New Journal of Chemistry最新文献

This study reports the green synthesis, comprehensive characterization, DNA and BSA binding assessment, and photocatalytic dye degradation activity of bimetallic copper–nickel nanoparticles (NS–CuNi) synthesized using water-soluble Nigella sativa seed extracts. The eco-friendly, plant-mediated approach utilizes phytochemicals as both reducing and stabilizing agents, eliminating the need for toxic chemicals and enhancing the nanoparticles’ biological compatibility. NS–CuNi nanoparticles with high elemental purity and surface functionalities were derived from the seed extract. Optical studies revealed distinct dual surface plasmon resonance peaks (260 and 325 nm), while XRD and electron microscopy evidenced a face-centered cubic morphology, narrow size distributions, and high surface area. The nanoparticles exhibited remarkable photocatalytic performance, achieving over 94% degradation of hazardous rhodamine B and methylene blue dyes within 70–80 minutes under visible light, with pseudo–first-order kinetic behavior (rate constants: 0.0405 min⁻¹ for rhodamine B and 0.038 min⁻¹ for methylene blue). Biomolecular interaction studies demonstrated strong DNA binding affinity (5.85 × 10⁵ M⁻¹) and reversible, moderate BSA interaction (K_sv: 8.1 × 10⁴ M⁻¹), supporting their biomedical compatibility. In vitro cytotoxicity assays revealed significant dose-dependent inhibition of MCF7 and HepG2 cancer cells, with IC₅₀ values (23.47 and 32.32 µg mL⁻¹, respectively) comparable to other green-synthesized bimetallic systems, though cisplatin exhibited superior potency. The synergistic effects of copper and nickel, combined with the natural capping biomolecules, imparted enhanced redox activity, bio-interactivity, and catalytic efficiency.

A high-permeance and high-selective Mg²⁺/Li⁺ separation membrane, synthesized through interfacial polymerization using a quaternized spiro-piperazine monomer (QSPIP) and trimesoyl chloride (TMC), named QSPIP–TMC, was studied via molecular dynamics simulations and quantum chemical calculations. We successfully constructed dry and hydrated QSPIP–TMC films, alongside PIP–TMC films as a control group. Theoretical results indicated that the voluminous QSPIP monomer leads to the formation of expanded cavity structures, enhancing water diffusion coefficients through the membrane. The restrained diffusion behavior of the QSPIP monomer toward the interface facilitates the fabrication of more uniform nanofiltration membranes, boosting membrane stability and separating behavior. Additionally, the Li⁺ diffusion coefficient within the QSPIP–TMC membrane is larger than that within PIP–TMC, suggesting that QSPIP–TMC has a slightly superior lithium-ion extraction capacity. These theoretical findings were highly consistent with the experimental observations. This work offers a solid theoretical foundation for designing new, highly efficient lithium–magnesium separation nanofiltration membranes.

In this study, a hybrid molybdenum disulfide anchored polythiophene (MoS₂@PTh) heterojunction photocatalyst has been synthesized via an in-situ chemical oxidative polymerization method. The structural, morphological, and optical properties have been studied. The photocatalytic activity of MoS₂@PTh was systematically evaluated for the degradation of different organic pollutants, including Tetracycline (TC), Ciprofloxacin (CIP), Rhodamine B (RhB), and Brilliant Blue (BB), under visible-light irradiation. The synthesized MoS₂@PTh composite exhibited significantly enhanced photocatalytic performance for pharmaceutical pollutants achieving 90% degradation of TC and 88% of CIP within 240 min. The corresponding rate constants (0.00861 min⁻¹ for TC and 0.00640 min⁻¹ for CIP) were markedly higher than those of pristine MoS₂ and PTh. Additionally, the composite efficiently degraded organic dyes, achieving degradation of 95% for RhB and 91% for BB within 240 min. Kinetic analysis confirmed that the degradation followed pseudo-first-order kinetics (R² = 0.997). A direct Z-scheme charge transfer pathway was identified, where hydroxyl (˙OH) and superoxide (˙O₂⁻) radicals served as the primary reactive species, supported by the participation of photogenerated electrons and holes. Stability assessment demonstrated excellent durability and reusability of the MoS₂@PTh photocatalyst, retaining high degradation efficiency over four consecutive cycles.

