Separation of Gd-humic complexes and Gd-based magnetic resonance imaging contrast agent in river water with QAE-Sephadex A-25 for the fractionation analysis.

Gadolinium complexed with naturally occurring, negatively charged humic substances (humic and fulvic acids) was collected from 500 mL of sample solution onto a column packed with 150 mg of a strongly basic anion-exchanger (QAE-Sephadex A-25). A Gd-based magnetic resonance imaging contrast agent (diethylenetriamine-N,N,N',N″,N″-pentaacetato aquo gadolinium(III), Gd-DTPA(2-)) was simultaneously collected on the same column. The Gd-DTPA complex was desorbed by anion-exchange with 50mM tetramethylammonium sulfate, leaving the Gd-humic complexes on the column. The Gd-humic complexes were subsequently dissociated with 1M nitric acid to desorb the humic fraction of Gd. The two-step desorption with small volumes of the eluting agents allowed the 100-fold preconcentration for the fractionation analysis of Gd at low ng L(-1) levels by inductively coupled plasma-mass spectrometry (ICP-MS). On the other hand, Gd(III) neither complexed with humic substances nor DTPA, i.e., free species, was not sorbed on the column. The free Gd in the effluent was preconcentrated 100-fold by a conventional solid-phase extraction with an iminodiacetic acid-type chelating resin and determined by ICP-MS. The proposed analytical fractionation method was applied to river water samples.

Ionic liquid-based extraction followed by graphite-furnace atomic absorption spectrometry for the determination of trace heavy metals in high-purity iron metal.

The analysis of high-purity materials for trace impurities is an important and challenging task. The present paper describes a facile and sensitive method for the determination of trace heavy metals in high-purity iron metal. Trace heavy metals in an iron sample solution were rapidly and selectively preconcentrated by the extraction into a tiny volume of an ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] for the determination by graphite-furnace atomic absorption spectrometry (GFAAS). A nitrogen-donating neutral ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), was found to be effective in the ionic liquid-based selective extraction, allowing the nearly complete (~99.8%) elimination of the iron matrix. The combination with the optimized GFAAS was successful. The detectability reached sub-µg g(-1) levels in iron metal. The novel use of TPTZ in ionic liquid-based extraction followed by GFAAS was successfully applied to the determination of traces of Co, Ni, Cu, Cd, and Pb in certified reference materials for high-purity iron metal.

Effective collection of hydrophobic organic pollutants in water with aluminum hydroxide and hydrophobically modified polyacrylic acid.

Polyacrylic acid was hydrophobically modified with dodecylamine and used as a coagulant for coprecipitation of hydrophobic organic pollutants from water. The polymer coagulant induced effective aggregation of aluminum hydroxide having hydrophobic regions which are essential for the incorporation of hydrophobic organic pollutants. Recoveries of the organic pollutants increased with increasing the dodecylamine content, which indicated that the dodecylamine moiety played an important role in the formation of hydrophobic area on the precipitate. Different hydrophobic organic pollutants that had hardly been removed by the conventional coprecipitation were successfully collected by the proposed method.

Collection of trace metals with cationic surfactant-silica particles followed by flotation with an anionic surfactant for seawater analysis.

The analysis of seawater for trace metals is important for pollution monitoring and better understanding of marine systems. The present paper describes an efficient preconcentration method for the determination of trace metals in seawater. Trace metals [Ni(II), Cu(II), Ga(III), Cd(II), Pb(II), and Bi(III)] in 1,000 mL of seawater sample were complexed with ammonium pyrrolidinedithiocarbamate and sorbed onto silica particles covered with cetyltrimethylammonium chloride. After the addition of sodium dodecyl sulfate, the particles were floated to the solution surface by bubbling and then collected by suction. The trace metals were desorbed with dilute nitric acid and determined by inductively coupled plasma-mass spectrometry. The rapid 200-fold preconcentration was demonstrated with certified seawater samples.

Surfactant-coated aluminum hydroxide for the rapid removal and biodegradation of hydrophobic organic pollutants in water.

