Synthesis and characterization of novel ferrocenyl glycidyl ether polymer,ferrocenyl poly (epichlorohydrin) and ferrocenyl poly (glycidyl azide)

Poly (ferrocenyl glycidyl ether) was synthesized by polymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane (FcEpo) using toluene solution of methylaluminoxane as the catalyst. Copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin was used for the synthesis of another ferrocenyl based poly (epichlorohydrin). Ferrocenyl based poly (glycidyl azide), GAP, was synthesized by treatment of sodium azide with this copolymer in DMF as solvent at room temperature. The synthesized ferrocenyl based polymers were characterized by FT-IR, ¹HNMR, UV–Vis, TGA, DSC and GPC analysis. The UV–Vis spectra of synthesized polymers show the absorption band of ferrocene moiety at about 450 nm. The TGA and DSC analysis show that poly (ferrocenyl glycidyl ether) has good thermal stability. The TGA analysis shows that the copolymerization of 2-[(4-ferrocenylbutoxy)methyl]oxirane with epichlorohydrin improved the thermal stability of the copolymer. The GPC analysis of poly (ferrocenyl glycidyl ether), ferrocenyl based poly (epichlorohydrin) and Ferrocenyl based poly (glycidyl azide) show the PDI between 1.14–1.17. The electrochemical behavior of synthesized polymers was investigated by cyclic voltammetry (CV) measurements. The CV curves of synthesized polymers show good electrochemical performance and there is one redox system with the single-electron reversible reaction that associated with ferrocene moiety in polymers structure. The anodic and cathodic peak currents increased with scan rate confirmed redox reactions in the system are kinetically fast diffusion-controlled reactions.     

The effect of brine salinity on water-in-oil emulsion stability through droplet size distribution analysis: A case study

Water-in-oil emulsion usually forms during waterflooding in some heavy oil reservoirs. The composition and salinity of the injected water critically affect the w/o emulsion droplet size distribution, which control the emulsion stability and emulsion flow in porous media. The aim of the present work is to assess the effect of different sea water salinities on w/o emulsion stability through microscopic imaging. Therefore, w/o emulsions were prepared with different sea water samples, which were synthesized to resemble Persian Gulf, Mediterranean, Red Sea, and North Sea water samples. The results showed that log-normal distribution function predicts very well the experimental data to track the emulsion droplet size distribution, and then it was used for the emulsion stability analysis. It was found that among the four emulsion samples, North Sea emulsion with the lowest NaCl and TDS concentration of 24.12?g/L and 34.44?g/L remained stable up to almost 24 hours, while Red sea emulsion with the highest NaCl and TDS concentration of 32.39?g/L and 41?g/L became unstable after 6-hour period. This indicated that as the brine concentration increases, the w/o emulsion droplets would be larger due to the higher rate of aggregation and coalescence, and the emulsion stability decreases.     

CuI-catalyzed thioarylation of active methylene compounds with in situ generated benzenethiols: Preparation of α-thioaryl-β-dicarbonyls and 4-thioaryl-5-pyrazolones

In this paper, a one-step copper-catalyzed procedure for oxidative coupling of active methylene compounds including cyclic β-diketones, cyclic β-ketoesters and 5-pyrazolone with benzenethiols is described. Benzenethiols are in situ generated in the reaction mixture from aryl halides and thiourea as sulfur transfer reagent. α-Thioaryl compounds are obtained in excellent yields and in short reaction time via the process which is free from the foul smell of thiols.     

Deferiprone solubility in some non-aqueous mono-solvents at different temperatures: experimental data and thermodynamic modelling

The solubility of deferiprone (DFP) in five organic solvents including ethyl acetate, chloroform, acetonitrile, 1,4-dioxane and dichloromethane was investigated by the flask-shake method under atmospheric pressure at temperatures ranging from 293.15 to 313.15 K. In general, the solubility (mol L^–1) obeyed the following order from high to low in different mono-solvents: dichloromethane > chloroform > acetonitrile > 1,4-dioxane > ethyl acetate. The solubility of DFP in the mono-solvents increased with a rise of temperature. The solubility data were successfully correlated with the van’t Hoff equation. The generated data in this work and the previously published data were used to calculate the thermodynamic parameters of the system using the modified van’t Hoff equation, and the derived thermodynamic properties were correlated using Abraham solvation parameters.     

Structure elucidation,DNA binding,DFT, molecular docking and cytotoxic activity studies on novel single crystal (E)-1-(2-fluorobenzylidene)thiosemicarbazide

Compound 3 {(E)-1-(2-fluorobenzylidene)thiosemicarbazide} – a new Schiff base of thiosemicarbazide has been synthesized, characterized and reported for crystal structure. Planer side chain in the crystal structure was observed co-planer with aromatic ring plane and molecules were connected into centrosymmetric dimmers via intermolecular hydrogen bonding. DFT geometry optimization and the relevant quantum parameters indicated unstable and reactive nature of compound 3. Experimental and theoretical findings for DNA binding by UV–visible, cyclic voltammetry and molecular docking studies showed consistency in kinetic (K_b) and thermodynamic (ΔG) parameters and that compound 3 significantly interacted with DNA via intercalation. Viscometric analysis further comprehended intercalation as possible binding mode of the compound with DNA and non-denaturing of DNA in the presence of 10% aqueous DMSO. Docked parameters further assured the drug like characteristics of the investigated compound as fit in Lipinski’s criteria. Dose dependant cytotoxic activity of compound 3 against human Huh-7 cell line indicated its anti-cancer potential at 100?µg/ml concentration.     

