Applied Organometallic Chemistry最新文献

Some novel biologically active tetraaza-macrocyclic complexes of Fe (III) and Cr (III) were synthesized by non-template method. In this methodology, first macrocyclic ligand was synthesized by condensation reaction between triethylenetetramine and dimedone which was further reacted with trivalent Fe and Cr ions to synthesize the macrocyclic complexes having general formula [M(C₁₄H₂₆N₄)(X)](X)₂ where X represents Cl⁻, NO₃⁻, CH₃COO⁻. Various physiochemical studies suggested the square pyramidal geometry around the metal ion of all complexes. With the aid of PXRD technique, it was found that some of the complexes possessed monoclinic crystal system while other complexes showed to have orthorhombic crystal system. The DFT study was also carried out to examine the various quantum descriptors of ligand and its complexes. Moreover, newly synthesized macrocyclic ligand and its complexes with Fe and Cr ions were tested against fungal strain as well various bacterial strains. The results of antibacterial study showed that all complexes exhibited remarkable ability to inhibit the growth of microbes as compared to ligand. All complexes were found to have drug-likeness behavior as indicated by in-silico studies. Furthermore, these complexes were also tested for their antioxidant activity and it was observed that complexes showed better antioxidant activity as compared to ligand and standard solution of ascorbic acid.

Three kinds of one-dimensional nickel-based coordination polymers (1D-S-Ni, 1D-D-Ni, and 1D-M-Ni) with different coordination environments and topological structures were synthesized and evacuated as heterogeneous catalysts for liquid phase slurry reaction of ethylene dimerization. Their crystal structures, morphology, chemical groups, and thermal properties were characterized by PXRD, SEM, FT-IR, TGA, ICP-AES, and EA, respectively. The catalytic performance of these catalysts was examined under various reaction conditions, including the amount of cocatalyst, reaction temperature, and reaction pressure. These catalysts showed high catalytic activity up to 10⁵–10⁶ g/(molNi·h) and high selectivity of butene (C4) over 78% at room temperature and 10 atm pressure. Especially the catalytic activity of 1D-D-Ni was up to 17.1 × 10⁵ g/(molNi·h), exceeding that of most Ni-based heterogeneous catalysts and reaching the level of nickel-based homogeneous catalysts. The stability and cyclic performance of 1D-D-Ni was also assessed. It was observed that the catalyst did not undergo decomposition during the reaction and maintained a high activity level of 12.0 × 10⁵ g/(molNi·h) even after three cycles. 1D-D-Ni has SBU similar to homogeneous nickel-based complex catalyst for ethylene dimerization, indicating that reasonable design of metal nodes is an effective way to synthesize heterogeneous ethylene dimerization catalysts with high catalytic performance.

The present work demonstrates the synthesis of ester and ferrocene groups containing new terpyridine-based ligands (FRL and RL) and their selected meal complexes FR-Fe, FR-Ru, RL-Fe, and RL-Ru. Investigations on the influence of the ester and ferrocene groups on binding to DNA/BSA and anticancer activity were carried out. All these products were structurally characterized by using spectroscopic and analytical techniques. Notably, the molecular structures of both the ligands and the ester-based Fe(III) complex were confirmed by single-crystal X-ray diffraction analysis. Additionally, theoretical calculations were employed to further establish the structures of the synthesized ligands and their metal complexes, which were subsequently utilized for molecular docking studies to evaluate their binding potential. The docking results revealed the best binding orientation with the lowest possible binding energy of −10.20 kcal/mol for the RL-Fe complex with BSA and −8.30 kcal/mol for the FR-Fe complex with DNA. Furthermore, the binding interactions of all the synthesized compounds were investigated using UV–visible absorption (UV) and fluorescence spectroscopy (FL). The binding sites and binding constants were determined using the Stern-Volmer equation. Moreover, cytotoxicity assays were performed against lung cancer (A549), liver cancer (Hep G2), and normal Vero cell lines, with results benchmarked against cisplatin. Notably, the ligand (FRL) exhibited significant cytotoxic action with an IC₅₀ of 54.51 μM compared to the related Fe(III) complex (FR-Fe) (i.e., 69.86 μM) against A549 cells. But the complex FR-Fe displayed IC₅₀ of 56.19 μM against Hep G2 cells, demonstrating better potency over cisplatin.

