Applied Organometallic Chemistry最新文献

Formation of a tridentate mono-basic hydrazone-quinoxalyl ligand was done through condensation of quinoxalyl-2-carbohydrazide with 2-hydroxy-1-naphthaldehyde (H₂dip). The coordination capability of H₂dip with Ni (II) and V (IV) ions was examined at molar ratios of 1:1 leading to the synthesis of two distinct complexes, Ni(dip) and VO(dip), respectively. The chemical structure was validated by many spectroscopic techniques. The characterization included carbon, hydrogen, and nitrogen elemental analyses and assessments of magnetic properties and conductivity behavior. The inhibited effects of H₂dip (organic molecules) and its Ni (II) and V (IV) chelating agents on the constrained proliferation of three specific bacterial/fungal types, beside three established human cancer cell lines, have been evaluated in relation to the structural impact of Ni(dip) and VO(dip) compared with their free ligand (H₂dip). The research aimed to determine the nature influence of Ni (II) and V (IV) ions and the structure of their metal chelates on the binding affinity of H₂dip, Ni(dip), and VO(dip) for ct-DNA, that is, calf thymus DNA, depending on the viscometric/spectrophotometric alterations in characters. Furthermore, the assessment of binding constants (13.12, 15.19, and 14.88 × 10⁷ mol⁻¹ dm³), Gibbs free energy (−40.21, −44.51, and −45.01 kJ mol⁻¹), and chromism modes for H₂dip, Ni(dip), and VO(dip), respectively, was used to examine the interaction mechanisms of Ni(dip) and VO(dip), attributing the increased binding affinity to ct-DNA in comparison with H₂dip. The antioxidant potential was examined for H₂dip, Ni(dip), and VO(dip) within SOD (superoxide dismutase) and DPPH (2,2-diphenyl-1-picrylhydrazyl) assays, reporting respectable antioxidant reactivity. Ni(dip) and VO(dip) chelating catalysts represented superior catalytic oxidative activity for 1,2-cyclooctene (unsaturated hydrocarbons, CyO) using hydrogen peroxide in a homogenous manner. At 80°C, the yield percentage of selective epoxy-cyclooctane (CyOO) was 90% after 3 h and 93% after 3 h in acetonitrile (the best solvent) using Ni(dip) and VO(dip), respectively. The disparity in optimum actions for these catalysts pertained to the differences in their electronegativity and Lewis's acidity, with a suggested mechanistic pathway.

Several unique transition metal chelates of ESSA = sodium;4-[(3-ethoxy-2-hydroxy-benzylidene)-amino]-benzenesulfonate and its Cu(II), Fe(III), VO(II), and Pd(II) chelates were developed. Various spectral and physicochemical experiments were carried out to ascertain the geometrical form of the compounds under exploration. Spectrum info of the ESSA imine azomethine ligand and its metal compounds was employed for clarification of the alterations to structure triggered by complex formation. The formation of complexes by deploying continuous variation and molar ratio was explored, and the findings coincided with those observed in solid compounds, with a molar ratio of (M:L) being (1:2) for all metal complexes, except for Pd(II) is (1:1) metal-to-ligand ratio. Electronic spectra and magnetic moments can be applied to derive data concerning geometric formations. The activation thermodynamic variables related to the thermal breakdown of ESSA complexes were identified by using the Coats–Redfern approach. The ESSA imine ligand coordinates with Cu(II) and Pd(II) through square planner geometry, Fe(III) into octahedral geometry, and VO(II) in square pyramidal geometry, based on the correlation of all physicochemical techniques used in the inquiry and DFT calculation. The novel compounds were tested for DNA binding using spectroscopy, viscosity, and gel electrophoresis. Intercalation or replacement binding modes were hypothesized for their interaction with CT-DNA. Molecular docking studies were conducted to analyze the protein-generated compounds' binding and affinity. The antibacterial, anticancer, and antioxidant properties of ESSA ligand and its complexes were evaluated in vitro. ESSAPd complex excelled over the free ligand ineffective therapy.

