Synthesis of new dinuclear dicopper(II) and dinickel(II) complexes. The kinetics of catechol oxidase and electrochemistry of a dicopper(II) complex

A new dinuclear ligand L, ethylene[OO-bis-salicylidene--diketone] bearing two symmetrical coordination sites was synthesized by the condensation of salicylaldehyde and acetylacetone, L, with 1,2-dibromoethane under reflux. The ligand L in a 1:1 ratio was treated with CuCl₂ and NiCl₂ to yield the complexes, tetrachloro bis[OO-bis- salicylidene--diketone copper(II)] and bis[OO-bis-salicylidene--diketone nickel(II)] chloride. The complexes were subsequently characterized by spectroscopic techniques, elemental analysis, i.r., ¹H-n.m.r., ¹³C-n.m.r., u.v.–vis., e.p.r. spectroscopy, and conductance measurements. The conductance measurements in DMF reveal that the Cu^II complex is covalent while the Ni^II complex is ionic and the spectral data support the Cu^II complex to be distorted octahedral whereas the Ni^II complex has square-planar geometry. The dioxygen binding was studied spectrophotometrically by the oxidation of tetrachloro bis[OO-bis-salicylidene--diketone copper(II)] with pyrocatechol in the presence of oxygen. The kinetic experiments were performed with the copper complex in DMF by monitoring the increase in absorbance over time at pH 8.0 in the presence of pyrocatechol at 25 °C. The kinetic parameters V_max and K_M were determined on the Michaelis–Menten Approach. Redox behavior of the dinuclear copper(II) complex was investigated by cyclic voltammetry in the presence of O₂ with the pyrocatechol (substrate) and also without the substrate. The large difference in potentials E⁰ is indicative of reversible oxygen binding of the complex and distinct catalytic activity.     

Efficacy of Phytochemicals Derived from Roots of Rondeletia odorata as Antioxidant,Antiulcer, Diuretic,Skin Brightening and Hemolytic Agents—A Comprehensive Biochemical and In Silico Study

Roots of Rondeletia odorata are a rich source of phytochemicals with high antioxidant potential and thus may possess health benefits. This study used the LC-MS technique to identify phytoconstituents in R. odorata roots extract/fractions. Results revealed that n-butanol fraction and ethanolic extract contained total phenolic and flavonoid contents with values of 155.64 ± 0.66 mgGAE/g DE and 194.94 ± 0.98 mgQE/g DE, respectively. Significant potential of antioxidants was observed by DPPH, CUPRAC and FRAP methods while the ABTS method showed moderate antioxidant potential. Maximum % inhibition for urease, tyrosinase and carbonic anhydrase was shown by ethanolic extract (73.39 ± 1.11%), n-butanol soluble fraction (80.26 ± 1.59%) and ethyl acetate soluble fraction (76.50 ± 0.67%) which were comparable with thiourea (standard) (98.07 ± 0.74%), kojic acid (standard) (98.59 ± 0.92%) and acetazolamide (standard) (95.51 ± 1.29%), respectively, while all other extract/fractions showed moderate inhibition activity against these three enzymes. Hemolytic activity was also observed to range from 18.80 ± 0.42 to 3.48 ± 0.69% using the standard (triton X-100) method. In total, 28 and 20 compounds were identified tentatively by LC-MS analysis of ethanolic extract and n-butanol soluble fraction, respectively. Furthermore, molecular docking was undertaken for major compounds identified by LC-MS for determining binding affinity between enzymes (urease, tyrosinase and carbonic anhydrase) and ligands. It was concluded that active phytochemicals were present in roots of R. odorata with potential for multiple pharmacological applications and as a latent source of pharmaceutically important compounds. This should be further explored to isolate important constituents that could be used in treating different diseases.     

Synthesis of new 14- and 16-membered macrocycles and their transition metal complexes

Summary Benzoylacetic acid (1 mol) interacts with ethylenediamine or with propanediamine (2 mol) to yield new N₄ macrocycles 1,5,8,12-tetraazacyclotetradeca-2,4,9,11-tetraphenyl-3, 10-dicarboxylic-4,11-diacetic acid- 1,8-diene (L¹) and 1,5,9,13-tetraazacyclohexadeca-2,4,10,12-tetraphenyl-3, 11-dicarboxylic-4,12-diacetic acid-1,9-diene (L²), respectively. These macrocycles have been successfully complexed with Cr^III, Fe^III, Mn^II, Co^II, Ni^II, Cu^II and Zn^II. The complexes of the divalent metal ions are non-electrolytes, while those of Fe^III and Cr^III are 1:1 electrolytes in DMSO. On the basis of ligand field spectra and magnetic moments an octahedral geometry has been proposed for all the complexes.     

