Simultaneous extraction of trace amounts of cobalt, nickel and copper ions using magnetic iron oxide nanoparticles without chelating agent

The present study investigates the application of Fe₃O₄ nanoparticles as an adsorbent for solid phase extraction and their subsequent determination of trace amounts of cobalt, nickel and copper from environmental water samples using flame atomic absorption spectrometry. The analyte ions were adsorbed on magnetic nanoparticles in the pH range of 10–12 and then, Fe₃O₄ nanoparticles were easily separated from the aqueous solution by applying an external magnetic field and decantation. Hence, no filtration or centrifugation was needed. After extraction and collection of magnetic nanoparticles, the analyte ions were desorbed using 1.0 M HNO₃. Several factors that may affect the preconcentration and extraction process, including pH, type and volume of eluent, sample volume, salt effect and matrix effect were optimized. Under the optimized conditions, linearity was maintained from 0.005–3.0 μg/mL for cobalt and nickel and 0.001 to 1.25 μg/mL for copper in the initial solution. The detection limits of this method for cobalt, nickel and copper ions were 0.9, 0.7 and 0.3 ng/mL, respectively. Finally, the method was successfully applied to the extraction and determination of the analyte ions in natural waters and reference plant samples.     

PVC‐Based on Thiopyrilium Derivatives Membrane Electrodes for Determination of Histamine

This study describes novel histamine‐selective electrodes, having their basis on thiopyrilium (TP) derivatives as suitable ionophores. The electrodes were prepared by incorporating the TP derivatives into plasticized poly(vinyl chloride) (PVC) membranes. These electrodes demonstrate high selectivity as far as the histamine response is considered, as compared with many common inorganic anions and other kinds of amino acids. The influence of membrane composition, pH and the effect of lipophilic cationic and anionic additives on the response characteristics of the electrode were investigated. The resulting sensor based on 2,6‐bis(4‐dimethyl amino phenyl)‐4‐phenyl thiopyrilium perchlorate (TP4) responds to histamine in a wide concentration range from 5.0 × 10^?6 to 1.0 × 10^?1 M with a slope of 54.8 ± 0.6 mV decade^?1 and detection limit of 3.0 μ mol L^?1 (～0.3 ppm). The electrode illustrates fast response time and good long‐term stability (more than 2 months). The ability to design histamine‐selective electrodes based on new thiopyrilium derivatives and both to alter selectivity and improve the response characteristics through structural changes to the charged ionophore, has been investigated. The prepared electrode was used for the determination of histamine in a synthetic human serum sample. Consequently, satisfactory recovery results were obtained over a wide concentration range of histamine.     

Novel Metronidazole Membrane Sensor Based on a 2,6‐(p‐N,N‐Dimethylaminophenyl)‐4‐Phenylthiopyrylium Perchlorate

A novel PVC‐based membrane sensor based on 2,6‐(p‐N,N‐dimethylaminophenyl)‐4‐phenylthiopyrylium perchlorate (DAPP) is described. The electrode exhibits a sub‐Nernstian response to 1‐(beta‐hydroxyethyl)‐2‐methyl‐5‐nitroimidazole (metronidazol) over a relatively wide concentration range (1.0 × 10^?1 to 1.0 × 10^?5 M) with a detection limit of 8.0 × 10^?6 M. The best performance was obtained with the membrane containing 30% poly (vinyl chloride), 50% dibutyl phthalate, 7% DAPP and 13% oleic acid. It has a fast response time (< 30 s) and can be used for at least four weeks without any major deviation. The proposed sensor revealed very good selectivity for metronidazole over a wide variety of common cations, anions and amino acids and could be used in the pH range of 6.0–7.5. It was successfully used for direct determination of metronidazole in an oral synthetic antiprotozoal as an antibacterial agent, in metronidazole tablets, and metronidazole injections and metronidazole gels.     

Fast Removal and Recovery of Methylene Blue by Activated Carbon Modified with Magnetic Iron Oxide Nanoparticles

A magnetic adsorbent was synthesized by modification of activated carbons with magnetic iron oxide nanoparticles (AC‐MIONs). The preparation method is fast and could be carried out in an ordinary condition. The AC‐MIONs were used as quite efficient adsorbents for separation of methylene blue (MB) from aqueous solution in a batch process. The effect of different parameters such as pH, temperature, electrolyte concentration, contact time and interfering ions on the removal of MB were studied. The adsorption data were analyzed by Langmuir and Freundlich isotherm models and a maximum adsorption amount of 47.62 mg g^‐1 and a langmuir adsorption equilibrium constant of 3.0 L mg^‐1 were obtained. The obtained results revealed that AC‐MIONs were effective adsorbents for fast removal of MB from different aqueous solutions. This adsorbent was successfully used for removal of MB from Karoon River water.     

Reaction of 2-Phenyl-4-(ethoxymethylene)-5(4H)-oxazolone with 3,4-Dithio-toluene in the Presence of Lewis Base

A convenient procedure for the synthesis of thiocoumarin by the condensation of 2-phenyl-4-(ethoxymethylene)-5-(4H)-oxazolone with 3,4-dithio-toluene in the presence of triethylamine is reported. Here, both thio groups are able to react with the carbonyl group to produce a mixture of isomeric products at ambient temperature. Only one of the isomers upon heating gives a new coumarin product.     

A mechanistic approach to photochemical behavior of 4‐anisyl‐4‐methyl‐2,6‐diphenyl‐4H‐thiopyran‐1,1‐dioxide

Photoisomerization of 4‐anisyl‐4‐methyl‐2,6‐diphenyl‐4H‐thiopyran‐1,1‐dioxide is described in the presence of a sensitizer and new mechanistic features are proposed. The relative molar ratios of the stereoselective photoproducts compared in the presence and the absence of sensitizer in different concentrations of the starting material using hplc. The results observed are discussed on the basis of a triplet excited state thiadi‐π‐methane rearrangement.     

Solid phase extraction and spectrophotometric determination of trace amounts of thiocyanate in real samples

A simple, selective and rapid method for solid phase extraction and spectrophotometric determination of thiocyanate using a manganese (III) tetrakis (p-sulfonatophenyl) porphyrin, [Mn (TPPS) OAC] bound to Amberlite IR-400 has been developed. The influence of pH, amount of solid phase, sample matrix, type and amount of eluting agent and flow rates i.e. variables affecting the efficiency of the extraction system were evaluated and conditions of the sample, eluting solution and active phase were optimized. The maximal capacity was found to be as 1.16 microg mL(-1) for 1200 mL. Thiocyanate ions can be eluted quantitatively with 8 mL 0.3 M ferric chloride. The enrichment factor was 150. The linear range of the determination is between 0.4-2.0 microg mL(-1) for preconcentration method with a limit of detection of 2.8 ng mL(-1). The method has been successfully applied for determination of trace amounts of thiocyanate in tap water, saliva sample and a synthetic mixture.     

Highly Selective PVC‐Based Membrane Electrode Based on 2,6‐Diphenylpyrylium Fluoroborate

A highly selective PVC‐membrane electrode based on 2,6‐diphenylpyrylium fluoroborate is presented. The electrode reveals a Nernstian potentiometric response for sulfate ion over a wide concentration range (5.0 × 10^?6‐1.0 × 10^?1 M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for sulfate over a wide variety of common organic and inorganic anions and could be used over a wide pH range (2.5–9.5). The detection limit of the sensor is 3.0 × 10^?6 M. It was successfully applied to the direct determination of salbutamol, paramomycin tablets, and as an indicator electrode for potentiometric titration of sulfate ions with barium ions.