Applied Organometallic Chemistry最新文献

Several physicochemical and analytical methods were employed to elucidate the structural analysis of some novel complexes derived from the {3,4-bis-[(3-ethoxy-2-hydroxy-benzylidene)-amino]-phenyl}-phenyl-methanone (ESAB ligand). Decomposition point determination, elemental analysis (CHN), spectroscopy (IR, NMR, and mass spectrometry), conductivity, magnetic susceptibility, UV–Vis spectrum study, and theoretical investigations were among these methods. With conductance values ranging from 7.5 to 15.12 Ω⁻¹ cm² mol⁻¹, molar conductance values showed that the Zn (II), Cu (II), and Ru (III) complexes are nonelectrolytes in fresh DMSO solutions, with the exception of the ESABRu complex, which is a monoelectrolyte. According to IR spectra, the ligand uses the (N & O) donor sites from the (C=N & C-O) groups in the ligand moiety to coordinate through the metal ions in a tetradentate form. A 1:1 (metal:ligand) molar ratio was proposed by Job's approach based on analytical data from solution complexation. According to the stability constant (K_f) values, the complexes' stability order was found to be ESABRu > ESABCu > ESABZn. The pH profile showed that the complexes under study are stable throughout a broad pH range, usually between pH = 4 and pH = 10. The complexes' geometric structures and ligand coordination capabilities were inferred with the use of magnetic and electronic spectrum studies. The DFT method uses quantum chemical simulations to evaluate the electronic structures of the ligand under investigation and its complexes. The unbound ligand's B3LYP level, B3LYP/6/311G* degree, and the complexes' B3LYP/6/311G**/LANL2DZ functional categories were employed in the computations of the density function concept (DFT). The findings revealed the consistency between the experimental and DFT computations. Natural bond orbital (NBO) analysis was used to investigate bond strength between molecules' charge exchange, hyperconjugative connections, and molecular equilibrium. By computing the hyperpolarizability (β) and molecular polarizability (α) parameters, the ensuing nonlinear optical properties were investigated, leading to a number of surprising optical properties for the produced compounds. The antipathogenic activity of the generated materials was experimentally verified against a subset of gram (+) and gram (−) bacteria as well as some fungi using the agar well diffusion method. Additionally, hepatic cellular carcinomas, cells from colon and breast cancer, were utilized to test the cytotoxic activity of the ESAB ligand and its metal chelates. Furthermore, the examined compounds' ability to suppress the DPPH radical was examined. Additionally, simulations of molecular docking were performed to ascertain how the produced compounds attached to the specific protein binding sites.

Aluminum nitride (ALN) finds extensive application across various fields, and further advancement is undergoing to explore efficiency of this compound in drug delivery. The significance of this research lies in its contribution to nano-based drug delivery systems for anticancer treatments. This study focuses on the preparation of ALN nanoparticle using a simple and cost-effective route in an NH₃ atmosphere and in the presence of hydrated aluminum chloride. The characterization techniques such as FT-IR, TEM, SEM, UV, XRD, XPS, and EDS are used to analyze the synthesized nanoparticles. Then, metformin is incorporated into the fabricated nanostructure to achieve a drug loading of ~67%, demonstrating effectiveness of the selected nanocarrier for encapsulating this important drug. The specific impact of pH and time duration on the release profile of metformin highlights the versatility and potential applicability of ALN delivery system. Moreover, the gradual release of drug under physiological conditions (pH 7.4) as well as the accelerated release at the lower pH of 5.1 within 48 h proofed the responsiveness of the nanostructure to varying environmental conditions. Finally, a density functional theory (DFT) calculation was carried out to investigate adsorption of metformin. These computational analyses validated again the potential of ALN as an effective sensor for detecting metformin in biological systems. The unique characteristics of this study involve introducing a pH-responsive nanocarrier to release drug selectively in response to pH of the environment, using a nanoparticle with sufficient stability that improves solubility of poorly soluble metformin. This bioavailable drug delivery system can reduce off-target effects and toxicity associated with conventional drug therapies.

