Preconcentration and selective metal ion separation using chelating micelles

Chelating aggregates consisting of Triton X100 host micelles and hydrophobic derivatives of PAN have been examined as suitable candidates for preconcentration and selective separation of transition metal ions through micellar-enhanced ultrafiltration. The effective accumulation in the surfactant-rich retentate of nickel(II), copper(II), cobalt(II), manganese(II) and zinc(II), present at trace levels in aqueous samples, has been achieved by operating at pH ca. 6 with a ligand having a binding constant to the host micelles higher than 2000 l./mol. The efficient separation of micelle-bound metal chelates from unreactive ions has been assessed, together with the feasibility of selective enrichment and purification of the investigated metal ions present in mixtures through a multistage process.     

Application of the zone melting technique to metal chelate systems-V Zone chromatographic separation of metal chelates on columns of some inert solid solvents

Binary mixtures of acetylacetone and 8-hydroxyquinoline chelates of copper(II), nickel(II), cobalt(II) and cobalt(III) were processed by zone-chromatography on columns of some naphthylalkyl ethers as inert solid solvents. The metal chelates were separated to give chromatograms on the columns according to the ratio of their distribution coefficients. Distribution coefficients of metal ions varied with the type of chelating agent used and the solid solvent, and were found to be strongly affected by operating conditions, especially zone length, zone travelling speed and initial concentration of the metal chelate.     

Concentration of heavy metal ions in water using thermoresponsive chelating polymer

Thermoresponsive polymers, poly(N-isopropylacrylamide) (PNIPAAm), having chelating functionalities were synthesized. PNIPAAm-imidazole (-Im) was precipitated and formed a gum-like aggregate in the neutral pH region at 50 °C, while PNIPAAm-carboxylic acid (---COOH) and PNIPAAm-iminodiacetic acid (-IDA) remained soluble even at pH 7. An addition of a paired ion, dodecyltrimethylammonium ion, was effective for inducing the precipitation of those polymers. PNIPAAm-Im was useful for collecting copper(II), nickel(II), cobalt(II), and lead(II), but was ineffective for cadmium(II) recovery. In contrast, PNIPAAm-COOH collected cadmium(II), while insufficiently recovered cobalt(II) and nickel(II). PNIPAAm-IDA was the best choice for collecting all metal ions in neutral pH's. After 20-folds concentration, the metal ions in river and seawater were successfully determined by graphite furnace atomic absorption spectrometry (GFAAS).     

Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Application of zone-melting technique to metal chelate systems-XI Refining of tetrakis(di-n-propionylmethanato)zirconium(IV) from hafnium and trace amounts of some other metals

The zone-melting method was applied to purification of tetrakis(di-n-propionylmethanato)zirconium(IV) which contained copper(II), nickel(II), cobalt(II and III), iron(III) and hafnium(IV) in the forms of their chelates with the common ligand. All minor components having effective distribution coefficients < 1 in the zirconium(IV) chelate were concentrated toward the terminal end of the refining column. When an aqueous solution of zirconium(IV) containing zinC(II) and manganese(II) in addition to the metal contaminants above was treated with di-n-propionylmethane to precipitate the chelate complexes, only zinc, iron and hafnium were found in the precipitated zirconium chelate. The first two were ettectively removed by zone-melting. Though the separation of hafnium was poorer, the technique was efficient enough for practical purposes.     

Preparation of Amberlite XAD resins coated with dithiosemicarbazone compounds and preconcentration of some metal ions

The Amberlite XAD resins coated with dithiosemicarbazones were prepared and their collection behavior of metal ions from aqueous solution was investigated. Among the resins used, the reagent-loaded Amberlite XAD-7 was found to be superior for the collection of metal ions to other reagent-loaded resins used. The quantitative collection of mercury(II), palladium(II) and copper(II) was obtained from acidic medium, while cadmium(II) and lead(II) was obtained from neutral medium by the Amberlite XAD-7 resin coated with dimethylglyoxal bis(4-phenyl-3-thiosemicarbazone) (DMBS). These metal ions collected on the resin were easily eluted with a small volume of N,N-dimethylformamide as their DMBS chelates. This collection-elution method was applied to the determination of their metal ions by reversed-phase high performance liquid chromatography with a spectrophotometric detection.     

