Applied Organometallic Chemistry最新文献

The growing global demand for water and persistent shortages have underscored the importance of wastewater treatment from industrial and urban sources. Among various approaches, the use of adsorbent materials, particularly metal–organic frameworks (MOFs), has gained significant attention over the past decade due to their exceptional adsorption properties. This study presents a rapid, water-based synthesis method for MIL-53(Al)-(NH₂) and its surface modification using polyaniline (PANI). The modified MOFs, MIL-53(Al)-(NH₂)@PANI, were utilized for the removal and photocatalytic degradation of tetracycline from aqueous solutions. Optimal operational conditions were determined to include an adsorbent dosage of 0.12 g/L, an initial tetracycline concentration of 30 mg/L, a reaction time of 30 min, and a solution pH of 2.5. Kinetic analyses revealed that the adsorption process conforms to the Pseudo-second-order kinetic model, with the surface modification by PANI significantly enhancing the adsorption efficiency. The proposed mechanism for photocatalytic degradation involves the generation of reactive radical species, including h⁺, ˙OH, and ˙O₂⁻, under sunlight irradiation, which synergistically improves the removal efficiency. This study highlights the potential of MIL-53(Al)-(NH₂)@PANI as an effective adsorbent and photocatalyst for the treatment of antibiotic-contaminated water, offering a sustainable solution to water pollution challenges.

A nitrogen-doped carbon-supported Fe-Fe₃C-Fe₃O₄ composite (Fe-Fe₃C-Fe₃O₄@CN) has been synthesized through a one-step pyrolysis of an iron-based complex (Fe@tremella-est), in alignment with the principles of surface organometallic chemistry (SOMC). The Fe@tremella-est complex was synthesized through a straightforward chelation process using N-containing alanine-modified tremella (tremella-est) as the raw material. This approach enhances the resulting catalyst by providing a large specific surface area, high dispersity, and an increased number of Fe-N species. These distinctive advantages confer upon Fe-Fe₃C-Fe₃O₄@CN a higher catalytic efficiency compared with traditional catalysts (Fe-Fe₃C@CN and Fe-Fe₃C@CN-550), along with enhanced stability during recycling experiments. This SOMC strategy may serve as a new framework for the synthesis of biomass-derived nanocatalysts for various catalytic reactions.

The exploration of diorganotin(IV) compounds as potential inhibitors of cancer cell growth is gaining attention. Here, we have emphasized the potential of diorganotin derivatives as promising candidates for anticancer therapy. Thus, a series of Schiff base core tin(IV) complexes, including dimethyl, diethyl, dibutyl, and diphenyl derivatives, were synthesized and examined utilizing mass spectrometry, FT-IR, NMR, and single crystal XRD. The acquired spectroscopy results disclosed that hydrazone ligands connected to tin atom in a tridentate fashion via phenolic O, imine N, and enolic O donor atoms and formed a pentacoordinated environment, which was further validated by X-ray crystallographic diffraction study of compound 9. Single crystal X-ray examination of compound 9 demonstrated that the Sn atom is arranged in a distorted five-coordinated square pyramidal geometry. The antimicrobial potential of all prepared compounds was examined against four bacterial and two fungal strains, and complexes 7, 11, and 15 having MIC values between 0.0043 and 0.0050 μmol/mL exhibit better effectiveness against Escherichia coli and Candida albicans. Further, synthesized compounds were examined for in vitro anticancer efficacy against MCF-7 and A549 cell lines and demonstrated substantial activity with standard Doxorubicin. Compounds 3 and 5, being the most active, were subsequently evaluated against normal cell line HEK 293T.

Herein, a novel CuS-anchored 2D-Ti₃C₂T_x composite material was synthesized by a one-pot hydrothermal method. This CuS/Ti₃C₂T_x hybrid was used to prepare a novel label-free electrochemical immunosensor for EpCAM antigen detection. The immunosensor has been fabricated by electrophoretic deposition of CuS/Ti₃C₂T_x hybrid onto the ITO electrode followed by the immobilization of anti-EpCAM. The electrochemical biosensing studies of this fabricated immunosensor, BSA/anti-EpCAM/CuS/Ti₃C₂T_x@ITO demonstrated a wide linear range (0.01 fg/mL to 100 ng/mL) and low LOD (0.0057 fg/mL), together with high sensitivity (461.85 μA fg⁻¹ mL cm⁻²) for EpCAM antigen detection. The clinical validation of the proposed immunosensor was conducted with serum samples. Moreover, the immunosensor was found to be reproducible, specific, selective, and stable over a long period of 42 days.

Photocatalytic degradation of pollutants under visible light is a propitious approach to address the issue of environmental pollution. The photocatalytic degradation by heterogeneous Cu₂O-based photocatalysts has been widely concerned. Herein, a ternary Cu₂O/UiO-66-NH₂@GO nanocomposite was successfully prepared by a two-step hydrothermal technique for the photodegradation of organic pollutants in water. The successful fabrication of a ternary heterostructure composed of Cu₂O, UiO-66-NH₂, and GO was confirmed by SEM, TEM, XRD, XPS, Raman, and FTIR characterization. The ternary heterostructure photocatalyst effectively improved the photoresponse and porous characteristics of Cu₂O. Under visible light, 98.6% of 4-nitrophenol (4-NP) and 99.2% of rhodamine B (RhB) were degraded by Cu₂O/UiO-66-NH₂@GO photocatalyst with 3 and 15 min, respectively. The K_app values of 4-NP and RhB photocatalytic degradation were calculated as 1.450 and 0.428 min⁻¹, respectively. The stability tests showed that the photocatalyst was reasonably excellent after four cycles. The enhanced efficiency benefited from the strengthened visible light harvesting, reduced recombination of photogenerated electron–hole pairs, and enhanced migration efficiency of charge carriers. The effects of scavengers confirmed that hole trapping species played a crucial role during the photodegradation process. The proposed study provides inspiration for designing a simple multiheterostructure visible light–driven photocatalyst with promising environmental remediation applications.