With the continuous development of industry, the issue of industrial wastewater emissions is increasing. Adsorption, as an effective means possessing the features of no pollution, high efficiency, and easy operation, has become one of the effective methods to treat industrial wastewater. Fe₃O₄@polypyrrole@sulfamic acid (Fe₃O₄@PPy@SA) composite is successfully prepare by hydrothermal method, in situ polymerization, and modification. Its adsorption behaviors of the composite on MG, MB, CV, and RhB are investigated by UV–Vis, and the impacts of temperature, dye concentration, and the contact time between the composite and the dyes on the adsorption efficiency are researched. The adsorption kinetics and adsorption isotherms exhibit that the adsorption of these four dyes is more in accordance with pseudo-second-order kinetic model and Langmuir adsorption isotherm model, the diffusion behaviors are affected through the combined effect of intraparticle diffusion and Boyd membrane diffusion, and the thermodynamic studies display that all these adsorption behaviors are spontaneous heat absorption behaviors. The prepared Fe₃O₄@PPy@SA is an efficient adsorbent in the field of applications.

Ferrite magnetic materials have emerged as capable materials in engineering, research, and medicine because of their exclusive and fascinating properties obtained from a variety of synthesis techniques. These ferrites are significant in commercial products, research, and biomedical applications. Green synthesis methods for ferrite nanocomposites and nanoparticles are becoming increasingly popular due to their usefulness in a range of industries, engineering, environmental, and medicinal remediation. Ferrite nanoparticles and nanocomposites (MFe₂O₄, where M = Ni, Cu, Mg, Co, Zn, and Mn) have recently gained popularity due to their many uses in biological, environmental, and chemical interactions. This review covers the most recent investigations over the last few years on green-synthesized ferrite nanoparticles, ferrites containing nanocomposites, and more elements, with a focus on microorganism-mediated and plant-based synthesis processes. The surface features of ferrite nanoparticles synthesized from green materials are discussed, as is their potential for sensors, energy, water treatment, antibacterial activity, biological, and heavy metal removal applications. This article presents an inclusive overview of green-synthesized ferrites, including the most recent research advances and findings. To fully realize the promise of nanoferrites in several fields, a thorough understanding of green manufacturing, properties, and applications is essential. Green-synthesized ferrites are chosen due to their potential for improved control over particle size and shape, lower cost, decreased toxicity, and environmental friendliness, all of which preserve magnetic properties that are better than those of conventionally synthesized ferrites, making them a more sustainable choice for a range of applications.

The selective detection of G-quadruplex DNA has the potential to reveal its biological function and provide important information for cancer diagnosis and treatment. Herein, a ruthenium(II) complex containing a two-armed benzimidazole ligand (bimbpy) (RC1) has been developed as a selective luminescence probe toward G4 DNA. RC1 exhibited distinguishable luminescence response to G4 DNA, such as HTDNA, c-MYC, and 22AG. Especially, in the presence of HTDNA, the luminescence intensity of RC1 increased to 6.1-fold. The limit of detection is 30 nM for HTDNA. However, it showed a small change in luminescence intensity against doubled-strand and single-strand DNA. The DNA binding experimental results indicated that RC1 effectively stabilized G4 DNA through hydrogen bonds and π-π stacking. The selectivity of RC1 to G4 DNA might be due to the increase in the rigidity of the two-armed benzimidazole ligand after binding to G4 DNA. Therefore, the design of ruthenium(II) complexes with a two-armed ligand will be an effective method to obtain Ru(II)-based G-quadruplex luminescent probes by adjusting the degree of rigidity of the two arms.

In recent years, some Cu-based complexes and nanomaterials that can better adapt to tumour microenvironments and produce better chemodynamic therapeutic effects have been synthesised. Ferrocene and its derivatives have garnered increasing attention as a therapeutic option in chemodynamic therapy owing to their excellent catalytic activity. Herein, two ferrocene-modified Cu(I) complexes, Fc-AD-Cu and Fc-IH-Cu, were synthesised with atomically precise structures. Both exhibit good Fenton/Fenton-like activity, inducing the generation of reactive oxygen species in Hep-G2 cells and improving chemodynamic therapeutic efficiency.