The removal of hydrophobic organic pollutants in water to surfactant-coated aluminum hydroxide [surfactant-Al(OH)(3)] was investigated. Anionic surfactants such as sodium dodecyl sulfate (SDS), sodium bis(2-ethylhexyl)sulfosuccinate (AOT), and sodium oleate were sorbed on positively charged aluminum hydroxide at pH 7 and formed hydrophobic aggregates that can incorporate hydrophobic organic pollutants in water. Because of the hydrophobic interaction and decrease in the positive charge, surfactant-Al(OH)(3) was coagulated into precipitates that can readily be separated from water. Hydrophobic organic pollutants such as alkylphenols, polycyclic aromatic hydrocarbons, estrogens, chlorinated antifungals, and pesticides were well collected to the precipitates and thus efficiently removed from water. The collection of hydrophobic organic pollutants was correlated to their aqueous-octanol distribution coefficient. The decomposition of hydrophobic organic pollutants was examined using a bacterial agent (Bacillus subtilis). Hydrophobic organic compounds collected to AOT-Al(OH)(3) or sodium oleate-Al(OH)(3) were insufficiently decomposed. On the other hand, nonylphenol, octylphenol, and pendimethalin collected to SDS-Al(OH)(3) were decomposed within 1 week. The decomposition was accelerated by the collection to SDS-Al(OH)(3).

Removal of phenols in water using chitosan-conjugated thermo-responsive polymers.

A chitosan-conjugated thermo-responsive polymer containing 15% chitosan, PNIPAAm-15CS, was used for the removal of different phenols in water. The polymer was synthesized by a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide-mediated condensation of poly(N-isopropylacrylamide-co-acrylic acid) and chitosan in the aqueous solution (pH 6). At 30 °C, phenol, 4-methylphenol, 4-methoxyphenol, and 4-chlorophenol were converted to dark brown oxidized compounds by the tyrosinase-induced enzymatic reaction and subsequently bound to the amino moiety of PNIPAAm-15CS. In the presence of 1.0 g L(-1) PNIPAAm-15 CS and 50 k UL(-1) tyrosinase, phenols (20 mg L(-1)) decreased to undetectable levels (<0.01 mg L(-1)) within 2h. By the vigorous mixing of the solution at 40 °C, the polymer deposited and became a small coagulate that can be easily taken up from water. Accompanying the polymer deposition, the oxidized compounds were completely (>98%) removed. The proposed method was successfully applied to the removal of phenols from wastewaters.

Heat-induced solution mixing in thermo-responsive polymer-coated microchannels for the fluorometric determination of polyamines in saliva.

We developed a simple and easy method for solution mixing based on the heat-induced regulation of capillary action in thermo-responsive polymer-coated microchannels. The channels having two T-junctions were fabricated on a glass plate by a sand-blast technique and then coated with a poly(N-isopropylacrylamide) film. The polymer-coating was performed by the modification with allyltrimethoxysilane and the subsequent radical polymerization of N-isopropylacrylamide and N,N'-methylenebisacrylamide. When the channel was warmed by a Peltier device, a capillarity-based solution flow completely stopped because of the water-repellency of channel surfaces. On the other hand, the cooling of the channels allowed the restart of the solution flow through hydrophilic channels. Solution mixing downstream a T-junction was readily conducted by a Peltier device that had placed at the junction. The technique was applied to the fluorometric analysis of polyamines in saliva. The saliva sample was mixed with nickel(II) chloride solution at the first junction to mask amino acids and then mixed with o-phthalaldehyde solution at the second junction to form the fluorometric derivatives of polyamines. Blue fluorescence was observed downstream the second junction. Linear correlation was obtained between the emission intensity and the spermine concentration in the range of 20-100 microM. No mechanical pump or valve was required for the fluid manipulation.

Determination of trace impurities in high-purity iron using salting-out of polyoxyethylene-type surfactants.

To an iron sample solution was added polyoxyethylene-4-isononylphenoxy ether (PONPE, nonionic surfactant, average number of ethylene oxides 7.5) and the surfactant was aggregated by the addition of lithium chloride. The iron(III) matrix was collected into the condensed surfactant phase in >99.9% yields, leaving trace metals [e.g., Ti(IV), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II), and Bi(III)] in the aqueous phase. After removing the surfactant phase by centrifugation, the remaining trace metals were concentrated onto an iminodiacetic acid-type chelating resin. The trace metals were desorbed with dilute nitric acid for the determination by inductively coupled plasma-mass spectrometry or graphite-furnace atomic absorption spectrometry. The proposed separation method allowed the analysis of high-purity iron metals for trace impurities at low microg g(-1) to ng g(-1) levels.

Admicelle-enhanced synchronous fluorescence spectrometry for the selective determination of polycyclic aromatic hydrocarbons in water.

