Selective solid-phase extraction and separation of trace gold, palladium and platinum using activated carbon modified with ethyl-3-(2-aminoethylamino)-2-chlorobut-2-enoate

Activated carbon was chemically modified with ethyl-3-(2-aminoethylamino)-2-chlorobut-2-enoate to obtain a material for selective solid-phase extraction of trace Au(III), Pd(II) and Pt(IV) prior to their determination by inductively coupled plasma atomic emission spectrometry. Experimental conditions such as effects of pH, shaking time, sample flow rate and volume, elution and interfering ions were studied. The ions Au(III), Pd(II) and Pt(IV) can be quantitatively adsorbed on the new sorbent from solution of pH 1. The adsorbed ions were then eluted with 0.1 mol L^?1 hydrochloric acid and containing 4% thiourea. Many common ions do not interfere. The adsorption capacity of the material is 305, 92, and 126 mg g^?1 for Au(III), Pd(II) and Pt(IV), respectively, and the detection limits are 5, 11 and 9 ng mL^?1. The relative standard deviation is less than 3.0% (n?=?8) under optimum conditions. The method was validated by analyzing two certified reference materials and successfully applied to the preconcentration and determination of these ions in actual samples with satisfactory results.

Dithizone-modified nanoporous fructose as a novel sorbent for solid-phase extraction of ultra-trace levels of heavy metals

We are introducing nanoporous fructose (np-F) modified with dithizone as a new solid-phase for extraction of heavy metals ions including cadmium(II), copper(II), nickel(II) and lead(II). Effects of pH value, flow rates, type, concentration and volume of the eluent, breakthrough volume, and of other ions were studied. Under optimized conditions, the extraction efficiency is >97 %, and the limits of detection are 0.025, 0.15, 0.5 and 1.2 ng mL^?1 for the ions of cadmium, copper, nickel, and lead, respectively, and the adsorption capacities for these ions are 101, 81, 74 and 178 mg g^?1. The modified np-F sorbent was characterized by thermogravimetric analysis, differential thermal analysis, transmission electron microscopy, Fourier transform infrared spectrometry, X-ray diffraction, and nitrogen adsorption surface area (BET) measurements.

Novel ion-imprinted polymer coated on nanoporous silica as a highly selective sorbent for the extraction of ultratrace quantities of gold ions from mine stone samples

We have developed a gold ion-imprinted polymer (GIP) by incorporating a dipyridyl ligand into an ethylene glycol dimethacrylate matrix which then was coated onto porous silica particles. The material was used for the selective extraction of ultratrace quantities of gold ion from mine stones, this followed by its quantitation by FAAS. The effects of concentration and volume of eluent, pH of the solution, flow rates of sample and eluent, and effect of potentially interfering ions, especially palladium and platinum, was investigated. The limit of detection is <0.2 ng?mL^?1, the precision (RSD%) is 1.03 %, and recoveries are >99 %. In order to show the high selectivity and efficiency of the new sorbent, the results were compared to those obtained with more simple sorbents possessing the same functional groups. The accuracy of the method was demonstrated by the accurate determination of gold ions in a certified reference material. To the best of our knowledge, there is no report so far on an imprint for gold ions that has such a selectivity over Pd(II) and Pt(II) ions.

Selective solid-phase extraction of trace Au(III), Pd(II) and Pt(IV) using activated carbon modified with 2,6-diaminopyridine

A new sorbent was prepared by immobilization of 2,6-diaminopyridine on activated carbon and then used as a solid-phase extractant for trace Au(III), Pd(II) and Pt(IV) before their determination by ICP-AES. Effects of pH, the shaking time, the sample flow rate and volume, the elution condition and the potentially interfering ions were investigated. The optimum pH value is 1. The maximum static adsorption capacity for the three ions is 202.7, 38.5 and 30.1?mg?g^?1, respectively. The adsorbed metal ions can be completely eluted by 2?mL of the eluent solution that contains 0.05?mol?L^?1 HCl and 5% thiourea. Common other ions do not interfere. The detection limits (3??) are 0.16, 0.33 and 0.29?ng?mL^?1, respectively. The relative standard deviation (RSD) was lower than 3.0% (n?=?8). The new sorbent was applied to the preconcentration of the three ions in ore and rock samples with satisfactory results.

