Properties and Application of a Chelating Sorbent Prepared by Modification of LiChroprep-NH<Subscript>2</Subscript> with Calcon

A new chelating sorbent for metal ions was prepared by modification of chemically modified silica – LiChroprep-NH₂ with Calcon. The molecular mechanism of binding this reagent to the surface of the applied carrier is presented. The properties of this sorbent were compared to analogous sorbents with a plain silica carrier and chemically modified silicas – LiChroprep-RP containing Calcon. The advantages of the new sorbent compared to the silica and LiChroprep-RP chelating sorbents are demonstrated. The sorbent obtained was applied as stationary phase in solid-phase extraction (SPE) for separations of some chosen mixtures of metal ions and for additional purification of aqueous solutions of salts of alkali metals from trace amounts of heavy metals. The multiple use of the sorbent based on LiChroprep-NH₂ in sorption-desorption processes of metal ions without deterioration of its sorption capacity is demonstrated.     

Retention of Some Metal Ions and Their Separation on Silica Gel Modified with Acid Red 88

 Acid Red 88 is strongly extracted by chloroform solutions of Aliquat 336 by an ion exchange mechanism and for its reextraction from the ion pair formed, relatively high concentrations of mineral acids are required. By impregnation of silica with the ion pairs between the cation of Aliquat 336 and the anion of the dye a chelating sorbent for metal ions can be obtained. The sorbent prepared may be successfully used for separation of mixtures of various metal ions by the column extraction chromatography technique, additional purification of sodium and potassium salts from ions of heavy metals and for concentration of trace amounts of ions of various metals from aqueous solutions followed by their quantitative determination. The sorbent can be used repeatedly in the process of sorption and desorption of metal ions (especially those forming less stable complexes with the reagent) after regeneration with solutions of perchloric acid. Received January 28, 1998. Revision March 1, 1999.     

Lipophilicity determination of some nitrostyrene derivatives on RP-2, PR-8 and RP-18 layers

Summary The lipophilicity of 33 nitrostyrene derivatives was determined by reversed-phase thin-layer chromatography on RP-2, RP-8 and RP-18 layers using methanol as the organic phase. The R_M value of each compound linearly decreased with increasing concentration of the organic solvent. The retention strength of RP-2 layer was lower than that of RP-8 and RP-18 layers. Between the retention strength of RP-8 and RP-18 layers no significant difference was detected. Minor differences among the selectivities of the layers were also observed. The impact of the change of methanol concentration on the retention was higher on RP-2 than on RP-18 layers probably due to the sterically favourable interaction of methanol with the shorter alkyl groups on the silica surface.     

Multielement Preconcentration and Removal of Trace Metals by Solid-Phase Extraction

ABSTRACT

The solid phase extraction of trace amounts of some metal ions from their mixtures using cation exchanger Dowex 50Wx4, cellulose sorbent with phosphonic acid groups Cellex P, chelating resin Chelex 100 and SIO₂-TPP sorbent which contains porphyrin ligand covalently attached to aminopropyl silica gel was investigated. With respect to multielement preconcentration Cellex P and Chelex 100 seem to be the best sorbents; the recovery test for Al, Be, Cd, Ni, Pb and Zn were > 90%. Additionally, Cellex P appeared to be suitable for enrichment of Co and Mn. Silica-TPP sorbent could be applied as a selective collector for Mo(VI) and V(IV).     

Chelating sorbents based on silica gel and their application in atomic spectrometry

This mini-review covers chelating sorbents anchored to silica gel and their analytical applications for the preconcentration, separation and determination of trace metal ions, focussing mainly on the last 20 years. The article summarizes also the experience gathered by our research group in the synthesis and characterization of new modified silica gels via silanization, and their affinity toward selective extraction and separation of trace elements. The introduction of 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide silica gel (DPTH-gel) and methylthiosalicylate silica gel (TS-gel) chelating sorbents in trace and ultratrace analysis provide vital breakthroughs in preconcentration methods. These home-made materials allow certain analytes to be selectively extracted from complex matrices without matrix interference and good detection limits. The advantages of these new chelating sorbents in comparison with 8-hydroxyquinoline chelating sorbent immobilized on silica gel are discussed.     

