Catalytic carbonylation for the synthesis of chemical intermediates

Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline, and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh₃ and NEt₄Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate. In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the presence of PdCl₂−PPh₃−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that is indispensable for an efficient overall reaction.     

Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl₂·2H₂O, NiCl₂·6H₂O or CoCl₂·6H₂O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, ¹H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag⁺, Hg⁺ and Hg²⁺. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday     

Plasma Induced Graft Polymerization of Three Hydrophilic Monomers on Nylon 6,6 Fabrics for Enhancing Antistatic Property

In this study, three hydrophilic monomers; 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-hydroxyethyl methacrylate, diallyldimethylammonium chloride (DADMAC) were selected and their performance as an antistatic finish on nylon 6,6 fabrics was investigated. A non-thermal, high density atmospheric pressure plasma was used to graft polymerize the monomers on nylon 6,6 fabrics. Fabrics were first treated with solutions of monomer in water, air dried and then treated with helium plasma to graft polymerize the monomer on the fiber surface. Surface resistivity values were measured before and after soxhlet extraction with water. Results showed that the DADMAC monomer provided better antistatic properties to fabrics. Further studies with DADMAC monomer were made; effects of plasma post exposure time, plasma pre-exposure time, plasma power, concentration of the monomer and existence of a crosslinker were investigated. Higher plasma power, higher concentration of the monomer and longer post exposure times all gave better antistatic properties to the nylon 6,6 fabrics. Acid dye staining, UV–Vis and FT-IR measurements were conducted and results confirmed a grafted poly-DADMAC layer on the fabric surface.     

Determination of Tetracyclines in Milk,Eggs and Honey Using in-situ Ionic Liquid Based Dispersive Liquid–Liquid Microextraction

In this study, in-situ ionic liquid based dispersive liquid?liquid microextraction method for enrichment of tetracyclines before liquid chromatographic analysis has been improved. A 1-benzyl-3- methylimidazolium chloride was used as an ionic liquid. To increase extraction efficiency, some optimization parameters (amount of ammonium hexafluorophoshate, extraction time, centrifugation time, ratio of ionic liquid/salt) were investigated. At optimized conditions, enrichment factors of four tetracycline antibiotics (tetracycline, chlortetracycline, methacycline, doxycycline) were between 25 and 98. The residues of tetracyclines were not found in the studied real samples. For the accuracy of the method, the concentration of 50 and 250 μg/L of standard tetracycline mixture solutions were spiked to the blank real milk, honey and egg samples and the percentage recoveries were obtained in the range of 75.8–109.7%.     

Chemical modification of silica gel with synthesized Schiff base hydrazone derivative and application for preconcentration and separation of U(VI) ions from aqueous solutions

Schiff base hydrazone derivative (HL) sorbent was synthesized according to the literature to be used in the adsorption and preconcentration of U(VI) ions from aqueous solution and it was exposed to immobilization, and new solid support material was obtained. For this purpose, Schiff base hydrazone derivative (HL) was chemically bonded to silica gel surface immobilized 3-aminopropyl trimethoxysilane, then analyzed by Fourier transform infrared, Brunauer–Emmett–Teller, scanning electron microscopy and elemental analysis. The influence of the solution pH, amount of sorbent, contact time, temperature, foreign ion effect and initial U(VI) concentration was investigated. The maximum U(VI) uptake capacity was found to be 8.46 mg/g.     

Synthesis of carrageenan coated silver nanoparticles by an easy green method and their characterization and antimicrobial activities

The aim of the present work was to synthesize carrageenan coated silver nanoparticles (CA–AgNPs) using carrageenan as reducing and stabilizing agent. For this purpose, 10 mL of 0.35% (w/v) carrageenan solution was mixed with 10 mL AgNO₃ solution at different concentrations (1, 5 and 10 mM), and the resulting mixture was stirred at 100 °C at high speed for 2 h. The formation of CA–AgNPs was proven with the surface plasmon peaks observed at approximately 420 nm. The sizes and zeta potentials of CA–AgNPs were determined by Zeta-Sizer. Negative zeta potentials of CA–AgNPs indicated that the obtained AgNPs were stable. With scanning electron microscope (SEM) and transmission electron microscope analysis, it was seen that CA–AgNPs have spherical structure. According to the energy dispersion spectrometer analysis based on SEM images, it was observed that the samples were elementally composed of carbon, oxygen, sulfur, potassium and silver. The chemical structures of CA–AgNPs were determined by Fourier transform infrared spectroscopy, and it was proved that the carbonyl and OH groups of carrageenan were involved in formation and stabilizing of AgNPs, respectively. According to thermal gravimetric analysis, it has been observed that CA–AgNPs were thermally more stable than pure carrageenan. Antibacterial activity of CA–AgNPs against gram-positive and gram-negative bacteria was investigated with agar well diffusion and liquid test. It has been observed that CA–AgNPs synthesized with 1 mM AgNO₃ did not have an antibacterial activity on Escherichia coli and Staphylococcus aureus. Inhibition zones of varying diameters were observed in the 5 mM and 10 mM S-AgNPs groups. The synthesized CA–AgNPs (5 and 10 mM) have the capacity to be used in wound dressing materials or topical agents applied to burns and wounds due to their antibacterial effects and stability.

     

Peripherally and Axially Carboxylic Acid Substituted Subphthalocyanines for Dye‐Sensitized Solar Cells

A series of subphthalocyanines (SubPcs) bearing a carboxylic acid group either at the peripheral or axial position have been designed and synthesized to investigate the influence of the COOH group positions on the dye‐sensitized solar cell (DSSC) performance. The DSSC devices based on SubPcs with axially substituted carboxylic acid groups showed low photovoltaic performance, whereas peripherally substituted one exhibited higher power conversion efficiency owing to improved injection from LUMO of SubPcs to the TiO₂ conduction band.     

The effect of competition between the frequency of the field and the frequency of the spin flipping on the kinetics of Ising metamagnet

We consider the effect of a variable representing the competition between the frequency of the field and the frequency of the spin flipping (Ω) on the dynamics of the metamagnetic Ising model in a cubic lattice under the presence of a time varying (oscillating) external magnetic field. The system is modelled with a formalism of master equation at a mean-field level. The time averaged staggered magnetization (Ms) acts as the order parameter and divides temperature field plane into three regions: anti-ferromagnetic, paramagnetic and coexistence of anti-ferromagnetic and paramagnetic phases. It is observed that the topology of the dynamical phase diagram depends strongly on Ω as well as the ratio between interlayer and intralayer couplings.