This paper introduced an innovative paper-based biosensor outlined for the precise and rapid detection of fenitrothion pesticide. In this work, CuS@rGO grafted PEDOT:PSS-based conducting paper has been fabricated by simple dip coating method. Further, the CuS@rGO/PEDOT:PSS/WP electrodes were doped with multiple organic solvents such as methanol, ethylene glycol (EG), dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF), and N-methyl pyrrolidone (NMP) to enhance the electrochemical parameters. Among all these solvents, the electrode doped with DMSO is found to have the highest conductivity. Subsequently, AChE enzyme is immobilized onto the modified electrode to accelerate the particular recognition of fenitrothion using glutaraldehyde as a cross-linking agent. Electrochemical studies have shown that this conducting paper-based electrode possesses high sensitivity and low detection limit of 0.505 mA/pM and 0.28 pM, respectively, under a physiological range of 1–80 pM for fenitrothion (FNT) detection. This paper electrode may be a very promising alternative to ITO, gold and glassy carbon electrodes, which are known to have few uses because of their high cost, fragility, restricted flexibility, and environment concerns. The recommended biosensor's accuracy was well evaluated in two real samples like rice and tomato thereby increasing its suitability for FNT detection in real-world circumstances.

Reaction of Organotin (IV) salts with tridentate Schiff bases (SBI and SBII) reacted in 1:1 M ratios where complexes (1–6) were afforded. Organotin (IV) complexes with the formula [Sn (CH₃)₂(SBI)ClH₂O]Cl (1), [Sn(C₄H₉)₂(SBI)Cl₂]H₂O (2), [Sn(C₆H₅)₄(SBI)] (3), [Sn (CH₃)₂(SBII)Cl₂]3H₂O (4), [Sn(C₄H₉)₂(SBII)Cl₂]2H₂O (5) and [Sn(C₆H₅)₄(SBII)]H₂O (6) (SBI = 2(E)-2-(((3-hydroxyphenyl)imino)methyl)phenol and SBII = (E)-2-(((3-aminophenyl)imino)-methyl)phenol were described. Every Tin (IV) complex (1–6) had a distinct color and was soluble in DMF and DMSO organic solvents. The complexes have all been thoroughly examined using mass spectrum analysis, FT-IR, UV–vis, ¹H-NMR, and CHN investigations. For both SBI and SBII, the Schiff bases chelated to the tin metal ion in a tridentate fashion through NOO and NNO atoms, including nitrogen atoms of the azomethine group. This was demonstrated by the spectroscopic data of the ligand and its related complexes (1–6). The tin atom was found to have pentagonal-bipyramidal geometry according to elemental analyses data coupled with electronic spectral data. The complexes were nonelectrolytes except Complex 1 is electrolyte. The complexes (1–6) thermal deterioration occurred between 200°C and 800°C, according to thermogravimetric analysis performed during thermal decomposition under nitrogen. The in vitro tests measured the efficacy of the Schiff base Tin (IV) complexes (1–6) to inhibit the growth of several types of bacteria and fungi. When compared to the Schiff bases ligand, it was shown that the complexes were more successful in killing bacteria and fungi organisms. In order to interpret the compounds' structure and reactivity, density functional calculations were done. Molecular docking by the protein locations of 2V5Z and 7KGW was utilized to evaluate possible medicines using MOE 2008. Without verifying results with MD simulations, the work was designed to explore molecular docking.

Four kinds of cyclometalated half-sandwich ruthenium(II) complexes 1–4 with air stability were synthesized, which were supported by C,N-donor Schiff base ligands as raw materials by C-H activation. These newly synthesized ruthenium(II) complexes were characterized and studied by infrared (IR), ultraviolet (UV), nuclear magnetic resonance (NMR), and other analytical or spectroscopic techniques, and their exact structures of ruthenium(II) complexes were confirmed by single-crystal X-ray analysis. Cyclometalated half-sandwich ruthenium(II) complexes 1–4 exhibited good catalytic activity in catalyzing the oxidative homo-coupling of primary amines, dehydrogenation of secondary amines, and cross-coupling reaction of amines with alcohols to synthesize imines, all of which were conducted in an open flask with air as oxidant. There was little effect of different substituents on ruthenium complexes ligands on catalytic efficiency. Ruthenium catalysts had the characteristics of mild reaction conditions, strong universality of substrate, good stability, and high catalytic efficiency, which had potential application in industrial production.