In this study, a novel aminodicarboxylic acid, 4,4′-(azanediylbis(methylene))dibenzoic acid (H₂amda), was utilized as a versatile building block to synthesize a new series of coordination polymers (CPs) via hydrothermal methods. These polymers were represented by the following formulas [Ni(Hamda)₂(μ-4,4′-bipy)(H₂O)₂]_n·2nH₂O (1), [Co(Hamda)(μ-Hamda)(μ-dpey)_0.5]_n·nH₂O (2), [Co(Hamda)(μ-Hamda)(μ-dpea)_0.5]_n·nH₂O (3), [Zn(μ-amda)(phen)]_n·0.5nH₂amda·nH₂O (4), [M(μ-amda)(2,2′-bipy)]_n (M = Co (5), Ni (6)), and [M(μ₃-amda)(μ-bpb)]_n·0.5nbpb·nH₂O (M = Co (7), Mn (8)). All synthesized compounds (1–8) were thoroughly characterized using elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. The structural analysis revealed that compounds 1–6 exhibit one-dimensional (1D) metal–organic chains, whereas compounds 7 and 8 display two-dimensional (2D) metal–organic sheet structures. A topological classification of the underlying metal–organic networks was identified: 2C1 topology in compounds 1 and 4–6, (4,4)(0,2) topology in compounds 2 and 3, and a new topology in compounds 7 and 8. The catalytic performance of compounds 1–8 were evaluated through cyanosilylation reactions under mild conditions, optimizing diverse reaction parameters and exploring substrate scope. Among the compounds tested, compound 2 demonstrated the highest efficiency as a recyclable heterogeneous catalyst, achieving up to 98% product yield.

One 3D Zn-MOF, namely, {[Zn₂(L)(OH)(DMF)]}_n was selected based on the flexible ether oxygen carboxylic acid 3-(3,5-dicarboxylatobenzyloxy)benzoic acid (H₃L). Zn-MOF was able to specifically recognize the biomarker methylmalonic acid (MMA) and antibiotic tetracycline (TC) through fluorescence enhancement and ratio mechanism, with the detection limits (LOD) as low as 1.29 and 0.26 μM, respectively. It also has high selectivity and rapid response characteristics. In particular, the visual detection was significantly enhanced in the presence of Tb³⁺ through antenna effect. To explore the potential application, fluorescent test strips and mixed matrix membrane (MMM) were successfully prepared to realize visual detection. The recovery rates of MMA and TC in simulated urine and actual water systems were 95.3%–100.5% and 93.5%–94.7%, respectively, indicating that Zn-MOF provided the possibility for detecting biomarker and antibiotic in practical systems.

Exploring cost-effective and high-performance adsorbents plays a crucial role in the efficient utilization of agricultural waste and the remediation of heavy metal contamination in water bodies. This study focuses on preparing biomass carbon (BC) from banana pseudostems for the remediation of heavy metals in water. A systematic investigation was conducted to evaluate the effects of initial solution concentration, pH, reaction time, reaction temperature, and coexisting cations on the adsorption of Mn(II), Cd(II), Pb(II), andCu (II) by BC. The results showed that the adsorption capacity of BC for all four heavy metals reached its peak at pH 6. The adsorption process was primarily governed by monolayer chemisorption. Furthermore, the process is spontaneous, endothermic, and accompanied by an increase in entropy. In a multimetal system, BC demonstrated the strongest selectivity for Pb(II). Even in the presence of interfering ions, BC maintained a high adsorption capacity for heavy metals. Notably, after 5 cycles of use, BC retained a significant removal rate of 40%–60% for heavy metals, underscoring its recyclability and environmental friendliness. Characterization studies indicated that the adsorption of heavy metals by BC involves multiple mechanisms, including ion exchange, mineral precipitation, functional group complexation, and cation-π interactions. The dissolved organic matter (DOM) derived from biochar plays a pivotal role in the adsorption process. Furthermore, the preparation of BC is both straightforward and cost-effective, combining economic viability with practical applicability.

Four new VO(II), Cu(II), Ru(III), and Ag(I) chelates were created from the ligand, 2-(phenylglycyl)-N-(p-tolyl)hydrazine-1-carbothioamide(H₂L). The structures of the new compounds were investigated using analytical and spectroscopic techniques and supported by the theoretical DFT study. In addition, all compounds exhibited strong anticancer effects against liver (Hep-G2), breast (MCF-7), and colon (HCT-116) human cancer cell lines. VO(II) complex observed the greatest activity with IC₅₀ reached to 14, 19, and 20 μM against Hep-G2, MCF-7, and HCT-116 cell lines, respectively. Molecular docking confirmed the resulted anticancer results. Also, the compounds observed microbial growth inhibition against S. pyogenes and E. coli organisms. The transmission electron microscope (TEM) demonstrated that the pure ligand's particle size decreased when it formed complexes with various metals. The electrical examination of complexes involved measuring their conductivity and dielectric characteristics to explore their application in electrical devices.

