Applied Organometallic Chemistry最新文献

The unique postsynthetic functionalization characteristic of metal–organic frameworks (MOF), especially those that possess a free -NH₂ group, encourages researchers to design nanocatalysts based on MOF with crystalline architecture. The present work reports a new nanocatalyst of UiO-66-NH-Glu-Mla@Pd, focusing on its design, synthesis, functionalization, and application in the Suzuki coupling reaction. UiO-66-NH₂ MOF was successfully synthesized via a solvothermal method and then functionalized with organic reagents of glutaraldehyde (Glu) and melamine (Mla) using the cocondensation and postsynthesis grafting strategies. Finally, the UiO-66-NH-Glu-Mla was decorated by palladium nanoparticles to generate UiO-66-NH-Glu-Mla@Pd. These modifications turn a low-active MOF into an ideal nanocatalyst with high catalytic activity in the Suzuki reaction. The results showed that the efficiency and durability of structure UiO-66-NH-Glu-Mla@Pd was still high after at least six consecutive uses.

In this work, a new heterogeneous cobalt and molybdenum hybrid-substituted polyoxometate was stabilized on mesoporous CMK-3 (PMo11Co@CMK-3) as a durable, effectual, recyclable, environment-friendly, and chemoselective nanocatalyst. PMo₁₁Co@CMK-3 catalyst was identified by various techniques such as BET, SEM, EDS, and FT-IR. Sulfoxides and disulfides were formed using PMo₁₁Co@CMK-3 through selective sulfides oxidation and oxidative coupling of thiols, respectively. The proposed method is an effective method, and the mentioned reactions are performed in a short time with very high efficiency. In order to produce sulfoxides and disulfides, hydrogen peroxide (H₂O₂) was selected as an environmentally friendly, safe, attainable, and inexpensive oxidant, with only water as a byproduct. This catalyst shows the heterogeneous and insolubility nature, notable chemoselectivity, good durability, and reusability in the oxidation of sulfides and oxidative coupling of thiols. In addition, sulfoxides and disulfides were synthesized under solvent-free conditions, which is an ideal condition for environmental health and economic savings. All sulfoxide and disulfide products were obtained with high yields within short reaction times.

Among the catalyst design strategies for α-diimine nickel systems, the C₂-symmetric strategy is an effective and widely used approach. To investigate the steric effect of the N-aryl substitutes on the isomerization behavior of C₂-symmetric catalysts and the properties of ethylene polymerization, a series of α-diimine nickel complexes were constructed by introducing phenyl and alkyl groups on the N-aryl ortho- and para-positions. From 40°C to 80°C, Ni1 ~ Ni5 exhibited highly ethylene polymerization activity (10⁷ g mol⁻¹ h⁻¹), yielding broadly distributed or bimodal polyethylene dominated by high molecular weight component. This is attributed to the rotation of the N-aryl bond resulting in the presence of both anti and syn isomers. Increasing the temperature or decreasing the size of the ortho-alkyl substitutes results in a faster conversion rate between the syn and anti isomers. It is believed that at higher temperatures or with larger N-aryl ortho-alkyl groups, the catalyst tends to exist in a more stable anti conformation. As a result, the bimodal polyethylene products are dominated by high molecular weight component in adjustable proportions and exhibit good mechanical and processing properties, showing great prospects for the application of solar cell package films.

The recent study evaluated the protective effect of the Tribulus platypterus green-synthesized silver nanoparticles against gentamicin-induced nephrotoxicity. The silver nanoparticles were characterized using XRD, UV-Vis, FT-IR, and FE-SEM. The nanoparticles exhibited a spherical morphology with an average diameter of 48 nm. Both traditional and innovative kidney injury indicators were employed to evaluate the nephroprotective effects of nanoparticles in a rat model. Administration of gentamicin resulted in a significant reduction (p ≤ 0.01) in Hb concentration, PCV, and RBC count. Conversely, the levels of creatinine, erythropoietin, serum iron, and urea increased significantly (p ≤ 0.01) in the gentamicin-treated group. The leucogram indicated the presence of leukocytosis, granulocytosis, and thrombocytopenia. Silver nanoparticles enhanced the parameters related to iron, leukogram, thrombocytes, erythropoietin, and erythrogram. In animals administered AgNPs, there was a significant decrease in the concentrations of creatinine, urea, AST, ALT, GGT, and ALP, whereas total protein and albumin levels showed a significant increase. Furthermore, AgNPs notably increased the levels of IL5, IL10, TGFβ, IL3, and IL4, while simultaneously reducing the levels of TNFα, IL6, IL12, IL18, and IL1. These results suggest that AgNPs could serve as a valuable nephroprotective agent derived from a biological source, potentially making them a suitable therapeutic supplement for conditions related to blood disorders.

A two-dimensional (2D) zinc(II) coordination polymer CP-1, [Zn(im₂bod)(bdc)]_n (im₂bod = 4,6-bis(imidazol-1-yl)-2,1,3-benzoxadiazole, bdc²⁻ = 1,4-benzenedicarboxylate), was synthesized and fully characterized. CP-1 crystallizes in the monoclinic crystal system, space group P2₁/n. Zn²⁺ ions adopt a four-coordinated distorted tetrahedral geometry. The structure of CP-1 comprises a two-dimensional layer consisting Zn²⁺ cations connected by im₂bod and bdc²⁻ ligands. The adjutant layers participate in π-π stacking interactions via the benzene and 2,1,3-benzoxadiazole rings. CP-1 demonstrated a blue emission with the maximum at 490 nm and a photoluminescence quantum yield 24%. Luminescent sensing properties of CP-1 in aqueous suspension toward metal cations were evaluated, and selective emission quenching response was observed toward Ga³⁺ cations with the limit of detection 10 μM.

Xanthenes are widely used in pharmacology, and other essential fields, making them a global derivative. An endeavor strategy for one-pot synthesis of 14-aryl-14-H-dibenzo[a,j]xanthene derivatives has been contributed through a reaction between various aldehydes and 2-naphthol in the presence of NiCuFe₂O₄ immobilized on carbon mesoporous (Ni/Cu/Fe₃O₄@MPCS) as a recoverable reactive catalyst. This mesoporous nanocomposite was used as a catalyst in this reaction to provide a quicker and easier process with energy in the readily available, biodegradable and non-toxic ethanol solvent. This catalyst provides a promising pathway to synthesize 14-aryl-14-H-dibenzo[a,j]xanthene, allowing for its recyclability without any noticeable decline in catalytic performance. Characterization of the prepared catalyst was conducted utilizing different methods, counting FT-IR, XRD, FE-SEM, EDS, BET, TGA, VSM, and Elemental mapping techniques. The results recommend that this novel catalyst possesses the potential to be a profitable tool for the improvement of modern engineered approaches for a broad range of applications.

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.