Copper ions are essential for human health but excessive intake can cause severe health issues. Fluorescence detection of copper ions typically relies on small-molecule probes, which suffer from slow reaction kinetics and low sensitivity at low concentrations. In contrast, metal–organic framework (MOF)-based fluorescent probes offer rapid response time and structural tunability, but often have low fluorescence quantum yields. This study presents a novel detection strategy using a functionalized zirconium-based MOF with naphthalimide as the luminescent moiety. A post-synthetic modification (PSM) strategy was used to graft Schiff base recognition units onto the MOF surface, which undergo specific coordination hydrolysis with copper ions, triggering fluorescence quenching. The resulting probe achieves a high fluorescence quantum yield (Φ = 36.88%) and ultra-fast response (<5 s), with a low detection limit (LOD = 0.167 µM) and excellent selectivity. The probe's broad linear detection range was successfully applied to real water samples. X-ray photoelectron spectroscopy (XPS), Gaussian theory calculations, and UV-visible absorption spectroscopy confirmed that the fluorescence quenching is mainly due to suppression of intramolecular charge transfer (ICT). This modular approach can be adapted for the rapid, sensitive detection of various pollutants using MOF-based probes.

Herein, cyclohexylalkyl (methyl-ED1, propyl-ED2, isobutyl-ED3, and n-octyl-ED4) dimethoxysilanes are synthesized and used as external donors (EDs) in a Ziegler–Natta (ZN) catalyst for propylene polymerization. The role of hydrocarbon groups on the structure of alkoxysilane, as an external donor, is examined. In this study, the roles of size and nature of hydrocarbon groups (methyl, propyl, isobutyl, and n-octyl), which play an important role in regulating the activity of the ZN catalyst, are investigated. The experimental results suggest that the productivity of the ZN catalyst can be increased by replacing the less sterically hindered methyl group with propyl/isobutyl/n-octyl hydrocarbon groups. It is observed that the productivity of propylene polymerization is 6.5 kg g_cat⁻¹ for the commercial donor cyclohexylmethyldimethoxysilane ED1 (known as C-donor) and 7.0–8.0 kg g_cat⁻¹ in the case of ED2–ED4. Therefore, the sterically hindered hydrocarbon group present on the external donor molecule plays an important role in increasing the productivity of propylene polymerization compared with the C-donor (ED1). Density functional theory calculations are utilized to gain deeper insights into the structure and electronic behavior of external donors. During propylene polymerization, external donors are added in combination with triethylaluminum (TEAL), and the ED–TEAL interaction is examined to elucidate the correlation between donor structure and ZN catalyst performance. The structure–activity correlation is derived from the calculated binding energy between the external donor and TEAL, which regulates the productivity of polypropylene. The results of polymerization data and DFT studies reveal that as the binding energy in the TEAL-ED complexes decreases, the productivity of the ZN catalyst increases, and alkoxysilanes with bulkier groups enhance the catalyst activity, isotacticity and molecular weight of polypropylene compared with the methyl group present in the commercial external donor ED1.

Laser-induced graphene (LIG) has emerged as a highly promising electrode material for energy storage applications owing to its unique advantages. However, the experimental capacitance of pristine LIG electrodes remains significantly lower than their theoretical limit, primarily due to limited active sites and insufficient charge carrier density. To address this challenge, the incorporation of heteroatoms into the graphene lattice can generate additional charge carriers, improving the electrical conductivity and overall properties. This leads to a significant enhancement in the electrochemical performance of laser-induced graphene (LIG) composites. In this study, we report a simple yet efficient laser-direct writing approach for the fabrication of N, B, and S tri-doped LIG (NBS-LIG) composite electrodes. The NBS-LIG electrodes were prepared through repeated laser scribing on a pre-fabricated B-doped S-LIG film with the same laser parameters. This synergistic multi-heteroatom co-doping not only induces structural defects that serve as electrochemically active sites but also enhances ion diffusion kinetics and electron-transfer capability. The resulting NBS-LIG electrode exhibits an outstanding areal specific capacitance of 240 mF cm⁻² at the current density of 0.5 mA cm⁻². The areal specific capacitance of the NBS-LIG electrode is maintained at 79.2% of its original value, as the current density is increased 20-fold to 10 mA cm⁻². Furthermore, the fabricated symmetric supercapacitor (SC) based on NBS-LIG delivers a high C_A (29 mF cm⁻²) at 0.4 mA cm⁻² and a high areal energy density of 4.03 µWh cm⁻² at an areal power density of 200 µW cm⁻². This study establishes a completely novel method for N, B and S co-doped LIG, which introduces N, B and S atoms into LIG to enhance the performance of supercapacitors and offers different insights into the synthesis of multi-atom co-doped LIG.