A highly selective fluorescent probe for the detection of palladium(II) ion in cells and aqueous media

We report on a fluorescent probe for the optical (and even bare eye) detection of palladium(II) ion which causes the probe to undergo a strong increase in absorbance and fluorescence. The probe is easily synthesized from rhodamine B hydrazide and 9-anthraldehyde and displays high selectivity over other metal ions. Fluorescence intensity and absorbance are linearly proportional to the concentration of Pd(II) in the 0–7 μM and 0–1 μM concentration range, respectively, with detection limits of 0.21 μM and 0.03 μM. The probe can detect Pd(II) with virtually no interferences by other metal ions and anions. It was applied to intracellular imaging of Pd(II) in living cells and to its determination in a palladium-containing catalyst and in spiked water samples.

Separation and preconcentration of gold and palladium ions with a carboxylated pillar[5]arene derived sorbent prior to their determination by flow injection FAAS

We report on the use of a water-insoluble pillar[5]arene derivative carrying ten carboxy groups as an adsorbent, packed in a glass microcolumn, for the separation and preconcentration of trace gold (Au) and palladium (Pd). Sample pH, sample loading time, sample flow rate, eluent concentration, and eluent flow rate were optimized. Effects of potentially interfering metal ions that are commonly encountered in soil were also investigated. Under the optimized conditions, the enrichment factors for Au and Pd are 12 and 16, respectively. Flow injection in combination with flame atomic absorption spectrometry was then applied for the quantitation of the elements. The analytical range is linear in the range between 0.05 and 1 μg mL^?1 for both Au and Pd. The limits of detection are 15.9 μg L^?1 for Au and 16.0 μg L^?1 for Pd, with relative standard deviations (for n?=?11) of 0.7 % (Au) and 0.4 % (Pd), respectively. The accuracy of the method was validated using certified reference materials (coal and ash) and geological samples. Figure

A pillar[5]arene derivative carrying ten carboxy groups was used for the adsorption of Au(III) and Pd(II) ions which then were determined by flow-injection FAAS. After optimization, the method was successfully applied to the determination of these ions in certified reference materials and geological samples     

Solid phase extraction of heavy metal ions based on a novel functionalized magnetic multi-walled carbon nanotube composite with the aid of experimental design methodology

We report that magnetic multiwalled carbon nanotubes functionalized with 8-aminoquinoline can be applied to the preconcentration of Cd(II), Pb(II) and Ni(II) ions. The parameters affecting preconcentration were optimized by a Box-Behnken design through response surface methodology. Three variables (extraction time, magnetic sorbent amount, and pH value) were selected as the main factors affecting sorption, and four variables (type, volume and concentration of the eluent; elution time) were selected for optimizing elution. Following sorption and elution, the ions were quantified by FAAS. The LODs are 0.09, 0.72, and 1.0 ng mL^?1 for Cd(II), Ni(II), and Pb(II) ions, respectively. The relative standard deviations are <5.1 % for five separate batch determinations at 30 ng mL^?1 level of Cd(II), Ni(II), and Pb(II) ions. The sorption capacities (in mg g^?1) of this new sorbent are 201 for Cd(II), 150 for Pb(II), and 172 Ni(II). The composite was successfully applied to the rapid extraction of trace quantities of heavy metal ions in fish, sediment, soil, and water samples.

A magnetic metal-organic framework as a new sorbent for solid-phase extraction of copper(II), and its determination by electrothermal AAS

We report on the synthesis of Fe₃O₄-functionalized metal-organic framework (m-MOF) composite from Zn(II) and 2-aminoterephthalic acid by a hydrothermal reaction. The magnetic composite is iso-reticular and was characterized by FTIR, X-ray diffraction, SEM, magnetization, and TGA. The m-MOF was then applied as a sorbent for the solid-phase extraction of trace levels of copper ions with subsequent quantification by electrothermal AAS. The amount of sorbent applied, the pH of the sample solution, extraction time, eluent concentration and volume, and desorption time were optimized. Under the optimum conditions, the enrichment factor is 50, and the sorption capacity of the material is 2.4 mg g^?1. The calibration plot is linear over the 0.1 to 10 μg L^?1 Cu(II) concentration range, the relative standard deviation is 0.4 % at a level of 0.1 μg L^?1 (for n?=?10), and the detection limit is as low as 73 ng L^?1. We consider this magnetic MOF composite to be a promising and highly efficient material for the preconcentration of metal ions.