Synthesis,Characterization, Solution Stability Studies,Electrochemistry, and DNA‐Binding Behavior of Cu(II) Complexes of D‐Gluconic Acid

The chemistry of saccharides has emerged as a new subarea of pharmaceuticals. Condensation reactions of D‐gluconic acid with [M(en)₂]Cl₂/[M(ea)₂]Cl₂ where M=Cu, Ni, en=ethylenediamine, and ea=ethanolamine were carried out and a new series of chiral complexes have been isolated and characterized. Molar conductance measurements show that the complexes are ionic, and the spectral data are indicative of octahedral geometry of the complexes [Cu(D‐GlcCO₂H en*)₂ (H₂O)₂] · Cl₂ (1b), [Cu(D‐GlcCO₂H ea*) (H₂O)₂] · Cl₂ (3b) and [Ni(D‐GlcCO₂H ea*) (H₂O)₂] · Cl₂ (4), and the square planar geometry of complex [Ni(D‐GlcCO₂H en*)₂] · Cl₂ (2b). Polarimetric data along with CD spectra establish the chiral nature of complexes. Solution stabilities of these complexes were evaluated by cyclic voltammetric techniques as a function of pH. Electrochemical behavior of the complexes was studied in aqueous solution and showed an irreversible Cu^II/Cu^I couple. Kinetic studies of complex 1b and 3b with calf thymus DNA have been investigated spectrophotometrically under pseudo‐first order conditions, and k _obs values have been evaluated. Circular dichroism, cyclic voltammetry determinations, and viscosity measurements have also been carried out to authenticate the binding of DNA with metal complexes. Complexes 1b and 3b bind to DNA by covalent bond formation.     

Aurones and Analogues: Promising Heterocyclic Scaffolds for Development of Antioxidant and Antimicrobial Agents

Russian Journal of General Chemistry - Synthesis of some new multi-functional analogues of 2′-hydroxy chalcone containing isoxazole and pyrazole functions were synthesized, and their...     

Facilitated kinetic transport of Cu(II) through a supported liquid membrane with calix[4]arene as a carrrier

In the present investigation, p-morpholinomethylcalix[4]arene (1) has been examined as a carrier in supported liquid membrane (SLM) for Cu(II) transport. The influence of different parameters, such as solvent, membrane dipping time, support membrane, co-anions, donor and acceptor pH, and carrier concentration on Cu(II) transport, was checked. The permeability values were calculated by using Danesi mass transfer model. Higher Cu(II) permeability was observed in diphenyl ether, with 1 h dipping time, Celgard 2500 and Cl^? as co-anion. The optimum pH for donor phase was 2 and that for acceptor phase was neutral at 10^?3 M carrier concentration. Diffusion coefficients were calculated using Reinhoudt's model, lag time measurements as well as by Wilke–Chang relation and compared. The transport was found to be diffusion-controlled in the membrane phase and the diffusion coefficient was calculated to be 1.54 × 10^?10 m/s whereas the extraction constant was calculated to be 1.19 × 10^?5 m/s.     

Transformation of Acetaminophen by Dichromate Oxidation Produces the Toxicants 1,4-Benzoquinone and Ammonium Ions

The reaction of the common pain reliever acetaminophen (paracetamol, 4-acetamidophenol) with dichromate was investigated over time under conditions that simulate wastewater disinfection. The occurrence of the acetaminophen in the water bodies, especially in drinking water resources, has received considerable attentions. In situ chemical oxidation is a promising cost-effective treatment method to remove acetaminophen from water body as it degrades the drug to large extent. Experimental results indicate that the reaction is second order overall and first order with respect to both dichromate and acetaminophen, and has activation energy of 14.1 kJ/mol. The second-order rate constant ranges from 1.56 × 10^?3 to 13.4 × 10^?3 min^?1 at temperature from 35 to 65°C. The acetaminophen degradation rates can be accelerated through increasing reaction temperature and oxidant concentration. The reaction under acid conditions was slightly faster than under alkaline or neutral conditions. Two of the products were unequivocally identified as the toxic compounds 1,4-benzoquinone and ammonium ions. These results demonstrate that acetaminophen is likely to be transformed significantly into toxic product if dichromate is used as an oxidizing agent during wastewater treatment.     

Synthesis and characterization of glycoconjugate tin(IV) complexes: In vitro DNA binding studies, cytotoxicity, and cell death

New glycosyl derived ligand and its complexes, with SnCl₄·5H₂O (1) and (CH₃)₂SnCl₂(2) were synthesized and characterized by spectroscopic (IR, ¹H, ¹³C, and ¹¹⁹Sn NMR, UV-vis, ESI-MS) and analytical methods. Interaction studies of 1 and 2 with CT DNA were studied by using various biophysical techniques, which showed high binding affinity of 2 with CT DNA. In vitro cytotoxicity of complexes 1 and 2 were evaluated against different human cancer cell lines of different histological origins by employing SRB Assay. The organotin(IV) complex 2 exhibited remarkable activity against DWD (oral cancer) cell lines with GI₅₀ values <10 μg/ml. Complex 2 induced apoptosis of DWD cell line at a very low concentration of 1-4 μg/mL.