Enzyme mimics attract wide attentions as detection sensors. However, the widespread application is limited by low efficiency and high cost. Herein, two novel enzyme mimics 1 and 2 were developed with peroxidase-like activities. The chain-like structure of 1 exhibited better stability, energy transformation efficiency, and catalytic property than 2. Both of them could generate •OH radicals to oxide chromogenic agents, realizing the colorimetric detection of H₂O₂. Additionally, under the synergy of glucose oxidase, a cascade strategy for detection of glucose was constructed. This method exhibited excellent selectivity, anti-interference, and storage performance, as well as a wide linear range (1–60 μM) at pH = 7.4, with the low detection limits of 0.095 and 0.061 μM for 1 and 2, respectively. Furthermore, the strategy was applied for detecting glucose in apple fruit samples. This work overcomes the shortcomings of current enzyme mimics and paves the way for bioanalysis and agricultural applications.

The catalytic conversion of carbon dioxide (CO₂) into valuable energy under light sources is one of the effective ways to achieve carbon cycle. The reported nonprecious metal complex catalysts still show the shortcomings of low catalytic activity and low selectivity in visible-light–driven CO₂ reduction, especially in aqueous systems. Herein, we report three dinuclear mixed-valence Co (II)/Co (III) complexes 1–3 bearing macrocyclic ligands that exhibit high activity and selectivity for visible-light–driven photocatalytic CO₂ reduction in an aqueous system. Moreover, the TON_CO and CO selectivity for macrocyclic dinuclear mixed-valence complex 3 reach as high as 4100 and 96%, respectively, which is about 4.9 times higher than that of mononuclear Co (II) complex 4. Through electrochemical and DFT calculations, we found that the increase in photocatalytic activity of 3 is due to the synergistic effect between the two metal centers, in which one Co site stabilizes the *COOH intermediate and reduces the energy barrier of the rate-determining step, thereby increasing the catalytic activity.

The development of efficient adsorbents with high selectivity is essential for mitigating environmental pollution. This study introduces a novel adsorbent comprising a metal–organic framework (i.e., MIL-101(Fe)-NH₂) and a covalent organic framework (COF) enriched with carboxyl groups, which is designated MIL-101(Fe)-NH₂/COF-COOH. The adsorbent is synthesized through a Schiff base reaction followed by carboxymethylation and is subsequently employed for Pb (II) adsorption. The structure of MIL-101(Fe)-NH₂/COF-COOH is confirmed using various characterization techniques, including Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and Brunauer, Emmett, and Teller surface area analysis. The adsorption capacity (q_e) value of MIL-101(Fe)-NH₂/COF-COOH is estimated through batch adsorption experiments^. The effects of several factors, including pH, adsorbent dosage, contact time, Pb (II) concentration, solution ionic strength, and temperature, on the adsorption process are systematically assessed. MIL-101(Fe)-NH₂/COF-COOH achieves the highest adsorption of 184 mg/g at pH 6. The adsorption kinetics, isotherms, and thermodynamics indicate that the adsorption process occur through a spontaneous monolayer chemical process. Moreover, MIL-101(Fe)-NH₂/COF-COOH displays remarkable anti-interference capability, and its q_e decreases by only 10% after 10 cycles. Based on the characterization results, the Pb (II) adsorption mechanism is determined to be primarily electrostatic and chelation interactions between Pb (II) and O- and N-containing functional groups. Thus, this highly efficient and recyclable adsorbent exhibits considerable potential for removing Pb (II) from aquatic ecosystems.

The extensive connectivity between organic ligands and inorganic metal ions enables precise design and physicochemical modification of metal–organic frameworks (MOFs) for various applications. The metal-based counterparts, nanoscale metal–organic frameworks (nMOFs), are among advanced classes of hybrid nanoparticles, with the fundamental characteristics of pristine MOFs and nanoscale dimensions that enhance their potential for clinical applications. The distinct structure, pore size tunability, easy surface functionalization, large surface area, and porosity enable loading of various therapeutic and imaging agents. In addition, nMOFs demonstrate biocompatibility, multifunctionality, and the relatively labile metal–ligand bonds impart biodegradability. Owing to such excellent properties, nMOFs exhibits biomedically relevant applications as therapeutic cargoes, bioimaging, biosensing and biocatalysts agents. This article elucidates the advantages of nMOFs over other existing nanocarriers (e.g., organic and inorganic) and focuses on new insights of synthesis, design strategies with surface modification techniques for hybrid material development. The biomedical applications with futuristic approach are discussed with relevant examples in detail to inspire further exploration of nMOFs as biomedically relevant agents with great market potential in biomedical sciences.