Because of the toxicity of traditional mercury catalysts, more economical and efficient nonprecious metal catalysts have attracted considerable concern in acetylene hydrochlorination reaction. Here, a series of copper-based catalysts coordinated with P-containing ligands were prepared by the incipient wetness impregnation method. The 12.5Cu-2L_7/1/AC catalyst (2L = tris(3-methylpheny) phosphine) achieved the initial acetylene conversion of 87.13%, which was 47.68% higher than that of 12.5Cu/AC under the acetylene gas hourly space velocity of 180 h⁻¹. The characterization results displayed that the employment of tris(3-methylpheny) phosphine not only constructed highly dispersed and hypervalent Cu-P/Cu-O-P active species but also improved the adsorption capacity of the catalyst to reactants and the ability of anticoke deposition, thereby improving the catalytic activity and stability of Cu-based catalysts.

Zinc, an important metal element in the human body, fulfills multiple biological roles, such as influence on cell division and differentiation. In this paper, a Maca polysaccharide-zinc (MPS-Zn) complex was prepared by water extraction and alcohol precipitation process. A granular MPS-Zn complex with 0.2360 μg/mg Zn was obtained at 60°C and pH = 3.0 for 60 min. The antioxidant activities of this MPS-Zn complex were evaluated by the free radical scavenging activity toward DPPH and ABTS. The rate of ABTS free radical scavenging of 4.0 mg/mL MPS-Zn complex is equal to that of control group (vitamin C). The abilities of this complex against three cancer cell lines including breast cancer MCF-7, colon cancer SW480, and liver cancer SMMC-7721 were used to evaluate its antiproliferative activity by MTS assay. The results demonstrate that this complex has an inhibitory effect on the above cancer cell lines. Especially, the inhibitory effect of it on colon cancer SW480 is more effective than that of cisplatin. The toxicity of this complex on human normal pulmonary epithelial cell BEAS-2B is lower than that of taxol and cisplatin. This complex has the potential use as the zinc-containing nutritional food and/or anticancer drug.

A convenient strategy to access cyclometalated platinum (II) N-heterocyclic carbene (NHC) complexes is reported herein, synthesized by treating a Pt (NHC)I₂Py precursor with Schiff-base (N^O) ligands in the presence of K₂CO₃ base under mild reaction conditions. These cyclometalated Pt(II) NHC complexes were fully characterized by ¹H and ¹³C NMR, mass spectrometry, and infrared spectroscopies, and the solid-state molecular structures of complexes 1, 2b, and 3b were unambiguously determined by single-crystal X-ray diffraction methods. To form these complexes, C-H bond activation and C-N cleavage and cycloplatination had to occur. In a bid to understand this transformation, density functional theory was carried out to rationalize the cycloplatination mechanism unveiling an intriguing anion assisted C-H activation and proton transfer process.

N-Arylated heterocyclic molecules are extensively found as key components in numerous pharmaceutical and agrochemical compounds. Herein, inexpensive 1,10-phenanthroline-assisted copper-catalyzed sustainable greener methodology has been developed for N-arylation of indoles and pyrrole under commercial base and additive-free conditions. Waste biomass–derived water extract of banana peel ash (WEB) has been used as safe reaction medium and base instead of hazardous solvents, and hence, the current green protocol has achieved an environmentally benign profile. Reaction of pyrrole with aryl iodides and electronically diverse indoles with aryl iodides/aryl bromides in the presence of CuI as catalyst, 1,10-phenanthroline as ligand, and WEB as a base and solvent at 100°C has furnished N-arylated product within 12 h. Reaction of indoles with aryl iodides furnished up to 93% yields while aryl bromides resulted in up to 54% yield of the desired product. The utilization of waste biomass derivative for organic transformation reaction is the key step of this protocol, which is in consistence with the goals of green chemistry.

In this research, as a new heterogenous nanocomposite, P-doped g-C₃N₄/Cu₂O was successfully synthesized by simultaneous reduction of copper salts and the resultant precipitation. The phosphor was doped onto the graphitic carbon nitrite by the calcination method. The various spectroscopic and imaging methods (XPS, X-ray diffraction [XRD], FTIR, Pl, BET, DRS, Map Scanning, EDS (EDAX), TEM, FESEM, and EIS) were devised to characterize the structural properties, morphology, and optical and photocatalytic activities of the synthesized nanocomposite. The synthesized nanocomposite was then used as photocatalysts in the reduction of nitroaromatic compounds to the corresponding amino aromatic species, with the results being highly promising. Indeed, the conversion of nitrobenzene to aniline was 100% accomplished within 30 min. In these reactions, hydrazine compounds were used as hydrogen suppliers. The proposed photocatalyst exhibits great recyclability and reusability so that no significant change in the catalytic activity of the nanocomposite and the resultant conversion efficiency was observed after six rounds of reuse.