Controlling the internal structure of giant unilamellar vesicles by means of reversible temperature dependent sol-gel transition of internalized poly(N-isopropyl acrylamide)

In this work, we present preparation and basic applications of lipid-bilayer-enclosed picoliter volumes (microcontainers) of solutions of poly(N-isopropylacrylamide) (PNIPAAm). Giant unilamellar vesicles (GUVs) were prepared from phospholipids using a standard swelling procedure and subsequently surface immobilized. Clear, slightly viscous solutions of PNIPAAm of varying concentration in aqueous buffer were directly pressure-microinjected into the GUVs, using a submicrometer-sized, pointed capillary. The GUV was subjected to changing temperature over a 21-40 degrees C range. The typical phase transition of the polymeric material upon heating and cooling across the lower critical solution temperature was followed using optical microscopy and shown to be reversible over multiple sequential heating/cooling cycles without compromising the integrity of the GUV membrane. Fluorescent, carboxylic acid modified 200 nm latex beads, co-injected with the PNIPAAm solution, were temperature-reversibly immobilized during the phase transition, practically freezing the Brownian motion of the entrapped particles in the volume. Furthermore, a co-injected water soluble fluorescent polysaccharide-dye conjugate was shown not to migrate from the aqueous phase into the hydrophobic polymer part upon heating, whereas the fluorescent beads were completely but reversibly immobilized in the hydrophobic domains of dense polymer agglomerates. The system reported here provides a feasible method for the reversible stabilization and solidification of GUV interior volumes, e.g., as a micrometer-sized model system for controlled drug release.     

Gas and liquid chromatography of metal chelates of pentamethylene dithiocarbamate

Capillary GC and HPLC of metal chelates of pentamethylene dithiocarbamate were examined. Copper(II), nickel(II), cobalt(III), iron(III), manganese(II) and chromium(III) chelates formed in slightly acidic media (pH 5) were extracted in methyl isobutyl ketone or chloroform. Capillary GC elution and separation was carried out on methylsilicone DB-1 column (25 m x 0.2 mm I.D.) with film thickness 0.25 microm. Electron-capture detection was used. Elution was carried at initial column temperature 200 degrees C with an increment at a rate of 5 degrees C/min up to 250 degrees C and maximum temperature was maintained for 10 min. Symmetrical peaks with baseline separation were obtained with the metal chelates investigated with linear calibration range between 5 and 25 microg/ml for each metal ion and detection limits in the range of 0.5-6.0 microg/ml corresponding to 27-333 pg of metal ion reaching to the detector. HPLC separation was carried out from LiChrosorb ODS, 5 microm column and complexes eluted with methanol-water-1 mM sodium acetate (70:28:2, v/v) with a flow-rate of 1.2 ml/ml. UV detection was at 260 nm. The detection limits obtained were in the range 2-6 microg/ml. The methods were applied to the determination of metal ions in canal water and coal samples with RSD values within 4.15%. The results when compared with a standard flame atomic absorption spectrophotometric method and revealed no significant difference.     