A simple and rapid method for the highly sensitive determination of polycyclic aromatic hydrocarbons (PAHs) in water was developed. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene in water were concentrated into sodium dodecyl sulfate (SDS)-alumina admicelles. The collection was performed by adding SDS and alumina particles into the sample solution at pH 2. After gentle mixing, the resulting suspension was passed through a membrane filter to collect the SDS admicelles containing highly concentrated PAHs. The filter was placed on a slide glass and then covered admicellar layer with a fused silica glass plate before setting in a fluorescence spectrometer. Benzo[a]pyrene, benzo[k]fluoranthene, perylene, and pyrene were selectively determined by the synchronous fluorescence scan (SFS) analysis with keeping wavelength intervals between excitation and emission to 98, 35, 29, and 45 nm, respectively. Because of the minimum spectral overlapping, 1-40 ng l(-1) of benzo[a]pyrene, benzo[k]fluoranthene, and perylene as well as 10-150 ng l(-1) of pyrene were selectively determined with eliminating the interferences of other 12 PAHs. The detection limits were 0.3 ng l(-1) for benzo[a]pyrene, benzo[k]fluoranthene, and perylene, and 1 ng l(-1) for pyrene. They were 2-3 orders of magnitude lower than the detection limits in normal aqueous micellar solutions. The application to water analysis was studied.

Phosphoester hydrolysis by cerium(IV)-thiacalix[4]arene complexes and its application to immunoassay.

Thiacalix[4]arenetetrasulfonate was treated with Ce(IV) in water at pH 9.5 to give novel phosphoester-hydrolyzing complexes. The dinuclear Ce(IV) complex promoted the hydrolysis of p-nitrophenyl phosphate with a turnover frequency of 6.8 h(-1) at 50 degrees C, showing fourfold higher activity than the mononuclear complex. The dinuclear complex was readily immobilized onto an antibody by simply mixing them in water, hence its phosphatase-like activity was applied to the color-developing reaction in immunoassay. The model assay using an antibody labeled with the dinuclear complex allowed the detection of as little as 10 ng mL(-1) of a tumor marker, Bence-Jones protein, in a 96-well microtiter plate format. Analysis of urine for Bence-Jones protein was performed by the proposed method.

Solid-phase extraction followed by HPLC for the determination of phosphorus(V) and arsenic(V).

Traces of P(V) and As(V) in sample solutions were converted into heteropoly molybdic acids at pH 1.5 and collected onto polyoxyethylene(20)-4-isononylphenoxy ether-coated Amberlite XAD-4 particles. The desorption was carried out with 0.3 M tetramethylammonium hydroxide solution for the HPLC analysis. Molybdophosphoric and molybdoarsenic acids were separated from excess molybdate by ion-pair reversed phase HPLC, though the peaks of P(V) and As(V) could not be resolved. However, the selective decomposition of molybdoarsenic acid with citric acid allowed the differential determination of P(V) and As(V) at the ng mL(-1) level. The proposed method was applied to the analysis of high-purity iron for P and As.

Concentration of chlorophenols in water to dialkyated catinonic surfactant-silica gel admicelles.

Chlorophenols including monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, and pentachlorophenol in water were extracted into dialkylated cationic surfactant-silica gel admicelles. The dialkylated cationic surfactants such as didecyldimethylammonium bromide (DC10) and didodedyldimethylammonium bromide (DC12) sorbed on silica gel surfaces to form admicelles at pH 9. Approximately 200mg of DC10 was quantitatively sorbed on 1g of silica gel. The sorption further increased by further addition of DC10. This is in contrast to the fact that the maximum sorption of mono-alkylated cetyltrimethyammonium chloride (CTAC) was only ca. 100mg. Based on the fluorescent spectra of a molecular probe, N-phenyl-1-naphthylamine, DC10- and DC12-silica gel admicelles were more hydrophobic than CTAC-silica gel admicelles. The extents of the extraction of chlorophenols into DC10-silica gel admicelles were greater than those into CTAC-silica gel admicelles. However, the extractions to DC12-silica gel admicelles were insufficient due to leakage of DC12 vesicles. Consequently, DC10-silica gel admicelles were the most adequate for concentrating chlorophenols in water. An admicelle column was prepared by passing aqueous buffer solution of DC10 through a Bond Elut Jr. silica gel solid-phase extraction cartridge. It was successfully applied to the 500-fold concentration of chlorophenols including hydrophilic mono-substituted chlorophenol in water samples prior to their HPLC analysis.

Admicelle-mediated collection followed by flotation for the preconcentration of trace metals in fresh waters.