Additional purification of alkali or alkaline earth salts by using silica gel modified with pyrocatechol violet as a sorbent

Sorption of 14 metal ions on silica gel impregnated with a mixture of Aliquat 336 and Pyrocatechol Violet was investigated. It was found that alkali metals and calcium are not retained on the sorbent, magnesium is retained from solutions of pH > 6, contrary to other metal ions. The sorbent was used for purification of some salts from trace amounts of heavy metals and magnesium. Some metals ion mixtures have also been separated by using column extraction chromatography stepwise elution with perchloric acid solutions.     

Evaluation of metal fractions in river sediments and waters: application of chelation chromatography-differential pulse anodic stripping voltammetry

The ability of chelation chromatography in combination with differential pulse anodic stripping voltammetry (DPASV) to provide a simple, fast and reliable way of dealing with interionic interferences, competitive complexations, re-adsorption of released metal ions and sorption of spiking metal ions by organic/inorganic materials in the complex matrixes of real natural samples has been critically examined. The technique is based on the selective complexation of target metal fractions on some novel sorbents which are polymeric chelating resins doped on stationary supports (Whatman No. 1 paper and silica gel). The usual complications of leaching of the resin and/or the chelating ligand and colloid retention on the sorption bed at any stage of separation were largely obviated with these sorbents under the operational conditions of metal sorption. A detailed study on the application of such sorbents to the differentiation of ionic (free), labile (ionic plus weakly complexed) and bound (strongly complexed) metal fractions present in local river-sediment and water samples was carried out. Chelating resin-impregnated paper (CRIP) and chelating resin-immobilized silica gel column (CRISC) methods of chromatographic separation of analyte trace metals in combination with the follow-up 'standard addition' procedure of the DPASV technique were employed. A modest attempt has been made to formulate a speciation (fractionation) scheme for metal contents present in river-sediments and waters on the basis of selective retention of ionic and labile fractions on complexing resins.     

Silica gel modified with Eriochrome Blue SE as a sorbent in trace analysis for metal ions

The sorption of 14 metal ions on silica gel impregnated with a mixture of Aliquat 336 and Eriochrome Blue SE was investigated. It was found that the sorption behaviour depends upon the species and the pH of the loading solution. Alkali metal ions were not retained under any of the investigated conditions. The retained metal ions can be eluted with dilute solutions of hydrochloric or perchloric acid without significant elution of the chelating reagent from the sorbent. The sorbent was used for the separation of metal ion mixtures by column — extraction chromatography and for additional purification of some salt solutions from trace amounts of Zn, Cd, Pb and Cu. The effectiveness of purification was confirmed by anodic stripping voltammetry.     

Synthesis and physicochemical properties of chelating sorbents containing functional groups of N-aryl-3-aminopropionic acids

Two types of chelating sorbents with different types of addition of iminodipropionate groups to a polymeric matrix were synthesized: carboxyethylated aminopolystyrene (sorbent 1) based on linear polystyrene and carboxyethylaminomethylpolystyrene (sorbent 2) based on the copolymer of styrene and divinylbenzene. The ionization constants and concentrations of functional groups of the sorbents (exchange capacity for hydrogen ions) were determined. The sorbents exhibit high selectivity for copper(II) ions with the maximum of sorption from ammonia—acetate buffer solutions lying in a range of pH 5.0–7.5. The time needed for a solution of copper(II)—sorbent system with continuous stirring to reach exchange equilibrium is 3.5 and 2 h for sorbents 1 and 2, respectively. The exchange capacity for copper(II) ions is 2.54 and 0.10 mmol g⁻¹, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 800–806, May, 2006.     