Polymerization of Acrylamide in Aqueous Solution of Poly(N‐isopropylacrylamide) at Lower Critical Solution Temperature

Acrylamide (AAm) was found to polymerize in a solution of poly(N‐isopropylacrylamide) (PNIPAAm) in water at around its lower critical solution temperature (LCST) (32°C) without any initiators. This phenomenon was specifically observed in aqueous solutions of the polymers having LCST such as PNIPAAm and poly(methylvinylether) (PMVE). AAm polymerized only when PNIPAAm and AAm were dissolved in water below LCST of PNIPAAm and then the solution was warmed up to the polymerization temperature (40°C). On the other hand, the polymerization of AAm did not proceed when AAm was added into aqueous PNIPAAm solution during and after the phase separation above 32°C. Furthermore the polymerizability of AAm was remarkably affected by the concentration and molecular weight of the PNIPAAm additives. Under the condition of lower PNIPAAm concentration (0.30 mol/L), the increase in the molecular weight of PNIPAAm considerably increased the molecular weight of the resulting PAAm but decreased the yield of PAAm. Under the condition of higher PNIPAAm concentration (0.60 mol/L) the polymerizability was not so affected by the molecular weight of PNIPAAm, while the molecular weight of PAAm formed by using higher molecular weight PNIPAAm was higher than those of PAAm formed by using lower molecular weight PNIPAAm. Moreover, the molecular weight of PAAm formed by the PNIPAAm induced polymerization of AAm was much higher than that of the polymer obtained by the radical polymerization using AIBN in THF or VA‐ 061 in water.     

Application of the zone melting technique to metal chelate systems-IV Concentration of metal-8-hydroxyquinoline chelates in 8-hydroxyquinoline

The zone melting technique has been applied to 8-hydroxyquinoline containing trace amounts of various metal 8-hydroxyquinolates such as the nickel(II), cobalt(II), zinc(II) and copper(II) chelates. The metal chelate in each system was concentrated in the direction of zone travel. The highest concentrating effect was observed in the copper(II) chelate system. The concentration ratio, defined as the fraction of the metal chelate concentrated in the bottom 15% of the column, was determined after the 30th passage. A trace amount of copper ion extracted with a large excess of 8-hydroxyquinoline, was concentrated by means of the zone melting technique. The concentration ratio was 96%.     

Effect of tetraalkylammonium salt on the retention of metal chelates in reversed phase-high performance liquid chromatography

Summary The retention of metal chelates with azo dye chelating agents was greatly reduced when tetraalkylammonium salts (TAAS) were added to the aqueous organic mobile phase in reversed phase-high performance liquid chromatography (RP-HPLC). TAAS was very effective for decreasing the retention time of the chelates including positively charged chelates strongly retained on the reversed phase stationary support. This was probably due to the preferential adsorption of TAAS on the support by the ion exchange process and the hydrophobic interaction. The use of TAAS was a promising means for improving column selectivity in RP-HPLC without depending upon the properties of a stationary support and of a mobile phase.     

新型钴酞菁接枝温敏聚合物的制备及性能

采用2,4,6-三氯-1,3,5-三嗪对四氨基钴酞菁进行改性,并以共价键接枝到聚N-异丙基丙烯酰胺上制得一种新型温敏性高分子催化剂——钴酞菁接枝温敏聚合物,并采用UV-Vis、TG等对其进行表征.对钴酞菁接枝温敏聚合物、温敏聚合物和小分子金属酞菁进行溶解性测试,结果表明与四氨基钴酞菁相比,所合成的钴酞菁接枝温敏聚合物能溶解于水和大多数有机溶剂,且该聚合物水溶液具有良好的温敏性,其最低临界溶解温度(LCST)为34.5℃.采用浊度法考察了不同比例的混合溶剂(乙醇/水、DMF/水)对LCST的影响,结果表明随着有机溶剂含量的增加,LCST先下降后升高,而当有机溶剂增加到一定程度时温敏性消失.本文还考察了钴酞菁接枝温敏聚合物对2-巯基乙醇的催化活性,结果表明随着温度升高,催化活性也不断提高,而当温度超过LCST时催化活性急剧下降,聚合物从溶液中析出.基于这些特性,该温敏聚合物负载酞菁作为一种新型的催化剂可实现均相催化、异相分离.     