Dithizone-impregnated admicelles were prepared by mixing silica particles with dithizone and cetyltrimethylammonium chloride in 0.1 mol L(-1) aqueous ammonia. The resulting admicelles were added to 1000 mL of sample solution and dispersed by stirring for 15 min. Traces of Ni(II), Cu(II), Ga(III), Cd(II), Pb(II) and Bi(III) in the solution were simultaneously incorporated into the admicelles at pH 7.5-9. With the aid of a rising stream of numerous tiny bubbles, the admicelles were floated on the solution surface and collected in a small sampling vessel by suction. The metals were desorbed from the admicelles with dilute nitric acid and determined by inductively coupled plasma-mass spectrometry. The proposed method offered a 100-fold multielement preconcentration and it was applicable to the analysis of river and pond waters.

Polymer-mediated extraction of the fluorescent compounds derived by Hantzsch reaction with dimedone for the sensitive determination of aliphatic aldehydes in air.

An extraction method based on the thermo-responsive precipitation of a water-soluble polymer, poly(N-isopropylacrylamide) [PNIPAAm], was applied to the concentration of dimedone (5,5-dimethylcycrohexane-1,3-dion) derivatives for the highly sensitive determination of aldehydes in air. Aliphatic aldehydes including formaldehyde, acetaldehyde, propanal, 1-butanal, 1-heptanal, and 1-hexanal in air were well solubilized into the aqueous solution of dimedone and ammonium acetate by mixing the solution and air sample in a polyvinyl fluoride bag. Fluorescent derivatives of aldehydes that had formed by the Hantzsch reaction with dimedone were concentrated by polymer-mediated extraction. The recoveries of the fluorescent compounds increased with increasing the carbon number of aldehyde and were more than 80% for the derivatives from aldehydes having more than three carbon atoms under the optimal conditions. Microgram per m3 (sub-ppb) levels of the aliphatic aldehydes, propanal, 1-butanal, 1-heptanal, and 1-hexanal, in ambient air were successfully determined by HPLC separation with fluorometric detection. The sampling volume and time required were only 1l and 20 s, respectively.

Redox-driven transport of copper ions in an emulsion liquid membrane system.

A new redox-driven type of emulsion liquid membrane separation is described. Milligram amounts of copper(II) in 0.2 M hydrochloric acid were reduced to copper(I) in the presence of ascorbic acid (1 M identical with 1 mol l(-1)). The copper solution was emulsified with a (1+4) mixture of toluene and n-heptane using Span-80 (sorbitan monooleate) as an emusifier. The resulting water-in-oil emulsion was dispersed in 0.2 M hydrochloric acid containing hydrogen peroxide and neocuproine (2,9-dimethyl-1,10-phenanthroline) by stirring for 10 min. The copper in the internal aqueous phase was selectively transported to the external one, leaving other heavy metals (e.g., Mn, Co, Ni, Cd and Pb) in the internal aqueous phase. After collecting the dispersed emulsion globules, they were demulsified by heating and the metals in the segregated aqueous phase were determined by graphite-furnace atomic absorption spectrometry (GFAAS). The selective transport of copper offered the multielement separation of trace heavy metals from a copper matrix, allowing the GFAAS determination of impurities at the 0.01% level in copper metal.

Laser ablation and low-pressure helium-ICP-MS for the analysis of alumina powder dispersed in glycerol.

A combined method of laser ablation (LA) and ICP-MS has gained much attention as a direct analytical method for solid samples. The determination of some elements, however, is seriously disturbed by isobaric interferences, mainly caused by argon and ambient air constituents. The use of low-pressure helium-ICP is a promising solution of the problem. A 1:1 mixture of alumina powder and glycerol was deaerated and irradiated with a pulsed laser beam (150 mJ) for 10 s. The sample aerosol was transported to the ICP with a stream of helium. Indium was used as an internal standard for correcting the ablated sample amount. Calibration curves were prepared from glycerol containing high-purity alumina, trace metals and indium. The detection limits for Cr, Mn, Fe, Co, Ni, and Cu approached the fractional ppm levels. The proposed method was successfully applied to the analysis of different alumina samples (99 - 99.995% purity).

Solid phase extraction of some precious metals from hydrochloric acid to polystyrene-divinylbenzene porous resin impregnated with polyoxyethylene-type nonionic surfactant.