Dipyridylamine-modified nanoporous silicas as new sorbents for the separation and pre-concentration of palladium

Nanoporous silicas of the type SBA-15 (Santa Barbara Amorphous) and MCM-48 (Mobile Composition of Material) were modified with dipyridylamine (dipy) and used as solid phases for the extraction of Pd(II) ions. The experimental conditions (pH, sample and eluent flow rates, type and quantity of eluent) were optimized. The recovery values were ~ 99.7 and ~ 93.4% for dipy-MCM-48 and dipy-SBA-15, respectively, the limits of detection were <0.08 and <0.11 ng L^?1, the pre-concentration factors were 725 and 550, and the adsorption capacity was >78 mg g^?1. The procedure was applied to the preconcentration of Pd(II) in real samples.

A nanosized cadmium(II)-imprinted polymer for use in selective trace determination of cadmium in complex matrices

We describe a nanosized Cd(II)-imprinted polymer that was prepared from 4-vinyl pyridine (the functional monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator), neocuproine (the ligand), and Cd(II) (the template ion) by precipitation polymerization in acetonitrile as the solvent. The imprinted polymer was characterized by X-ray diffraction, thermogravimetric analysis, differential thermal analysis, and scanning electron microscopy. The maximum adsorption capacity of the nanosized sorbent was calculated to be 64 mg g^?1. Cadmium(II) was then quantified by FAAS. The relative standard deviation and limit of detection are 4.2 % and 0.2 μg L^?1, respectively. The imprinted polymer displays improve selectivity for Cd(II) ions over a range of competing metal ions with the same charge and similar ionic radius. This nanosized sorbent is an efficient solid phase for selective extraction and preconcentration of Cd(II) in complex matrices. The method was successfully applied to the trace determination of Cd(II) in food and water samples.

A nanoflower shaped gold-palladium alloy on graphene oxide nanosheets with exceptional activity for electrochemical oxidation of ethanol

We report on a new and facile method for the preparation of well-dispersed gold-palladium (AuPd) flower-shaped nanostructures on sheets of graphene oxide (GO). Transmission electron microscopy and high angle annular dark field STEM were used to characterize the morphology and composition of the new nanohybrids. The AuPd/GO composites display high electrocatalytic activity for the oxidation of ethanol in strongly alkaline medium as examined by cyclic voltammetry and chronoamperometry. Both the current density (13.16 mA?·?cm^?2 at a working potential of ?0.12 V) and the long-time stability are superior to a commercial Pd-on-carbon catalyst which is attributed to the cooperative action of the catalytic activities of Au and Pd, and the good dispersion of the alloy on the nanosheets.

Differential pulse anodic stripping voltammetric determination of Cd and Pb at a bismuth glassy carbon electrode modified with Nafion, poly(2,5-dimercapto-1,3,4-thiadiazole) and multiwalled carbon nanotubes

A simple, cheap, and nonpolluting method was developed for the cloud point extraction of gold (Au) and palladium (Pd). It is based on the complexation reaction of Au and Pd with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and micelle mediated extraction of the complex using the non-ionic surfactant poly(ethylene glycol) mono-p-nonylphenyl ether (PONPE 7.5). Under the optimized experimental conditions, the enrichment factors are 16 and 17 for Au and Pd, respectively, for 15?mL of preconcentrated solution. The limits of detection are 3.8???g?L^?1 and 1.8???g?L^?1 for Au and Pd, respectively. The relative standard deviations are 1.4% for Au and 0.6% for Pd (n?=?11). The method was successfully applied to the determination of Au and Pd in certified reference materials and mine samples.