Solubility of metal chelates and their extraction from an aqueous environment via supercritical CO(2)

Solubility of nickel(II), copper(II), and chromium(III) hexafluoroacetylacetone and chromium(III) acetylacetone chelates was measured in supercritical CO(2) at two different pressures (200 and 400 atm) and 60 degrees C. Solubility of fluorinated acetylacetone chelates was at least an order of magnitude higher than the non-fluorinated complexes. These pre-formed metal chelates as well metal diethyldithiocarbamate (DDC) and metal bis(trifluoroethyl)dithiocarbamate (FDDC) have also been extracted from aqueous environment using pure supercritical CO(2). It was demonstrated that metal HFA chelates while exhibiting higher solubility in supercritical CO(2) compared with metal FDDC chelates, exhibited lower extraction efficiency using the same extraction conditions. This behavior of metal HFA chelates is related to their stability in an aqueous environment. Direct extraction of Ni(+2) and Cu(+2) from an aqueous matrix was also achieved via in-situ chelation using diethyldithiocarbamate and bis(trifluoroethyl)dithiocarbamate as the ligands. Bis(trifluoroethyl)dithiocarbamate proved to be a more effective ligand for direct extraction of metal ions from aqueous environment using supercritical CO(2).     

Extraction of some metal phenylacetates into chloroform

Phenylacetic acid has been found to be very useful as a reagent in the extraction of large quantities of certain ions, notable iron(III), cobalt(II), copper(II), lead, zinc, cadmium and uranyl. A 1M solution of the reagent in chloroform is used to extract up to 200 mg of certain ions from small volumes of aqueous phase. Selectivity is increased by pH control and masking.     

Stability constants of some metal dithizonates

The overall stability constants of electroneutral dithizonates of bismuth, cadmium, cobalt(II), copper(II), iron(II), lead(II), manganese(II), mercury(II), nickel, palladium(II), silver, tin(II) and zinc were determined by means of stoichiometric dilution in aqueous solution stabilized by hydroxylamine hydrochloride, at pH 5.50-10.02. Stability constants of complexes ML of bivalent metals were determined under similar conditions but with an excess of metal.     

New chromogens of the ferroin-type-IV Oximes of substituted methyl and phenyl 2-pyridyl ketones

The spectral characteristics, and solution conditions requisite for formation, of the iron(II), cobalt(II), and copper(I) chelates of some newly synthesized oximes containing the ferroin functional grouping have been determined. For some of the oximes, both syn- and anti-isomers were available for study. NMR spectra of the isomers differed, enabling structural distinctions to be made. None of the anti-isomers formed coloured metal chelates. A practical method for distinguishing between the isomers can be based on these findings. Two of the compounds proved very promising as highly sensitive chromogens for determining iron in strongly alkaline materials.     

Determination of transition metal ions in tobacco as their 2-(2-quinolinylazo)-5-dimethylaminophenol derivatives using reversed-phase liquid chromatography with UV-VIS detection

This paper reports the utilization of solid-phase extraction and the reversed-phase high-performance liquid chromatography for the determination of six important transition metal ions: iron, cobalt, nickel, copper, zinc and manganese in tobacco with 2-(2-quinolinylazo)-5-dimethylaminophenol (QADMAP) as chelating reagent. Iron, cobalt, nickel, copper, zinc and manganese ions react with QADMAP to form colored chelates in the medium of acetic acid-sodium acetate buffer solution (pH 4.0). These chelates can be enriched by solid-phase extraction with Waters Sep-Pak-C18 cartridge, and eluted the retained chelates from cartridge with tetrahydrofuran. The chelates were separated on a Waters Nova-Pak-C18 column (150x3.9 mm, 5 microm) by gradient elution with methanol (containing 0.5% of acetic acid) and 0.05 mol/l pH 4.0 acetic acid-sodium acetate buffer solution as mobile phase at a flow-rate of 0.5 ml/min. The detection limits of iron, cobalt, nickel, copper, zinc and manganese are 10, 12, 8, 13, 17 and 22 ng/l, respectively. This method had been applied to the determination of iron, cobalt, nickel, copper, zinc and manganese in tobacco with good results.     

