Polythionine-decorated magnetic nanoparticles as a robust and highly effective sorbent for mercury determination in environmental water samples

Extraction, pre-concentration and determination of trace amounts of mercury ions from water samples were investigated by magnetic solid phase extraction (MSPE) method using Fe₃O₄ nanoparticles decorated with polythionine as an adsorbent. A simple chemical synthesis by catalytic reaction of thionine in the presence of FeCl₃ and hydrogen peroxide was used for preparation of the magnetic sorbent. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, vibrating sample magnetometer analysis and Fourier transform infrared spectroscopy were used to characterise the adsorbent. Mercury ions were determined by cold vapour atomic absorption spectrometry. The parameters for MSPE procedure, such as pH of the extraction solution, adsorption time, weight adsorbent, elution conditions (type, concentration and volume of the eluent), volume of the sample solution and effects of coexisting ions were investigated. The obtained optimal conditions were: sample pH of 4; sorbent amount of 4 mg; sorption time of 20 min; elution solvent of HNO₃ (0.3 mol L^?1)/thiourea (2% w/v) with volume of 2 mL, and breakthrough volume of 400 mL. A good linearity in the concentration range of 0.025–40 µg L^?1 (R² > 0.999) with the pre-concentration factor of 198 was obtained. The limits of detection and quantification were achieved as 0.008 and 0.025 µg L^?1, respectively. Furthermore, sea and river water samples were analysed and good recoveries (97.1–99.6%) were obtained.     

Set amenability for semigroups

In this paper a concept of amenability for an arbitrary subset A of discrete semigroup S called A-amenable is introduced and studied. This concept is characterized by several equivalent statements which are analogues of properties characterizing left amenable semigroups. We also obtain the relationship between this version of amenability and Følner’s condition.     

Rattle-type Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SnO<Subscript>2</Subscript> core-shell nanoparticles for dispersive solid-phase extraction of mercury ions

The synthesis of rattle-type nanostructured Fe₃O₄@SnO₂ is described along with their application to dispersive solid-phase extraction of trace amounts of mercury(II) ions prior to their determination by continuous-flow cold vapor atomic absorption spectrometry. The voids present in rattle-type structures make the material an effective substrate for adsorption of Hg(II), and also warrant high loading capacity. The unique morphology, large specific surface, magnetism property and the synergistic effect of magnetic cores and SnO₂ shells render these magnetic nanorattles an attractive candidate for solid-phase extraction of heavy metal ions.The sorbent was characterized by transmission electron microscopy, scanning electron microscopy, FTIR, energy-dispersive X-ray spectroscopy and by the Brunnauer-Emmett-Teller technique. The effects of pH value, adsorption time, amount of sorbent, volume of sample solutions, concentration and volume of eluent on extraction efficiencies were evaluated. The calibration plot is linear in the 0.1 to 40 μg·L^?1 concentration range, and the preconcentration factor is 49. The detection limit is 28 ng·L^?1. The sorbent was applied to the analysis of (spiked) river and sea water samples. Recoveries ranged from 97.2 to 100.5%.

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Graphical abstract A yolk-shell structure based on a Fe₃O₄ core and SnO₂ shell was developed as an efficient MSPE sorbent. A middle silica layer was etched by alkaline solution. The resulting sorbent was utilized for preconcentration of mercury ions from aqueous media.

     

A strategy to enhance the thermal stability of a nanostructured polypyrrole-based coating for solid phase microextraction

We report on a nanostructured self-doped polypyrrole (SPPy) film that was prepared by an electrochemical technique in an electrolyte containing fluorosulfonic acid as the sulfonation reagent. The film was applied as a new fiber material for solid-phase microextraction (SPME) of the pesticides lindane, heptachlor, aldrin, endosulfans I and II prior to their quantitation by GC with electron capture detection. The SPPy nanoparticles have a diameter of <100?nm. The introduction of covalently bound sulfo groups into the backbone of the polymer resulted in improved temperature resistance (~350?°C) and satisfactory extraction efficiency. The thermal stability of the SPPy fiber is superior to common polypyrrole fibers. Extraction was optimized by means of the Taguchi orthogonal array experimental design with an OA₁₆ (4⁵) matrix including extraction temperature, extraction time, salt concentration, stirring rate, and headspace volume. The method displays good repeatability (RSD?<?6%) and linearity (in the range from 0.78 to 100?ng?mL^?1; with an R² of >0.998. The detection limits are <0.23?ng?mL^?1. The method was successfully applied to the analysis of the pesticides in skimmed milk and fruit juice samples, and recoveries are from 84?±?1 to 105?±?1%.