Thermally treated bare gold nanoparticles for colorimetric sensing of copper ions

We demonstrate a sensitive and rapid colorimetric assay for selective detection of copper ions based on the strong coordination between Cu(II) ions and the tetrahydroxyaurate anions [Au(OH)₄]^? on the surface of thermally treated bare gold nanoparticles (GNPs). The method for making the unmodified GNPs is simple and results in a nanomaterial with a highly specific response to Cu(II). The thermal treatment of the bare GNPs and the recognition of Cu(II) ions is accomplished in a single step within 5 min. The presence of Cu(II) causes the color to change from red to purple-blue. The limit of detection (LOD) is 0.04 μM of Cu(II) when using UV–vis spectrometry and ratioing the absorbances at 650 and 515 nm, respectively. The method also is amenable to bare eye (visual) inspection and in this case has an LOD of 2.0 μM of Cu(II).

Preconcentration of mercury(II) using a thiol-functionalized metal-organic framework nanocomposite as a sorbent

A novel type of porous metal-organic framework (MOF) was obtained from thiol-modified silica nanoparticles and the copper(II) complex of trimesic acid. It is shown that this nanocomposite is well suitable for the preconcentration of Hg(II) ions. The nanocomposite was characterized by Fourier transfer infrared spectroscopy, X-ray powder diffraction, energy-dispersive X-ray diffraction and scanning electron microscopy. The effects of pH value, sorption time, elution time, the volume and concentration of eluent were investigated. Equilibrium isotherms were studied, and four models were applied to analyze the equilibrium adsorption data. The results revealed that the adsorption process obeyed the Langmuir model. The maximum monolayer capacity and the Langmuir constant are 210 mg g^?1 and 0.273 L mg^?1, respectively. The new MOF-based nanocomposite is shown to be an efficient and selective sorbent for Hg(II). Under the optimal conditions, the limit of detection is 20 pg mL^?1 of Hg(II), and the relative standard deviation is <7.2 % (for n?=?3). The sorbent was successfully applied to the rapid extraction of Hg(II) ions from fish, sediment, and water samples.

Polythiophene-coated Fe3O4 nanoparticles as a selective adsorbent for magnetic solid-phase extraction of silver(I), gold(III), copper(II) and palladium(II)

We have developed a fast method for sensitive extraction and determination of the metal ions silver(I), gold(III), copper(II) and palladium(II). Fe₃O₄ magnetic nanoparticles were modified with polythiophene and used for extraction the metal ions without a chelating agent. Following extraction, the ions were determined by flow injection inductively coupled plasma optical emission spectrometry. The influence of sample pH, type and volume of eluent, amount of adsorbent, sample volume and time of adsorption and desorption were optimized. Under the optimum conditions, the calibration plots are linear in the 0.75 to 100 μg L^?1 concentration range (R²?>?0.998), limits of detection in the range from 0.2 to 2.0 μg L^?1, and enhancement factors in the range from 70 to 129. Precisions, expressed as relative standard deviations, are lower than 4.2 %. The applicability of the method was demonstrated by the successful analysis of tap water, mineral water, and river water.

Micro-solid phase extraction of ochratoxin A, and its determination in urine using capillary electrophoresis

We describe a simple, environmentally friendly and selective technique for the determination of ochratoxin A (OTA) in urine. It involves (a) the use of a molecularly imprinted polymer as a sorbent in micro-solid-phase extraction in which the sorbent is contained in a propylene membrane envelope, and (b) separation and detection by capillary electrophoresis (CE). Under optimized conditions, response is linear in the range between 50 and 300 ng mL^?1 (with a correlation coefficient of 0.9989), relative standard deviations range from 4 to 8 %, the detection limit for OTA in urine is 11.2 ng mL^?1 (with a quantification limits of 32.5 ng mL^?1) which is lower than those of previously reported methods for solid-phase extraction combined with CE. The recoveries of OTA from urine spiked at levels of 50, 150 and 300 ng mL^?1 ranged from 93 to 97 %.