High preconcentration of ultra-trace metal ions by liquid–liquid extraction using water/oil/water emulsions as liquid surfactant membranes

A high preconcentration method by liquid–liquid extraction using liquid surfactant membranes was developed. The water-in-oil (w/o) emulsion containing dilute hydrochloric acid, 2-ethylhexyl hydrogen 2-ethylhexylphosphonate (PC-88A), liquid paraffin, and kerosene was used for the extraction. In a resulting volume of 1000 cm³ of an aqueous sample solution (pH 5.0) containing less than 1 mg of each metal ion, 2 cm³ of w/o emulsion droplets coated with sorbitan monooleate were dispersed. The analyte metal ions in the outer bulk aqueous phase were extracted into the organic phase to form a complex with PC-88A and successively back-extracted into the inner aqueous phase. The analytes in the resulting inner aqueous phase were determined subsequently by graphite furnace atomic absorption spectrometry applied as a detector. By this procedure, concentration factors of 570, 820, 750, 970, 860, and 880 were achieved for chromium(III), manganese(II), cobalt(II), nickel(II), copper(II), and cadmium(II), respectively, and also the respective detection limits (3σ) of 0.4, 20, 1.2, 18, 18, and 0.7 pg cm⁻³ were obtained.     

Protecting enzymes against heat inactivation by temperature-sensitive polymer in confined space

At high temperature, many enzymes are inactivated by aggregations at hydrophobic sites which are exposed on denaturation. Isolating denatured enzymes via hydrophobic interactions with other material is a significant method to prevent enzymes from aggregation. But the temperature-sensitive polymer poly(N-isopropylacrylamide) (PNIPAAm), supposed to protect enzymes spontaneously at high temperatures, can not efficiently complex denatured carbonic anhydrase B (CAB, as a model enzyme) in bulk aqueous solution due to different phase transition speeds. Here, we present a novel method for protecting enzymes against heat inactivation, in which PNIPAAm and CAB are encapsulated in a confined space constructed by reverse microemulsion. At high temperatures, PNIPAAm forms nanoscale aggregates possessing both large specific surface areas and hydrophobic surfaces, and then adsorbs denatured CAB via hydrophobic interactions to avoid intermolecular aggregation of CAB. With cooling, CAB is released spontaneously and recovers its activity. The assays for enzymatic activity demonstrate that CAB is effectively protected against heat inactivation through this method (protection efficiency is up to 83.2%).     

Determination of cadmium, zinc, nickel and cobalt in tobacco by reversed-phase high-performance liquid chromatography with 2-(8-quinolylazo)-4,5-diphenylimidazole as a chelating reagent.

A sensitive and selective method has been developed for the simultaneous determination of cadmium, zinc, nickel and cobalt. The method is based on the chelation of metal ions with 2-(8-quinolylazo)-4,5-diphenylimidazole (QAI) and the subsequent reversed-phase (RP) high-performance liquid chromatographic separation and spectrophotometric detection of the metal chelates. The chelates were separated on an RP column with acetonitrile-water containing ethylenediamine tetraacetic acid and sodium acetate (pH 7.5). Though Zn(II) and Cd(II) chelates with azo compounds were generally labile in the RP column, these chelates with QAI were successfully detected. When analyses were carried out at 575 nm and at 0.001 absorbance unit full scale, the peak height calibration curves were linear up to 2.0 ng for Cd(II), 2.4 ng for Zn(II), 0.14 ng for Ni(II) and 0.72 ng for Co(II) in 100-microL injections, respectively; the detection limits (3sigma, three times of the standard deviation for the blank signal) for Cd(II), Zn(II), Ni(II) and Co(II) were 4.8, 24, 2.4 and 7.2 pg in 100 microL of injected solution, respectively. The proposed method was successfully applied to the analysis of tobacco without any preliminary concentration or separation.