Spectroscopic Study of Some Alkali and Alkaline Earth Complexes with Benzo Crown Ethers in Ethanol Solution

The interaction between Na⁺, K⁺, Mg²⁺ and Ca²⁺ ions and benzo crown ethers B15C5, DB18C6, DB21C7, DB24C8 and DB30C10 in ethanol solution has been studied spectrophotometrically at 25°C. The formation constants for 1:1 complexes were determined by computer fitting of the resulting UV-absorbance-mole ratio data. In the case of all crown ethers used, K⁺ ion was found to form the most stable complexes. The observed selectivities of different benzo crowns for the cations used are discussed in terms of the cavity-cation size ratio, number of the donating oxygens participating in the cation binding, conformations of the free and complexed ligands and ionic solvation.     

Hydrolysis of diphenylmethyltin(iv) chloride in different aqueous solutions of ethanol

The hydrolysis of [(Ph)₂MeSn(IV)]⁺ has been studied spectrophotometrically at 25ˆC and constant ionic strength of 0.1 mol dm⁻³ sodium perchlorate. Over a wide pH range, 1–11, the investigation has been performed in different aqueous solutions of ethanol. The species formed together with their formation constants have been determined using the computer program Squad. The hydrolysis constants at different media were analyzed in terms of Kamlet and Taft's parameters. A single‐parameter correlation of the formation constants, K_1‐1 and K_1‐2, versus α (hydrogen‐bond donor acidity), β (hydrogen‐bond acceptor basicity), and π^* (dipolarity/polarizability) for both cases are relatively poor in all solutions, but multiparameter correlation represents significant improvement with regard to the single‐parameter models. In this work, we have also used the normalized polarity parameter, E, alone and in combination with the Kamlet–Taft's parameters to find a better correlation of the formation constants in different aqueous solutions of ethanol. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:654–660, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20484     

A Sensitive Catalytic-Photometric Method for the Determination of Trace Amounts of Palladium(II) by Using a Computerized Probe-Type Photometer1, 2

A simple and sensitive catalytic-photometric method for the determination of trace amounts of palladium(II) based on its heterogeneous catalytic effect on the reduction of neutral red (NR) by hypophosphite (HP) has been developed. The reaction was monitored at 530 nm and the time elapsed (At) for the absorbance to decrease from its initial value by 1.5 absorbance units was recorded using the variable time method. The influence of reaction variables is discussed. The ranges of linearity were 0.108–6.533 ppm and 0.032–0.653 ppm palladium(II) at temperatures of 30 and 55°C, respectively. The relative standard deviations of the developed method were 2.5 and 2.7% (for 8 replicate determinations of 1.110 ppm Pd(II)) at 30 and 55°C, respectively. The effect of interferences from other metal ions and some anions was studied. The developed method has been successfully tested for determination of Pd(II) in Al–Si–Pd catalysts.     

Calculation of combined conduction-radiation heat transfer reduction using thick concentric spheres with temperature-dependent emissivity as radiation shields

In this study, the rate of conduction-radiation heat transfer between two thick concentric spheres is analytically investigated because of the ever-increasing importance of radiation shield applications. The heat transfer rate, the percentage of reduction in heat transfer, temperature and emissivity of surfaces are calculated when one and two thick radiation shields are placed between two thick spheres. The calculations show that the use of a radiation shield with a lower emissivity is better than two radiation shields with a higher emissivity to reduce the heat transfer rate. In addition, optimal combinations of radiation shields with different materials are proposed.     

Magnetite nanoparticles surface-modified with a zinc(II)-carboxylate Schiff base ligand as a sorbent for solid-phase extraction of organochlorine pesticides from seawater

Magnetite nanoparticles were surface-modified with mercaptoacetic acid (MAA), complexed with Zn(II), and then treated with the dual Schiff base (referred to as imine-based ligand; IBL; obtained by reaction of p-aminobenzoic acid and 2,3-butanedione) to give particles with an architecture of type Fe₃O₄@MAA@IBL. These are shown to be viable sorbents for magnetic solid phase extraction of organochlorine pesticides (OCPs) from seawater samples. Efficient extraction of the OCPs probably is due to lone pair-π, π-complexation and π-interactions. The sorbent was characterized by transmission electron microscopy, scanning electron microscopy, FT-IR and energy-dispersive X-ray spectroscopy. The effects of the volumes of sample, sorbent dosage and eluent, adsorption and desorption times, and the salinity of the sample on the extraction efficiencies were optimized. The OCPs (heptachlor, aldrin, dieldrin, p,p’-DDE and p,p’-DDT) were quantified by gas chromatography with microelectron capture detection. Under optimal conditions, the limit of detections range was between 1.0 and 1.9 ng L^?1. The enrichment factors are between 84.1 and 99.9 %. The sorbent was applied to the rapid extraction of trace quantities of OCPs from seawater samples and gave good relative recoveries (78 to 108 %) and relative standard deviations (<8.3 %).

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Graphical Abstract Fe₃O₄ nanoparticles were functionalized with mercaptoacetic acid. The carboxylate was coordinated with Zn(II) and the ligands were immobilized via coordination with Zn(II). The lone pair-π, π-complexation and π-interaction of modified magnetite nanoparticles made this sorbent effective for extraction of organochlorine pesticides.