Utility and Synthetic Uses of Mannich Reaction: An Efficient Route for Synthesis of Thiadiazino‐[1,3,5][3,2‐a]benzimidazoles

The utilities of the Mannich reaction in synthetic organic chemistry are reviewed. The behaviors of Mannich reactions on several bifunctional heterocyclic compounds have been reported. A new class of heterocyclic compounds, thiadiazino[1,3,5][3,2‐a]benzimidazoles 12a–g, were obtained by reaction of 2‐mercaptobenzimidazole with primary aliphatic amines in a one‐step synthesis. An attempt to apply this reaction using primary aromatic amines lead to the formation of the well‐known Mannich bases 11a–g rather than the N‐substituted thiadiazines 13.     

Electrocatalytic Oxidation of Cysteine at a CoSalophen/ n‐(butyl)4SiW12O40 Carbon Paste Electrode

In the present study, a novel mixture consisting of N,N′‐bis(salicylidene)‐1,2‐phenylenediamino cobalt (CoSalophen, CoSal) complex and (n‐butyl)₄SiW₁₂O₄₀ (SiW₁₂), have been used to chemically modify a carbon paste electrode (CPE) for sensitive determination of cysteine (CySH). The electrocatalytic effect of the newly developed modified CPE towards oxidation of CySH was evaluated by comparing cyclic and differential pulse voltammograms in the presence of cysteine at bare, CoSal, SiW₁₂ and CoSal/SiW₁₂ modified CPE. The differential pulse voltammetry method was applied as a sensitive method for quantitative detection of CySH trace amounts, the experimental conditions being optimized in order to evaluate the best analytical parameters of the sensor. Reproducibility and stability studies were also performed and the sensor was applied for the determination of CySH in a pharmaceutical sample and in human blood serum and urine samples.     

Synthesis, Characterization, Photoluminescence and Photocatalytic Properties of CeO2 Nanoparticles by the Sonochemical Method

Uniform CeO₂ nanoparticles were synthesized via a facile sonochemical reaction between ceric ammonium nitrate and ammonia. Nanoparticles were synthesized via a surfactant free reaction at room temperature in solvent of water. Products were characterized using X-ray diffraction, scanning electron microscopy, photoluminescence (PL) spectroscopy, and energy dispersive X-ray analysis. The effect of different parameters such as precursor, power of pulsation, surfactant and reaction time on the morphology of the products was investigated. It was found that the as-obtained CeO₂ nanoparticles exhibit a strong PL peak at 381 nm at room temperature that can be ascribed to the high level transition in the CeO₂ semiconductor. The photocatalytic behavior of CeO₂ nanoparticles was evaluated using the degradation of a methyl orange aqueous solution under ultraviolet light irradiation. The results show that CeO₂ nanoparticles are promising materials with excellent performance in photocatalytic applications.     

Synthesis,characterization, thermal,electrochemical, and DFT studies of mononuclear cyclopalladated complexes containing bidentate phosphine ligands and their biological evaluation as antioxidant and antibacterial agents