Indirect Determination of Trace Copper(II) by Adsorptive Stripping Voltammetry with Zincon at a Carbon Paste Electrode

Traces of copper(II) can be determined by adsorptive stripping voltammetry using 2‐carboxy‐2′‐hydroxy‐5′‐sulfoformazyl benzene (Zincon) as complex forming reagent. First in phosphate buffer pH 6.4, copper(II)‐Zincon complex was adsorbed on carbon paste electrode (CPE) with an accumulation potential of 0.6 V. Following this, adsorbed complex was oxidized and detected by differential pulse voltammetric (DPV) scan from 0.6 to 1.0 V. The effective parameters in sensor response were examined. The detection limit (DL) of copper(II) was 1.1 μg/L and relative standard deviations (RSDs) for 10 and 200 μg/L Cu(II) were 1.81 and 1.03%, respectively. The calibration curve was linear for 2–220 μg/L copper(II). The resulting CPE does not use mercury and therefore, has a positive environmental benefit. The method, which is reasonably sensitive and selective, has been successfully applied to the determination of trace amount of copper in water and human hair samples.     

Generation of Haploid Spermatids on Silk Fibroin-Alginate-Laminin-Based Porous 3D Scaffolds

In vitro production of sperm is a desirable idea for fertility preservation in azoospermic men and prepubertal boys suffering from cancer. In this study, a biocompatible porous scaffold based on a triad mixture of silk fibroin (SF), alginate (Alg), and laminin (LM) is developed to facilitate the differentiation of mouse spermatogonia stem cells (SSCs). Following SF extraction, the content is analyzed by SDS-PAGE and stable porous 3D scaffolds are successfully prepared by merely Alg, SF, and a combination of Alg-SF, or Alg-SF-LM through freeze-drying. Then, the biomimetic scaffolds are characterized regarding the structural and biological properties, water absorption capacity, biocompatibility, biodegradability, and mechanical behavior. Neonatal mice testicular cells are seeded on three-dimensional scaffolds and their differentiation efficiency is evaluated using real-time PCR, flow cytometry, immunohistochemistry. Blend matrices showed uniform porous microstructures with interconnected networks, which maintained long-term stability and mechanical properties better than homogenous structures. Molecular analysis of the cells after 21 days of culture showed that the expression of differentiation-related proteins in cells that are developed in composite scaffolds is significantly higher than in other groups. The application of a composite system can lead to the differentiation of SSCs, paving the way for a novel infertility treatment landscape in the future.     

New 3D and 2D supramolecular heteroleptic palladium(II) dithiocarbamates as potent anticancer agents

Three new heteroleptic palladium(II) dithiocarbamates with better in vitro anticancer activity than cisplatin were synthesized and characterized by different analytical techniques, elemental analysis, FTIR, NMR, and single crystal X-ray diffraction analysis. The Pd center is chelated by dithiocarbamate ligand {4-benzylpiperazine-1-carbodithioate (1) and (3) or (4-(2-methoxyphenyl)piperazine-1-carbodithioate (2)}, triorganophosphine {tris-(4-flourophenyl)-phosphine (1) and (2) or tris-(4-chlorophenyl)phosphine (3)}, and a chloro-group, resulting in a square planar geometry. The packing diagram reveals a 3D network (1 and 2) and a 2D network (3) composed of various 1D chains in which the molecules are linked via hydrogen bonds (1–3) and halide?π (1, 3) interactions. The anticancer activities of complexes against HeLa cell line varies in the sequence 2 (23.438 μM) > 1 (38.293 μM) > 3 (47.554 μM) > cisplatin (78.075 μM). The cytotoxicity of these complexes is due to their strong induction of oxidative stress and DNA-damage ability leading to apoptosis.     

Sulfonic acid–functionalized magnetic Fe3-xTixO4 nanoparticles: New recyclable heterogeneous catalyst for one-pot synthesis of tetrahydrobenzo[b]pyrans and dihydropyrano[2,3-c]pyrazole derivatives

In this work, titanomagnetite nanoparticles (Fe_3-xTi_xO₄) have been used as a novel suppport for the synthesis of a magnetic acidic catalyst. These nanoparticles were functionalized with sulfonic acid groups to prepare the Fe_3-xTi_xO₄@SO₃H nanoparticles. The synthesized acidic nanoparticles have been explored as new and efficient recyclable heterogeneous catalyst for a one-pot, three-component synthesis of tetrahydrobenzo[b]pyrans known as 4H-chromenes and 1,4-dihydropyrano[2,3-c]pyrazoles. The structure of the catalyst was established by infrared, energy dispersive x-ray (EDX), and scanning electron microscopy analyses. The reactions proceed smoothly to furnish the respective products in excellent yields and short reaction times. The facile reaction conditions, easy isolation of the products, versatility, and easy magnetic separation and reusability of the catalyst with no significant loss of activity are the main merits of the present method.     

Diastereoselective synthesis of novel <Emphasis Type="Italic">N</Emphasis>-substituted pyrrolidine-2-one containing piperazine derivatives

Synthesis of novel hybrid derivatives of two known scaffolds, pyrrolidine-2-one and piperazine, is described. Initially, the Ugi reaction of phenylglyoxal, aromatic amines, coumarin-3-carboxylic acid and isocyanides in methanol resulted in the formation of dihydrochromeno[3,4-c]pyrrole-3,4-diones. The obtained products were then treated with N-alkylpiperazines in dichloromethane to afford the novel N-substituted pyrrolidine-2-one containing piperazine derivatives in satisfactory yields. The proof of the structures was carried out by means of spectroscopic information and X-ray crystallography.