Bulk polymer nanoparticles containing a tetrakis(3-hydroxyphenyl)porphyrin for fast and highly selective separation of mercury ions

We report on the synthesis of polymeric nanoparticles (PNPs) containing a tetrakis(3-hydroxyphenyl)porphyrin, and their use for the separation of mercury(II) ion. The PNPs were prepared by bulk polymerization from methacrylic acid (the monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator) and the mercury(II) complex of 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin. The Hg(II) ion was then removed by treatment with dilute hydrochloric acid. The PNPs were characterized by colorimetry, FT-IR spectroscopy, and scanning electron microscopy. The material is capable of binding Hg(II) from analyte samples. Bound Hg(II) ions can be eluted with dilute nitric acid and then quantified by cold vapor AAS. The extraction efficiency, the effects of pH, preconcentration and leaching times, sample volume, and of the nature, concentration and volume of eluent were investigated. The maximum adsorption capacity of the PNPs is 249 mg g^?1, the relative standard deviation of the AAS assay is 2.2 %, and the limit of detection (3σ) is 8 ng.L^?1. The nanoparticles exhibit excellent selectivity for Hg(II) ion over other metal ions and were successfully applied to the selective extraction and determination of Hg(II) ion in spiked water samples.

Anodic stripping voltammetry of silver(I) using a carbon paste electrode modified with multi-walled carbon nanotubes

We describe a silver(I)-selective carbon paste electrode modified with multi-walled carbon nanotubes and a silver-chelating Schiff base, and its electrochemical response to Ag(I). Effects of reduction potential and time, accumulation time, pH of the solution and the stripping medium were studied by differential pulse anodic stripping voltammetry and optimized. The findings resulted in a method for the determination of silver over a linear response range (from 0.5 to 235 ng?mL^?1) and with a detection limit as low as 0.08 ng?mL^?1. The sensor displays good repeatability (with the RSD of ±?2.75 % for 7 replicates) and was applied to the determination of Ag(I) in water samples and X-ray photographic films.

One-Pot Synthesis of 3,5-Disubstituted 1,2,4-Oxadiazoles Directly from Nitrile and Hydroxylamine Hydrochloride Under Solvent-Free Conditions Using Potassium Fluoride as Catalyst and Solid Support

A one-pot synthesis of 3,5-disubstituted 1,2,4-oxadiazoles with two identical substituents directly from the reaction of nitriles and hydroxylamine hydrochloride in the presence of potassium fluoride as catalyst and solid support under solvent-free condition is described. Moreover, the formation of products has been discussed, and a plausible mechanism has been presented. Simplicity of the process, workup in aqueous media, and excellent yields are some advantages of this method.     

Facile Synthesis of Benzotriazole Derivatives Using Nanoparticles of Organosilane-Based Nitrite Ionic Liquid Immobilized on Silica and Two Room-Temperature Nitrite Ionic Liquids

Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica, 1-butyl-3-methylimidazolium nitrite, and 1-(3-trimethoxysilylpropyl)-3-methylimidazolium nitrite were used as effective reagents for the preparation of benzotriazole derivatives from 1,2-diaminobenzenes at room temperature under mild solvent-free conditions. These ionic liquids play as nitrosonium sources in this procedure.1,2-Diaminobenzene derivatives have been treated with ionic liquids to give the related diaminobenzenes in very good to excellent yields in short reaction times.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the full experimental and spectral details.     

Isolation and biological evaluation of chromone alkaloid dysoline,a new regioisomer of rohitukine from Dysoxylum binectariferum

The chromone alkaloid dysoline (1), a new regioisomer of rohitukine (2) along with rohitukine and rohitukine-N-oxide (3) were isolated from the stem barks of Dysoxylum binectariferum. The structure of dysoline (1) was determined by extensive 2D-NMR studies and the absolute configuration was established by NOESY and CD spectra. Dysoline (1) consisted of a 5,7-dihydroxy-2-methylchromone nucleus substituted with a 2′-hydroxylated N-Me piperidine ring at the C-6 position. Dysoline differs from rohitukine by the position of the piperidine ring on the chromone nucleus. Dysoline displayed promising cytotoxicity in HT1080 fibrosarcoma cells with an IC₅₀ of 0.21 μM, and also displayed significant inhibition of proinflammatory cytokines TNF-α and IL-6.     