The non-symmetric phosphorus ylides and their Pd(II) complexes have been synthesized as potential antioxidant and antibacterial compounds and their structures were elucidated using a variety of physicochemical techniques. The reaction of 1 equiv non-symmetric phosphorus ylides, Ph₂PCH₂PPh₂C(H)C(O)PhX (X = Br (Y¹), Cl (Y²), NO₂ (Y³), OCH₃ (Y⁴)) with [Pd(dppe)Cl₂] (M¹), followed by treatment with 2 equiv AgOTf led to monomeric chelate complexes, [(dppe)Pd(Ph₂PCH₂PPh₂C(H)C(O)PhX)] (OSO₂CF₃)₂ (X = Br (C¹), Cl (C²), NO₂ (C³), OCH₃ (C⁴)), which contain a five-membered P,P chelate ring in one side and a five-membered P,C chelate ring in the other side. Palladium ion complexes were synthesized and investigated by cyclic voltammetry, FT-IR, UV–visible, multinuclear (¹H, ³¹P and ¹⁹F) NMR, thermal analysis and ESI-mass spectroscopic studies. Some complexes and ligands have been studied by powder XRD and single crystal X-ray diffraction techniques. FT-IR and ³¹P NMR studies revealed that the ylides Y are coordinated to the metal ions via the terminal phosphorus (P_c) of the ylides and methene group (CH). The proposed coordination geometry around the Pd atom in these complexes is defined as slightly distorted square planar by UV-Visible and DFT studies. Thermal stability of all complexes was also shown by TG/DTG methods. Furthermore, the electrochemical behavior of the complexes was investigated by cyclic voltammetry. The results indicate that all complexes are successfully synthesized from the initial ligands. All complexes were analyzed for their antioxidant properties by DPPH free radical scavenging assay. In addition, the antibacterial effects of the hexane-solved complexes were investigated by disc diffusion method against four Gram positive and negative bacteria. All complexes represented antibacterial activity against bacteria tested especially on Gram positive ones. A theoretical study on the structure, ¹H and ³¹P NMR chemical shifts and the interaction energy between the Pd²⁺ ion and ligands dppe and ylide Y is also reported.     

Regio‐controlled and Stereo‐controlled Ring Expansion of N‐Substituted‐2 Benzoylaziridines Using Fe(NO3)3

Several N‐acyl‐2‐benzoylaziridines were previously prepared conveniently and used in the preparation of 5‐benzoyl‐2,4‐diaryl oxazolines in the presence of NaI. In this work, synthesis of some trans‐4‐benzoyl‐2,5‐diaryl oxazolines by a regio‐controlled and stereo‐controlled reaction in the presence of Iron (III) nitrate at room temperature is reported. A plausible mechanism has been proposed for ring expansion of N‐acylaziridines to oxazolines.     

Study of complex formation of 5,5′-(2E, 2′E)-2,2′-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

In this paper the complexation reaction of the 5,5′-(2E,2′E)-2,2′-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd²⁺ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd²⁺ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (ΔG ^°, ΔH ^°, and ΔS ^°) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van’t Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.     

Direct Numerical Simulation of Pore-Scale Trapping Events During Capillary-Dominated Two-Phase Flow in Porous Media

Transport in Porous Media - This study focuses on direct numerical simulation of imbibition, displacement of the non-wetting phase by the wetting phase, through water-wet carbonate rocks. We...     

All optical switching in azo-polymer planar waveguide

In this paper all optical switching in planar methyl red doped poly (methyl methacrylate) (MR/PMMA) waveguide and the effects of different parameters on this process are presented. Switching was achieved by a 488 nm Ar ion laser (pump beam) on a 633 nm He-Ne laser (probe beam) when passed through the waveguide. The effect of temperature and pump intensity, polarization and chopping frequency on switching is investigated. The switching process is attributed to trans-cis-trans photoisomerization of azo dyes in the polymer host. By studying the absorption spectrum of the sample, it is shown that both pump and probe laser beams are effective on the switching process.     

A Simple Chemical Method for Synthesis of NiFe2O4 Nanoparticles and Polystyrene-Based Magnetic Nanocomposites

Magnetic NiFe₂O₄ (NiFe) nanoparticles were synthesized via a facile chemical reaction between Ni(NO₃)₂ and Fe(NO₃)₃. Different percents of NiFe nanoparticles were then added to polystyrene (PS) matrix. Nanoparticles were characterized using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The magnetic properties of the samples were also investigated using an alternating gradient force magnetometer. The nanoparticles exhibit ferromagnetic behaviour at room temperature, with a saturation magnetization of 20.8 emu/g and a coercivity of 99.6 Oe. Preparation of NiFe₂O₄ -PS nanocomposite leads to decrease in the coercivity.     

ENTROPY GENERATION ANALYSIS FOR A NON-AXISYMMETRIC FLOW OVER A ROTATING POROUS DISK

Journal of Applied Mechanics and Technical Physics - In the present study, entropy generation in a non-axisymmetric steady-state incompressible viscous flow over a single rotating porous disk is...