This article, describe the synthesis of 4-ethynylaniline derived 1,2,3-bis-triazole (3) via Cu(I) catalyzed click reaction and various spectroscopic methods such as FT-IR, TGA, ¹H and ¹³C NMR, and mass spectrometry are used for characterization. The probe 3 exhibits high sensitivity and selectivity to Sn (II) in UV–visible spectroscopy, with a limit of detection of 27 μM and association constant 8.32 MM⁻¹, respectively. The synthetic sensor practical application was further explored by detecting Sn (II) in real sample analysis. The computational analysis using the DFT techniques shows the binding mechanism of sensor with Sn (II). Additionally, molecular docking investigation was conducted against cyclooxygenase-2 to shows the anti-inflammatory properties of the synthesized ligand having a good binding energy −10.26 Kcal mol⁻¹.

The chemical synthesis via utilizing carbon dioxide as an easily accessible, low-price, nonpoisonous, and versatile C1 elementary unit is a remarkably appealing but complex and challenging conversion from the point of industrial and academic aspects. The cycloaddition of carbon dioxide (CO₂) and epoxides (EPs) is an eco-friendly route in the fixation of CO₂ into useful cyclic carbonate (CY) products, which have been broadly operated regarding the industrial utility of polymeric and CYs. Magnetic nanocatalysts are vastly utilized in diverse organic reactions owing to their magnetic isolation and recoverability features. The usage of magnetite (Fe₃O₄) nanoparticles as solid support for the immobilization of a diversity of metals, bimetals, organocatalysts, and organoligands has shown massive development in benign organic conversions largely owing to their enormous surface area, low-cost nature, and ease of preparation. The significant benefits of magnetic nanocatalysts are superior yields, short-time reaction, moderate reaction conditions, recyclability, and easy workup. This current review highlights the applications of magnetite nanocatalysts in the chemical fixation of CO₂ into CYs. This research will be helpful and valuable to researchers due to the reaction of cycloaddition of CO₂ to EPs to make CY intermediates significantly employed for the synthesis of an extensive diversity of organic compound products.

The detection of samarium (Sm) and its isotopes/ions is gaining significant importance across various fields, including nuclear energy, materials science, environmental monitoring, and biomedicine. Accurate and sensitive detection methods are crucial for ensuring safety, quality control, and compliance with regulatory standards. Despite the growing need, existing detection strategies often face challenges such as being time-consuming, inaccurate, cumbersome, and expensive. Surprisingly, fluorometric sensing has been explored minimally for Sm detection. In this study, we introduce a novel approach for detecting Sm (III) ions using a fluorescent metal–organic framework (MOF), Cu-PTC, synthesized via a one-pot, green, room temperature method. This represents the first reported use of a fluorescent MOF for Sm (III) detection. The Cu-PTC MOF was synthesized using the potassium salt of perylene-3,4,9,10-tetracarboxylic acid and Cu (II) ions from Cu (OAc)₂. Structural analysis revealed the formation of a 3D network with well-defined pores. Photophysical characterization confirmed the absorption and emission properties of Cu-PTC. The MOF was successfully employed for the selective detection of Sm (III) ions, with a detection limit of 6.53 μM.

One-dimensional coordination polymer La-CP, {[La(H₂O)₂(HL_O) (L_O)]·H₂O}_n containing a new luminescent ligand 4,7-di(4-carboxypyrazol-1-yl)-2,1,3-benzoxadiazole (H₂L_O) was synthesized. Upon excitation at 400 nm, the compound shows a strong emission with the maximum at 550 nm with high photoluminescence quantum yield of 43%. La-CP demonstrates sensing properties toward aluminum and gallium cations, as well as dihydrogen phosphate and sulfate anions through the emission enhancement response. The limits of detection were 0.42, 0.70, 0.37, and 0.40 μM, respectively. La-CP is the first example of a sensor for sulfate anion among all types of coordination polymers. The uptake of the analytes under the sensing conditions was evaluated, and a strong absorption enhancement as a result of such uptake was proposed as a probable emission response mechanism.