In this investigation, a novel core-shell photocatalyst, denoted as Fe₃O₄@SiO₂/PAEDTC (FSP)-doped MIL-101 (Fe) (FSPM), was synthesized through the sol–gel method and applied for the degradation of bisphenol A (BPA) and pyrocatechol (PCT) in aqueous solutions. Various analytical techniques were employed to assess the characteristics of the core-shell photocatalyst. The resultant nanocomposite displayed specific attributes, including a saturation magnetization of 12 emu/g, a pore size of 1.35 nm, and a surface area of 992 m²/g, allowing for facile separation using a magnetic field. The optimal conditions for achieving highest BPA (%94.2) and PCT (%100) degradation efficiencies were found to be a pH of 7, 50 mg/L pollutant, a nanocomposite quantity of 0.8 g/L, and a radiation intensity of 8 W after 1 h. The BOD₅/COD (biological oxygen demand during 5 days/chemical oxygen demand) ratio exceeded 0.4, accompanied by total organic carbon (TOC) and COD removal rates surpassing 85%. The tests conducted on scavenging suggested the formation of ^•OH, hole, and electron in the studied system. Among these, ^•OH was found to be the foremost species responsible for degrading BPA and PCT. Stability tests revealed that the photocatalyst could be recycled with a minimal reduction of only 7% during five reaction steps. The energy consumed by the system during different reactions ranged from 10.2 to 27.1 kWh/m³ for BPA degradation and from 10.9 to 29.4 kWh/m³ for PCT degradation at time of 10 to 60 min. Finally, the results of this study showed that the use of all three sources of radiation in the photocatalytic process can effectively destroy pollutants.

Gold(I)-catalyzed highly regioselective hydration of alkynylsulfonamides for synthesis of N-ketosulfonamides in 85%–96% yields. The reaction used water as a nucleophile, which had the advantages of mild reaction conditions, good functional group tolerance, high regioselectivity, high yield, and 100% atomic economy (without generating by-products or waste). This might endow this method with great potential in green synthesis of N-ketosulfonamides compounds.

The United Nations sustainable development goals 9 and 12 discuss about adoption of sustainable and green chemistry concept for manufacturing of pharmaceuticals and chemicals. Water is universally accepted as a green solvent for organic reactions, and solvent-free reactions are considered as green, sustainable methods for synthesis of heterocyclic compounds. Pd/C is a heterogeneous, recyclable catalyst and has been used for several cross-coupling reactions. A ligand-free Pd/C-catalyzed homocoupling reaction of haloarenes in water is reported. The reaction condition is mild (reaction temp. 40°C), and the desired products were isolated in moderate to good yield (56%–81%). Activation of phase transfer catalyst under microwave irradiation reduced the catalyst loading and reaction time (from 24 h to 30 min). The major advantages of this method over existing methods are (i) ligand-free homocoupling reaction, (ii) lower Pd/C catalyst loading, and (iii) use of water as a green and sustainable solvent. This reaction along with continuous-flow bromination, and amine deprotection reactions were successfully applied for synthesis of antiviral drug daclatasvir.

CeO₂-H₂SO₄ (C-S), CeO₂-TiO₂ (C-T), and CeO₂-TiO₂-H₂SO₃ (C-T-S) were used for the selective catalytic reduction of NO with NH₃ (NH₃-SCR). Nearly 100% NO_x conversion of C-T-S was achieved at 250°C–450°C. When the concentration of Ce₂(SO₄)₃ was excessively high, it causes tightly binding with Ce³⁺ ions in CeO₂, prevents some Ce³⁺ ions from effectively participating in redox reactions, and results in the inferior SCR activity. Consequently, C-T-S possessed the superior catalytic performance due to the optimal content of sulfates. Furthermore, the presence of NO₂ facilitated the rapid SCR reaction on C-T-S, thereby further enhancing the catalytic activity. Additionally, the formation of Ce₂(SO₄)₃ on C-T-S could increase the number of acid sites, particularly Brönsted acid sites, resulting in the improvement of SCR performance. C-S, C-T, and C-T-S mainly followed the Langmuir–Hinshelwood (L–H).