Modification of the Scaled Particle Theory for Solubility of Non-Polar Gases in Water

In this work based on the modified scaled particle theory (SPT), the solubility of non-polar gases (He, Ar, N₂, H₂, O₂, CO₂ and CH₄) in water has been studied over a wide range of temperatures. Calculations of Henry’s law constant by the SPT are related to the inherent physical properties and parameters of solvent and solute, all of which are considered temperature dependent. The temperature dependence of molar volume and hard sphere diameter of solvent and polarizability of solute have the most significant effects on the solubilities of gases in water. The average relative deviation is less than 3 %. Also, the effect of different mixing rules in the application of SPT to prediction of gas solubility has been studied.     

The electrocatalytic behavior of electrodeposited Ni–Mo–P alloy films towards ethanol electrooxidation

Ternary Ni–Mo–P thin films have been electrodeposited from citrate‐based electrolyte onto graphite substrates for application as anode catalysts for ethanol electrooxidation. The operating deposition parameters were optimized to produce Ni–Mo–P alloy films of outstanding catalytic activity. The phase structure of the deposits was evaluated employing X‐ray diffraction technique. Morphology and chemical composition of the deposited alloy films were studied using scanning electron microscopy and energy‐dispersive X‐ray analysis, respectively. The results demonstrated that the rate of Ni–Mo–P deposition increases with increasing the ammonium molybdate concentration in the plating electrolyte up to 10 g l^?1. Also, the amount of Mo in the deposits increases with increasing the ammonium molybdate concentration up to 7.5 g l^?1, and the maximum Mo content in the film was 9.1 at.%. The catalytic activity of Ni–Mo–P/C alloy films has been evaluated towards electrooxidation of ethanol in 1.0 M NaOH solution by using cyclic voltammetry and chronoamperometry. The catalytic performance of the prepared anodes as a function of the amount of Mo was studied. The results showed an increase in the oxidation peak current density of ethanol with increasing the Mo at.% in the deposited alloy films. Additionally, Ni–Mo–P/C electrodes displayed significantly improved catalytic activity and stability towards electrooxidation of ethanol compared with that of Ni–P/C electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of Interglycosidically S‐Linked 1‐Thio‐Oligosaccharides Under Microwave Irradiation*

Microwave irradiation (MWI) has accelerated the synthesis of S‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)thiouronium bromide (2a), whose reaction with 2,3,4,6‐tetra‐O‐acetyl‐α‐D‐glucopyranosyl bromide (1a) in the presence of Et₃N afforded stereoselectively the acetylated β,β‐1‐thiotrehalose 4a. Similarly, the respective D‐galactopyranosyl 4b and 2‐acetylamino‐2‐deoxy‐D‐glucopyranosyl 4c analog as well as 4,4′‐di‐O‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐galactopyranosyl) 4d and 4,4′‐di‐O‐(2,3,4,6‐tetra‐O‐acetyl‐α‐D‐glucopyranosyl) 4e derivatives of 2,2′,3,3′,6,6′‐hexa‐O‐acetyl β,β‐1‐thiotrehalose were prepared.     

Uranium recovery from UCF liquid waste by nanoporous MCM-41: breakthrough capacity and elution behavior studies

Adsorption and recovery of uranium by nanoporous MCM-41 from aqueous solutions (synthetic solution and uranium conversion facility liquid waste) were investigated by use of a fixed-bed column (1.2 cm diameter and 3.0 cm height). Adsorption was carried out at flow rates 0.2 and 0.5 mL min^?1, which correspond to retention times of 10 and 6 min. The maximum breakthrough capacity for uranium ions was achieved by use of nanoporous MCM-41 at the optimum pH of 3.6 and flow rate 0.2 mL min^?1 (61.95 μg g^?1). The Thomas and Yan models were applied to the experimental data, by use of linear regression, to determine the characteristics of the column for process design. The breakthrough curves calculated from the models were in good agreement with the experimental data. The elution behavior of uranium on nanoporous MCM-41 was studied with different eluents; the results showed that 0.1 M HCl is good eluent for uranium recovery. The regenerated column could be used in a multitude of adsorption–desorption cycles.     

Synthesis and performance of electroless Ni–P–TiCN composite coatings on Al substrate

Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H₂SO₄ with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd.