Inorganica Chimica Acta最新文献

Zinc oxide has been increasingly gaining popularity due to its various multifunctional features and applications in nanotechnology. Zinc oxide nanoparticles (ZnO NPs) are versatile, as these are utilized in multiple areas like gas sensing, biomedical applications, rubber composites, cosmetics formulations, food, and agriculture industry, etc. ZnO NPs have excellent features like biocompatibility, electrochemical activities, chemical stability, non-toxic nature, high surface area, high-electron communicating properties, ease of synthesis, and many more. This review paper comprehensively explores the advancements and trends of synthesis, characterization, and industrial applications of ZnO NPs. Synthesis methods including physical, chemical, and green manner are discussed herewith. General exploration of fields and applications, with special emphasis on rubber, biomedical, and sensors has been elucidated. Investigators have emphasized the photocatalytic applications, of the ZnO NPs especially in the removal of pollutants from wastewater. Further emphasizing the need for eminent research to unlock the full potential of ZnO NPs in commercializing from the laboratory to the industry.

Silver nanoparticles were synthesized by ionic exchange with zeolites and further reduction with hydrogen flux. Core electron binding energies were determined by X-ray photoelectron spectroscopy at different times of the reduction process. Electron propagator calculations of core electron binding energies were performed including scalar relativistic effects using effective core potentials and zero order regular approximation. Theoretical results were compared to the experiment to get insight into the origin of the experimental signals for carbon, oxygen, silicon, aluminum and silver. Small model molecules and zeolite fragments were used for the calculation of core electron binding energies. It is evidenced that although binding energies tend to converge, fluctuations of more than 1 eV are found for non-symmetric structures in neutral and cationic silver clusters. Detailed analysis shows that these fluctuations originate on the different coordination numbers of ionized silver atoms and charge fluctuations.

CO₂ adsorption on Pt₄ and on Pt₂M₂ (M = Co, Ni, and Cu) clusters supported on N-doped graphene (PNG) was analyzed using density functional theory. The Pt₂M₂ (M = Co, Ni) clusters supported on PNG had the maximum binding energy and charge transfer. Furthermore, the adsorption energy and charge transfer of CO₂ were high for Pt₂M₂ (M = Co, Ni, and Cu) supported on PNG. In addition, bond elongation and bending angle were observed in the CO₂ molecule after it was adsorbed on metal clusters supported on PNG. Non-covalent interaction contours revealed a repulsive interaction due to the steric effect between Pt₂M₂ (M = Co, Ni, and Cu) and PNG, whereas the Pt₄/PNG composite showed a combination of repulsive and van der Waals interactions. This investigation proved that Pt₂M₂ (M = Co, Ni, and Cu) clusters supported on PNG are promising candidates for CO₂ adsorption and activation.

Developing simple and effective receptors for instantaneous detection of l-amino acids is vital for the recognition of life-threatening diseases in their early stage. Here, we report the synthesis and characterization of 2,6-di(pyrazin-2-yl)pyridine (dppy) based ligand L (L = 2,2′-(4-(3,4-diethoxyphenyl)pyridine-2,6-diyl)dipyrazine) and its copper (II) complex, [Cu(NO₃)₂L]. The in-situ prepared [Cu(H₂O)₂L](NO₃)₂ receptor in aqueous acetonitrile (4:1 v/v, 10 mM HEPES buffer, pH 7.4) medium displayed instantaneous responses towards biologically important bio-thiol l-Cysteine (Cys) and essential amino acid l-Histidine (His) over other l-amino acids through UV–Visible absorption spectral studies. Additionally, the competitive experiments confirmed that in-situ prepared [Cu(H₂O)₂L](NO₃)₂ receptor selectively detects Cys (1 equivalent) in the presence of other l-amino acids. The detection limits of Cys and His were calculated to be 8.23 × 10⁻⁷ M and 2.55 × 10⁻⁶ M, respectively. The density functional theory (DFT) calculation shows that selectivity of [Cu(H₂O)₂L](NO₃)₂ towards Cys is due to the reduction of Cu(II) to Cu(I) in the presence of Cys, while Cys is oxidized to cystine (Cys-Cys). For His, selectivity observed due to the formation of [Cu(His)₂] moiety between Cu(II) ion with one His via N,O coordination mode and another His via N,N,O-coordination mode.