An efficient hydrodehalogenation reaction was developed using RANEY® nickel as the catalyst. In aqueous media, a wide range of aryl halides (F, Cl, Br, and I) were efficiently reduced to the corresponding arenes with excellent yields using hydrogen gas as the reductant. Additionally, alkyl halides (F, Cl, Br, and I) can also undergo efficient dehalogenation. This method features a broad substrate scope, a ligand-free catalytic system, and excellent atom economy.

Two chemosensors derived from acenaphthene-imidazole namely, 4-(2-(7H-acenaphtho[1,2-d]imidazole-8-yl)-4-bromophenoxy)butyl acetate (1) and 4-(1-(7H-acenaphtho[1,2-d]imidazole-8-yl)naphthalen-2-yloxy)butyl acetate (2) were synthesized for the purpose of detecting tin (Sn²⁺) and copper (Cu²⁺) ions. The chemosensors were comprehensively characterized using various spectroscopic techniques, including FT-IR, ¹H NMR, ¹³C NMR, mass spectrometry and single crystal X-ray diffraction analysis. Upon exposure to Sn²⁺ and Cu²⁺ ions in acetonitrile (ACN) solutions, chemosensors 1 and 2 exhibited selective increases in fluorescence intensity at 570 nm and 615 nm, respectively. This behavior was attributed to the chelation-enhanced fluorescence (CHEF) mechanism. The binding constants for the formation of the 1-Sn²⁺ and 2-Cu²⁺ complexes were determined using the modified Benesi–Hildebrand equation to be approximately 1.6 × 10⁴ M⁻¹ and 3.3 × 10⁴ M⁻¹, respectively. The results indicated that the sensors exhibited specific coordination with Sn²⁺ and Cu²⁺ ions. The detection limits for Sn²⁺ and Cu²⁺ ions using sensors 1 and 2 were calculated to be 1.2 × 10⁻⁹ M and 2.1 × 10⁻⁹ M, respectively. Additionally, the sensors were shown to be suitable for live cell imaging, with minimal cytotoxicity, highlighting their potential for cellular detection of Sn²⁺/Cu²⁺ ions.

Hydrogen fluoride (HF), a highly corrosive and toxic industrial emission, poses severe environmental and health risks, necessitating the development of efficient solid adsorbents for its capture. In this study, a series of cross-linked 4-vinylpyridine (4-VP)/divinylbenzene (DVB) porous resins were synthesized via suspension polymerization, and their HF adsorption properties were systematically evaluated. By tuning the 4-VP/DVB ratio, the pore-forming agent dosage, and the polymerization temperature, the resins' surface area, pore structure, and nitrogen content were effectively controlled. Saturation adsorption experiments revealed that nitrogen content plays a dominant role in HF uptake, whereas the contribution of specific surface area is comparatively minor. The optimized resin, WPD-25-1-0.1, achieved a high saturated adsorption capacity of 853 mg g⁻¹. Isotherm fitting demonstrated that HF adsorption follows the Freundlich model and is exothermic with heterogeneous surface characteristics. Thermodynamic analysis confirmed a strong synergistic adsorption mechanism, where pyridine nitrogen sites act as chemisorption centers and subsequently induce the formation of (HF)_n hydrogen-bonded clusters. The resin also demonstrates excellent regenerability, maintaining over 97% capacity retention after five adsorption–desorption cycles using only N₂ purging at 373 K. These results highlight the strong potential of 4-VP-based porous resins for industrial HF emission control and resource recovery.

Correction for ‘Revised efficient and reproducible synthesis of an Fmoc-protected Tn antigen’ by Peihan Xu et al., New J. Chem., 2025, 49, 19418–19425, https://doi.org/10.1039/D5NJ02399H.