Separation of Pyrimidine Bases on a HPLC Stationary RP-18 Phase Coated with Calix[4]resorcinarene

Lipophilic calix[4]resorcinarenes, derived from lauryl aldehyde and resorcinol, are strongly adsorbed on the modified silica gel RP-18 for HPLC chromatography, while their solutions are passed through the column. The calix[4]resorcinarene-coated RP-18 phases were found to be useful beds for HPLC separation of uracil, thymine and cytosine.     

Calcon-modified silica gel sorbent. Application to preconcentration or elimination of trace metals

Silica gel impregnated with a mixture of Aliquat 336 and Calcon was used as chelating sorbent for preconcentration of metals from dilute aqueous solutions and their separation as well as for additional purification of analytical grade sodium and potassium salts from other metals. The relative capacities of sorbent towards 33 metal ions were determined in the pH range 1-9 as well as the concentrations of hydrochloric and perchloric acid eluting the retained metals. It was found that Calcon was not eluted from sorbent with 5M perchloric and 10M hydrochloric acids. The rate of sorption for Mg, Ca, Cu, Zn, Al, Cr(III) and Fe(III) was also studied and it was found that relatively high flow-rates (up to 5 ml/min) can be used for solutions passed through the column. The sorbent was used for preconcentration of traces of some metals from aqueous solutions before their determination by AAS, for separation of metal ion mixtures by column extraction chromatography and for additional purification of potassium chloride solutions used as supporting electrolyte in determination of some heavy metals by anodic stripping voltammetry.     

Sorption of Cobalt on Modified Silica Gel Materials

Various silica gel materials were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzod-18-crown-6 (DB18C6). The degree of functionalization of the covalently attached molecule was calculated from C, H, N analysis and ranged between 0.270 and 0.552 mmol/g (for sorbents with imidazole) and between 0.043 and 0.062 mmol/g (for sorbents with DA18C6 and DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.050 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter <40 Å was used too. Change of pore diameters of silica gel support to larger pores should have a positive influence on access of cobalt ion to sorption centers to increase of sorption capacity of sorbents. The sorption kinetics of cobalt and the influence of cobalt concentration, pH of various kinds of silica gel matrix with immobilized imidazole group in static conditions on sorption were measured. The sorption of cobalt in various conditions (pH, contact time of phases) with constant liquid-solid ratio (V/m = 50 ml/g) was studied. The distribution coefficients ranged between 200 and 50 000 ml/g (for imidazole), 85 and 120 ml/g (for DB18C6) and between 230 and 500 ml/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. Protons significantly competes to sorption of cobalt in acidic solutions. The influence of presence of other heavy or toxic metals (Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was investigated. Sorption of cobalt decreases in order Hg > Cu > Cd > Zn, Fe > Mn > Al, Cr. The presence of sodium and potassium ions at concentration 0.05 mol/l significantly influences on the sorption of cobalt with sorbent with immobilized DB18C6 functional group.     

Preparation,properties and analytical application of silica with chemically grafted hydroxamic acid groups

The synthesis of silica chemically modified with propanohydroxamic acid groups and salicylhydroxamic acid is described. Sorption of 13 metal ions is studied as a function of pH. The composition of the sorbed complexes is determined and the apparent stability constants of the complexes in the sorbent phase are calculated. A correlation between the stabilities of the complexes in the sorbent phase and in aqueous solution is observed in some cases. Some analytical applications of the sorbents are demonstrated: trace amounts of elements can be concentrated from large volumes; molybdenum(VI) and zirconium(IV) can be separated from 10⁴-fold amounts of accompanying elements, and vanadium(V) can be determined in the sorbent phase by using diffuse reflection and photoacoustic spectrometric techniques.     