Two new nickel (II) substituted thiosemicarbazone Schiff base complexes [Ni(meph)₂] (1) [where H₂meph = (2E)-N-methyl-2-[1-(pyridin-2-yl)ethylidene]hydrazine-1-carbothioamide] and [Ni(hmm)₂](NO₃)₂·2H₂O (2) [where H₂hmm = (2E)-2-[(2-hydroxyphenyl)methylidene]-N-methylhydrazine-1-carbothioamide] have been designed and synthesized by the condensation of 4-methyl-3-thiosemicarbazide with 2-acetylpyridine and salicylaldehyde respectively. Both the metal complexes 1 and 2 are characterized using different available spectroscopic techniques like FT-IR, UV–Vis spectroscopy, elemental analysis, and single crystal X-ray structure analysis. X-ray crystal structure analysis reveal that complex 1 and 2 are octahedral Ni(II) complexes. The calf-thymus CT-DNA-binding property of 1 and 2 has been evaluated by employing UV–Vis and fluorescence spectral titration. All the results show that CT-DNA binds with both nickel(II) complexes 1 and 2. In vitro cytotoxicity activity of complexes 1 and 2 toward A375 and MDA-MB-231 was evaluated using MTT assay and other methods which confirm that both complexes 1 and 2 behave as promising anti-cancer agents.

The reaction of [X][Hfe(CO)₄] (X = mainly PPh₄, but also NEt₄, K and Ph₃PNPPh₃) with chlorophosphines for the synthesis of low coordinated phosphorus complexes is reviewed. Diphosphene (PP), phospha-alkene (PC<), phospha-allene (PCC<), and phosphide (>P) iron complexes have been in particular obtained, and characterized by ³¹P NMR, and by X-ray diffraction in several cases.

This study presents a new uncharged platinum(II) complex with a pyrazolyliodonium ligand, which features an exceptionally large σ-hole on the iodine atom. Single-crystal X-ray diffraction analysis reveals the structure of the [LPtCl₃]·2DMF complex, highlighting two types of intermolecular halogen bonds: a C−I⋯O bond with DMF and C−I⋯Cl bonds with the platinum complex. Quantum chemical calculations confirm the high positive electrostatic potential on the iodine σ-hole, demonstrating its significant halogen bond donor ability.

The regioselectivity of the ligand substitution reaction of square-planar Pt(II) complexes with chelating ligands pyridyl-NHC (Py-NHC), phenyl-NHC (Ph-NHC), and phenyl-pyridine (ppy, Ph-Py) was studied. The reaction of the dichlorido Pt(II) complex bearing these chelating ligands in the presence of pyrazole (pz) ligands afforded mono-pyrazole adducts [PtCl(ChL)(pz)]ⁿ⁺ (n = 0 and 1; ChL=chelating ligand (Py-NHC, Ph-NHC, Ph-py)). The structures of the PtCl(pz) complexes with the Py-NHC, Ph-NHC, and Ph-Py chelating ligands were confirmed by X-ray crystallographic analysis. The regioselectivity of the ligand substitution reaction between the pyrazole moieties and chloride ions can be controlled by the strength of the trans effect of the chelating ligands. Based on the structures of the products, a clear trend of Py < NHC < Ph was observed in the trans effect of the chelating ligands. This finding provides a rational synthetic procedure for asymmetric Pt(II) complexes with chelating ligands in a stepwise manner.

This study concerns the synthesis of zinc isoporphyrin (2), from zinc porphyrin [Zn(4-Cl)TPP], (1), where TPP- tetraphenylporphyrin ligand. Because of the prospective applications such as an infrared dye and catalyst in photomedicine, isoporphyrin has been in high demand. However, there is limited documentation of metalloisoporphyrins. Here, we have discussed the synthesis, characterization, coordination chemistry and theoretical studies of zinc isoporphyrin, 2. Compound 2 was characterized using UV–visible, ¹H NMR, ¹³C NMR and ESI Mass analysis. Electrochemical studies were carried out using cyclic voltammetry. Theoretical studies including structure optimization, analysis of electronic transition, and natural bond analysis (NBO) were performed for both 1 and 2. Besides that, the global reactivity indices of 1 were compared with 2. The lower HOMO-LUMO energy gap in 2 (1.95 eV) supports the shifting of Q bands to a lower energy region. The molecular docking studies of 1 and 2 were performed for the first time and found that isoporphyrins can act as a potential inhibitor of G-quartet DNA associated with cancer disease. These results may be useful in designing effective therapeutics for the treatment of cancer.

A 6-(thiophen-2-yl)benzo[4,5]thieno[3,2-c]quinoline (QTP), with thiophene and quinoline based moieties as binding sites, has been synthesized and characterized with spectroscopic methods, and DFT. The synthesized probe QTP showed highly sensitive and highly specific fluorescent ‘turn-on’ effect (λem = 280 nm) for the 1:1 binding with Fe³⁺ ions to form probe QTP.Fe³⁺ complex in semi-aqueous medium (acetonitrile:water (50:50; v/v)) and live cells. The 1:1 binding stoichiometry of probe QTP and Fe³⁺ ions were proposed by DFT calculations and confirmed by the NMR spectroscopy, and mass spectrum of probe QTP.Fe³⁺ complex. Importantly, with the LOD 6.37 µM for the detection of Fe³⁺ ions, receptor QTP did not show any interference from potentially competing ions, indicates its biocompatibility. The micromolar limit of detection (6.37 µM), cell permeability, and low cytotoxicity allows the probe QTP to be an outstanding tool for the live-cell imaging and detection of ferric ions in live cells.