences between the absorption spectra of Rhodamine and RhoCAT compounds.

The steel industry faces the dual pressures of carbon reduction and ultra-low emissions throughout production, making integrated CO₂ capture and deep desulfurization of blast furnace gas essential. Conventional alcohol amine-based scrubbing agents have limitations such as low absorption capacity, regeneration difficulties, and high corrosivity. To address these issues, a CO₂, COS (carbon oxysulfide), and H₂S integrated high-efficiency removal biphasic absorbent was developed. The novel biphasic absorbent composed of sulfolane (SF), diethanolamine (DEA), 2-amino-2-methyl-1-propanol (AMP), piperazine (PZ), and H₂O, achieved a removal rate of over 90% for CO₂, COS, and H₂S, under the tested conditions, while exhibiting low rich-phase viscosity and acceptable anti-corrosion performance. Optimal regeneration was attained at 110–120 °C, with regeneration efficiencies exceeding 85% and an estimated energy consumption of approximately 2.51 GJ per ton CO₂ (about 33.9% lower than 30 wt% MEA), while exhibiting stable cyclic regeneration. Spectroscopic analyses (FTIR, ¹H/¹³C NMR) indicate that H₂S undergoes proton transfer to amine sites to form bisulfide containing quaternary ammonium salts, whereas CO₂ and COS react with amine functionalities to yield carbamate and thiocarbamate species that preferentially partition into the aqueous-rich phase; sulfolane remains in the organic phase, enabling liquid–liquid separation. This research provides a promising basis for simultaneous pollution control and CO₂ mitigation in the steel sector, aligning ultra-low emission targets with decarbonization efforts and offering potential environmental and economic benefits.

The research on the photophysical properties and structure–activity relationships of staurosporine derivatives is highly meaningful to develop staurosporine as a new type of anticancer therapeutic. In this work, three staurosporine derivatives (Y1, Y2 and Y3) with aggregation-induced emission (AIE) characteristics and theranostic potential were designed and synthesized by using cyano electron-withdrawing groups to modify the natural staurosporine. These new staurosporine derivatives exhibited AIE properties and solvatochromism. The photoluminescence quantum yields of Y1, Y2, and Y3 are enhanced by factors of 4.3, 5.9, and 7.1 in the aggregated state, respectively. These fluorescent probes also showed protein kinase C (PKC) inhibitory activity and anti-cancer activity for NCI-N87 and MCF-7 cells. The docking calculations revealed that the probes retained antitumor activity by preserving key interactions between the staurosporine core and the protein kinase C (PKC). Cellular imaging demonstrated bright fluorescence emission within tumor cells. This work provides a design strategy for integrating fluorescence performance and pharmacological activity, offering a promising approach for cancer diagnosis and therapy.

A self-assembly paradigm is provided in green photosynthetic bacteria by the chlorin macrocycle bacteriochlorophyll (BChl) c, which contains a 3-(1-hydroxyethyl) substituent, central magnesium ion, and 13-keto group. The assembled BChl c structure is a powerful light-harvesting apparatus that can support life even under extreme low-light conditions. Here, inspired by the work of Balaban, two far simpler porphyrins have been synthesized, 5,15-bis(hydroxymethyl)-10,20-diphenylporphinatozinc(II) (Ph/CH₂OH) and 5,15-bis(hydroxymethyl)porphinatozinc(II) (H/CH₂OH), and analogues wherein ethyl replaces hydroxymethyl (Ph/Et and H/Et). Examination of Ph/CH₂OH and H/CH₂OH by time-resolved spectroscopy showed an ∼2-fold enhancement in the singlet excited-state lifetime compared to meso-tetraphenylporphinatozinc(II) (ZnTPP). The single-crystal X-ray diffraction revealed distinct packing patterns. Porphyrin Ph/CH₂OH exhibited double staircases wherein (1) each zinc is pentacoordinate (by apical coordination of one hydroxymethyl group of a porphyrin in the same staircase), (2) the second hydroxymethyl group is hydrogen-bonded to an apically coordinated hydroxymethyl oxygen atom in the adjacent staircase, (3) the porphyrins in a given staircase are coplanar but cofacially offset with each other, and (4) the adjacent staircases are oriented approximately 72° relative to each other. Porphyrin H/CH₂OH assembled wherein (1) each zinc is hexacoordinate by ligation of hydroxymethyl moieties, (2) each hydroxymethyl –OH is hydrogen-bonded with an acetonitrile solvent molecule in the lattice, and (3) the planes of the four nearest neighbor porphyrins are essentially perpendicular to a given porphyrin. Study of the solid-state packing patterns of sparsely substituted porphyrins enables insights into how the structural design of tetrapyrroles can guide their aggregate self-assembly.

Poly(3-hydroxybutyrate) (P3HB) is a fully biodegradable polyester used for applications such as drug delivery, tissue engineering and food packaging. However, it presents some drawbacks including brittleness, narrow processing window, high water vapour permeability and low thermal stability. The addition of different nanofillers can improve its performance. In this research, P3HB/sepiolite (SEP)/carbon nanotube (CNT)/tungsten disulfide (WS₂) hybrid nanocomposites were prepared via a simple, cheap, and ecological solvent casting method. FE-SEM images reveal a good dispersion of the three nanofillers within a continuous matrix. FT-IR spectra corroborate the strong interactions among the nanocomposite components via hydrogen bonding. A synergistic stabilization effect is observed in the hybrids, showing an unprecedented increase in the temperature of maximum rate of weight loss of 125 °C. A very strong reduction in the water vapor permeability and oxygen permeability is also observed for the nanocomposite with 1 wt% CNT, 2 wt% SEP and 2 wt% WS₂. Further, two regression methods and different machine learning approaches, namely support vector regression (SVR), support vector machines (SVM), artificial neural networks (ANNs), decision tree (DT) and random forest (RF) have been applied to predict their properties. The correlation coefficient, mean absolute error and mean square error are used as statistical indicators to compare their performance. The best models to predict the barrier properties are ANNs and SVR, while for thermal properties, SVM for classification and SVR for regression showed the most reliable performance. This triple filler strategy is a novel approach to develop hybrid nanocomposites for use in biomedicine or the food packing industry.

During the extraction of gold, the cyanidation step poses significant environmental risks. In this study, an environmentally friendly alternative was proposed based on the use of alkaline sodium hypochlorite (NaClO) to leach Carlin-type gold ores. Thermodynamic analysis confirmed that NaClO simultaneously liberated and dissolved gold. Single-factor optimisation achieved a limited leaching efficiency of 88.31% owing to the secondary encapsulation of the Fe(OH)₃ precipitates. To overcome this issue, Na₂CO₃ and sodium carboxymethyl cellulose (CMC-Na) were introduced as regulatory agents. Comprehensive analyses using scanning electron microscopy-energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and electrochemical measurements revealed that sodium carbonate prevented Fe(OH)₃ formation via complexation, while CMC-Na dispersed existing aggregates. Consequently, the gold leaching efficiency was increased significantly to 93.95% and 92.47%, respectively. This work provides theoretical guidance and technical support for the efficient and environmentally sustainable leaching of Carlin-type gold ores.