Applied Organometallic Chemistry最新文献

Metformin, a widely used medication, is primarily employed as an anti-hyperglycemic drug for diabetes management, with emerging roles in cancer suppression and as a potential weight loss treatment. The widespread use of this medication has led to its accumulation in aquatic and sewage environments. Even in small quantities, this drug poses risks to both humans and other animals, particularly in aquatic environments. In this study, alkyl and sulfonic groups were linked to a metal–organic framework (MOF) for Zr-MOF-NH-(CH₂)₃-SO₃H synthesis using a post-synthetic method. Subsequently, the performance of Zr-MOF-NH-(CH₂)₃-SO₃H as a nano-adsorbent for the removal of metformin pharmaceutical pollutants was investigated. Under optimal conditions (pH = 9, contact time 90 min, adsorbent dose = 0.1 g/L, and metformin concentration 25 ppm), the maximum adsorption capacity for removal was approximately 160 mg/g. The interactions between the framework and metformin, the effect of pH on these interactions, and the possible mechanisms were investigated. The final results showed that the Zr-MOF-NH-(CH₂)₃-SO₃H framework has a high adsorption capacity to remove the metformin drug, and this high adsorption probably occurs mostly via electrostatic attraction, which results in more interactions, such as H-bonding, π-π, and acid and base interactions. Additionally, the freely rotating alkyl chains (−(CH₂)₃SO₃H) in the MOF can further enhance the material's ability to capture metformin by improving the penetration of metformin into the framework, thus significantly enhancing the adsorption performance. This study demonstrates the potential of Zr-MOF-NH-(CH₂)₃-SO₃H as an effective nano-adsorbent for mitigating pharmaceutical pollutants in aquatic environments.

We report the electrocatalytic performance in hydrogen evolution reaction (HER) of three Ni(II) complexes based on benzil bis(thiosemicarbazone) ligands derived from 1,2-diphenylethanedione and 4-isopropyl-3-thiosemicarbazide (L¹H₂), 4-methyl-3-thiosemicarbazide (L²H₂) or 3-thiosemicarbazide (L³H₂). Cyclic voltammetry in dimethylformamide (DMF) exhibit two diffusion-controlled reversible processes at negative potentials, corresponding to [Ni^IIL³]/[Ni^IIL^3·]⁻ and Ni^II/Ni^I reduction processes. The catalytic activity in DMF was evaluated using acetic acid as proton source, showing the appearance of a catalytic cathodic current associated with the Ni^II/I redox couple. Analysis of the gas evolved from controlled potential coulometry (CPC) confirmed that the three complexes can effectively catalyse hydrogen evolution and that the catalytic activity depends on the substituent attached to the terminal amine. Electrolysis induces electrodeposition of the complexes on the electrode surface forming a film, which were also tested as HER catalysts. The results showed that the total charge produced by the films is, in all cases, lower than with the dissolved complex, but they exhibit higher faradaic efficiencies. DFT calculations were made to establish the catalytic route, and the results support an ECEC mechanism, in which E represents an electrochemical step and C is a chemical one (protonation), centred in the metal assisted by the ligand.

As a new catalytic technology, photocatalytic technology has received extensive attention in alleviating the energy crisis and controlling environmental pollution, and photocatalytic materials are the key to achieve efficient water splitting to produce hydrogen while removing organic pollution, so in this paper, [Zn(HL)(L)₂]·4H₂O (ZnL, HL = 2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10] phenanthroline) was first synthesized and combined with g-C₃N₄ to form ZnL/CN, which were applied to the water splitting water to produce hydrogen in norfloxacin wastewater system. Through quantitative calculation, it can be found that ZnL and g-C₃N₄ have a matching band gap, which can form a heterojunction structure, and ZnL/CN built by the heterostructure solves the problem of photogenerated carrier recombination from the internal structure. On the other hand, through a series of related characterizations, it was further proved that 6% ZnL/CN has excellent photocatalytic performance, which lays a theoretical foundation for the research of ZnL/CN in the production of hydrogen from water splitting and environmental treatment and provides a research idea for the synergistic removal of organic pollutants from efficient water splitting to hydrogen.

A Cu(I)–amidine complex–functionalized lightly cross-linked polyacrylamide was successfully synthesized using Cu(I) iodide as copper source CPAM_Amd–CuI and comprehensively characterized using ICP, CHN, DR-UV/vis, FTIR, XRD, FE-SEM, EDAX, TG/DTG, TEM, and elemental analysis. As shown by TEM, Cu(I) particles are well dispersed and average 23.36 nm in diameter. An evaluation of the catalytic performance of CPAM_Amd–Cu(I) as a nano-sized heterogeneous catalyst was conducted in one-pot, three-component 1,3-dipolar cyclization (click) reactions. In the title reaction of sodium azide, alkyl halide, and a terminal alkyne in water, the polymeric Cu(I) catalyst displayed excellent activity and stability, yielding a high yield of up to 98% of 1,4-disubstituted 1,2,3-triazoles. Furthermore, the newly developed polymeric Cu(I) catalyst revealed excellent stability and recyclability in the heterogeneous title reactions over six cycles, losing only a minor amount of catalytic activity. Moreover, the designed support did not leach Cu(I) very readily.

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.