MALDI-Q-TOF mass spectrometric determination of gold and platinum in tissues using their diethyldithiocarbamate chelate complexes

A rapid determination method is presented for gold (Au³⁺) and platinum (Pt⁴⁺) in tissues using matrix-assisted laser desorption ionization quadrupole time-of-flight mass spectrometry (MALDI-Q-TOF-MS). Au and Pt ions in wet-ashed tissue solution were reacted with diethyldithiocarbamate (DDC), and the resulting chelate complex ions Au(DDC)₂ ⁺ and Pt(DDC)₃ ⁺ were detected by MALDI-Q-TOF-MS using α-cyano-4-hydroxycinnamic acid as a matrix. The limit of detection (LOD) was 0.8 ng/g tissue and the quantification range was 2–400 ng/g for Au, and the LOD was 6 ng/g tissue and the quantification range was 20–4,000 ng/g for Pt. The Pt levels detected by MALDI-Q-TOF-MS in several tissues of a patient overdosed with cisplatin were nearly the same as those detected by flow-injection electrospray ionization mass spectrometry. The LODs of Au and Pt were 0.04 pg per well (sample spot) and 0.3 pg per well, respectively. To our knowledge, this is the first attempt to quantify Au³⁺ and Pt⁴⁺ ions in tissues by MALDI-Q-TOF-MS.

Removal of heavy metals from industrial wastewaters using amine-functionalized nanoporous carbon as a novel sorbent

Nano-porous carbon (NPC) was synthesized by hydrothermal condensation of fructose and characterized by X-ray powder diffraction and also nitrogen adsorption analysis. It was then modified with amino groups and used as a sorbent for the removal of heavy metal ions. The formation of amino-modified NPC was confirmed by X-ray powder diffraction, infrared spectroscopy, thermogravimetric and elemental analysis. NPC was applied for removal of Pb(II), Cd(II), Ni(II) and Cu(II) ions. The effects of sample pH and the adsorption kinetics were studied, and the adsorption capacity was determined. The sorbent was applied to the removal of heavy metal ions in industrial waste water samples.

Preconcentration of trace lead via formation of the bis(2,2-bipyridyl) complex and its adsorption on oxidized multiwalled carbon nanotubes

A solid phase extraction method is presented for the preconcentration of trace lead ions on oxidized multiwalled carbon nanotubes (ox-MWCNTs). In the first step, the cationic Pb(II) complex of 2,2-bipyridyl is formed which, in a second step, is adsorbed on ox-MWCNTs mainly due to electrostatic and van der Waals interactions. The Pb(II) ions were then eluted with dilute nitric acid and quantified by FAAS. The effects of pH value, mass of sorbent, concentration of 2,2-bipyridyl, stirring time, of type, concentration and volume of eluent, of eluent flow rate and sample volume were examined. Most other ions do not affect the recovery of Pb(II). The limits of detection are 240 and 60 ng L^?1 for sample volumes of 100 and 400 mL, respectively. The recovery and relative standard deviation are >95 % and 2.4 %, respectively. Other figures of merit include a preconcentration factor of 160 and a maximum adsorption capacity of 165 mg g^?1. The method was successfully applied to the determination of Pb(II) in spiked tap water samples. The accuracy of the method was verified by correctly analyzing a certified reference material (NCS ZC85006; lead in tomatoes).

Cetyltrimethylammonium-coated magnetic nanoparticles for the extraction of bromate,followed by its spectrophotometric determination

We report on a combination of magnetic solid-phase extraction and spectrophotometric determination of bromate. Cetyltrimethylammonium ion was adsorbed on the surface of phenyl-functionalized silica-coated Fe₃O₄ nanoparticles (Ph-SiO₂@Fe₃O₄), and these materials served as the sorbent. The effects of surfactant and amount of sorbent, the composition of the desorption solution, the extraction time and temperature were optimized. Under optimized conditions, an enrichment factor of 12 was achieved, and the relative standard deviation is 2.9 % (for n?=?5). The calibration plot covers the 1–50 ng mL^?1 range with reasonable linearity (r ²?>?0.998); and the limit of detection is 0.5 ng mL^?1. The method is not interfered by ionic compounds commonly found in environmental water samples. It was successfully applied to the determination of bromate in spiked water samples.