The solid phase extraction of gold(III), platinum(II), and palladium(II) to surfactant-impregnated polystyrene-divinylbenzene porous resin (XAD-4) was studied. The extracting media could be prepared just by mixing the resin in aqueous surfactant solutions. XAD-4 impregnated with a nonionic surfactant, polyethylene glycol monooleyl ether, was useful for extracting gold(III) from hydrochloric acid. The extractions of platinum(II) and palladium(II) were improved in the use of XAD-4 impregnated with a nitrogen-containing nonionic surfactant, polyethylene glycol stearyl amine. On the other hand, base metals such as copper(II), cobalt(II), nickel(II) and zinc(II), were hardly extracted.

Removal of an iron matrix with polyoxyethylene-type surfactant-coated amberlite XAD-4 for the determination of trace impurities in high-purity iron.

Admicellar sorbents for the removal of an iron matrix were prepared for the determination of trace impurities in high-purity iron. A 1.0-g amount of Amberlite XAD-4 (macroreticular styrene-divinylbenzene copolymer) was coated with 0.14-1.3 mmol of polyoxyethylene-type surfactants, including polyoxyethylene-4-tert-octylphenoxy ethers (Triton X series) and polyoxyethylene-4-isononylphenoxy ethers (PONPEs). The surfactant-coated XAD-4 was packed into a polypropylene column (7 mm i.d. x 50 mm high). A 5.0-cm(3) volume of sample solution was passed through the column at a flow rate of 0.5 cm(3) min(-1). Milligram amounts of iron(III) were effectively sorbed on the column from 8 mol dm(-3) hydrochloric acid solutions. Among the surfactants tested, polyoxyethylene(20)-4-isononylphenoxy ether (PONPE-20) showed the best performance: the iron leaked from the PONPE-20 column was 4 microg when 25 mg of iron(III) was introduced onto the column. Trace elements, such as Ti(IV), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Cd(II), Pb(II), and Bi(III), were not retained on the column and thus quantitatively recovered in the column effluent. The effective separation of trace elements from an iron matrix allowed their accurate determinations by inductively coupled plasma-mass spectrometry or graphite furnace atomic absorption spectrometry. The detection limits (3sigma blank) were in the nanogram per gram range. The proposed method was successfully applied to the determination of trace impurities in high-purity iron samples.

Concentration of polyaromatic hydrocarbons in water to sodium dodecyl sulfate-gamma-alumina admicelle.

Polyaromatic hydrocarbons (PAHs) in water were concentrated into sodium dodecyl sulfate (SDS)-gamma-alumina and di-2-ethylhexyl sodium sulfosuccinate (Aerosol-OT, AOT)-gamma-alumina admicelles. The comparison of the binding constants (Kad[={adsorbed concentration of the solute (mol/g surfactant)}/{the concentration in the bulk aqueous phase (mol/ml)}] indicated almost the same extraction abilities of the both admicelles. However, better and more reproducible recovery was obtained in the concentration of PAHs into the SDS-gamma-alumina admicelle. PAHs in tobacco smoke that were trapped in water were successfully concentrated into SDS-gamma-alumina admicelle for the HPLC analysis.

Protein separation with surfactant-coated octadecylsilyl silica involving Cibacron blue 3GA-conjugated nonionic surfactant.

A novel medium for protein separation, namely affinity admicelle, was prepared by mixing of octadecylsilyl (ODS) silica gels, a polyoxyethylene-type nonionic surfactant (Triton X-100), and a surfactant-conjugated substrate (affinity ligand) in an aqueous solution. The ligand was synthesized by mixing a triazine dye (Cibacron Blue 3GA, CB) and a polyethylene glycol monooleyl ether (C18EO7, C18EO10, or C18EO20) having different length of polyoxyethylene moiety in weakly alkaline solutions. The amount of Triton X-100 sorbed on 1 g of ODS silica was 0.2 mmol. Affinity ligands having highly hydrophobic oleyl group were predominantly sorbed on ODS silica. The losses of Triton X-100 and affinity ligand were within 0.3% and negligible by washing the admicelles were with a 25-fold volume of 1 mM Tris-HCl solution (pH 7.4). The coating ODS silica with Triton X-100 was effective to prevent the irreversible sorption of albumin (bovine, serum). An NADH-dependent enzyme, alcohol dehydrogenase (ADH, yeast), was successfully collected on the admicelles involving CB-conjugated ligands (CB-C18EO20). The maximum collection of ADH to 90 mg/ml of affinity admicelles was 68+/-4%. However, CB-C18EO7 and CB-C18EO10 having shorter polyoxyethylene unit were not available, suggesting the requirement of the spacer moiety in the affinity ligand. The recovery and purification factor based on the ratio of activity (unit)/protein (mg) from Whatman DE52-treated yeast extract was 27% and 12, respectively.