Solid-phase extraction using multiwalled carbon nanotubes and quinalizarin for preconcentration and determination of trace amounts of some heavy metals in food,water and environmental samples

A solid phase extraction procedure has been developed using multiwalled carbon nanotubes (MWCNTs) as a solid sorbent and quinalizarin [1,2,5,8-tetrahydroxyanthracene-9,10-dione] as a chelating agent for separation and preconcentration of trace amounts of some heavy metal ions, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) before their determination by flame atomic absorption spectroscopy (FAAS). The influences of the analytical parameters, including pH, amounts of quinalizarin and adsorbent, sample volume, elution conditions such as volume and concentration of eluent, flow rates of solution and matrix ions, were investigated for the optimum recoveries of the analyte ions. No interference effects were observed from the foreign metal ions. The preconcentration factor was 100. The detection limit (LOD) for the investigated metals at the optimal conditions were observed in the range of 0.30–0.65 μg L^?1. The relative standard deviation (RSDs), and the recoveries of standard addition for this method were lower than 5.0% and 96–102%, respectively. The new procedure was successfully applied to the determination of analytes in food, water and environmental samples with satisfactory results.     

High-Performance Chelation Chromatography of Metal Ions on Sorbents with Grafted Iminodiacetic Acid

The chromatographic behavior of some alkaline-earth, transition, heavy, and rare-earth metals on a number of complexing sorbents containing surface iminodiacetic acid (IDA) functional groups is studied. The conditions under which metal retention is determined by complexation on the sorbent surface were established, and the main principles of a new variant of the liquid chromatography, i.e., high-performance chelation ion chromatography (HPCIC), are formulated. The efficiency and selectivity of separation of the metal ions are considered depending on the type of the IDA bonding, the sorbent matrix parameters, the eluent composition, and the temeprature of the chromatographic column. Under optimal conditions, the metal retention is shown to linearly correlate with the stability constants of the respective complexes in the double-logarithmic scale. The application of HPCIC to the analysis of multicomponent systems is considered.     

New Inexpensive and Selective Sorbent Phases for Rapid Thin Layer Chromatographic Analysis of Metal Ions

Abstract

New sorbent phases have been developed by impregnating silica gel G with different inorganic salts for the analysis of metal ions by thin layer chroma to graphy in carboxylic acids media. Thin layers prepared from silica gel G impregnated with ammonium chloride or barium nitrate show the unusual selectivity towards metal ions in comparison to the thin layers prepared from plain silica gel G or silica gel impregnated with silver nitrate or aluminium nitrate. Many qualitative separations     

Retention behaviour of some high-intensity sweeteners on different SPE sorbents

The objective of this paper is to provide information about application of solid-phase extraction (SPE) for isolation of nine high-intensity sweeteners (acesulfame-K, alitame, aspartame, cyclamate, dulcin, neotame, saccharin, sucralose and neohesperidin dihydrochalcone) from aqueous solutions. The influence of several types of LC-MS compatible buffers (different pH values and compositions) on their recovery has been studied and discussed. A number of commercially available SPE cartridges, such as Chromabond C18ec, Strata-X RP, Bakerbond Octadecyl, Bakerbond SDB-1, Bakerbond SPE Phenyl, Oasis HLB, LiChrolut RP-18, Supelclean LC-18, Discovery DSC-18 and Zorbax C18 were tested in order to evaluate their applicability for the isolation of analytes. Very high recoveries (better than 92%) of all studied compounds were obtained using formic acid-N,N-diisopropylethylamine buffer adjusted to pH 4.5 and C₁₈-bonded silica sorbents. Behaviour of polymeric sorbents strongly depends on their structure. Strata-X RP behaves much like a C₁₈-bonded silica sorbent. Recoveries obtained using Oasis HLB were comparable with those observed for silica-based sorbents. The only compound less efficiently (83%) retained by this sorbent was cyclamate. Bakerbond SDB-1 shows unusual selectivity towards aspartame and alitame. Recoveries of these two sweeteners were very low (26 and 42%, respectively). It was also found that aspartame and alitame can be selectively separated from the mixture of sweeteners using formic acid-triethylamine buffer at pH 3.5.     

A facile and novel process for the preparation of <Superscript>147</Superscript>Pm source

Aiming the selective recovery of palladium from high level radioactive liquid waste (HLW), a chelating thiamide type sorbent, CWP–TU, was prepared by the modification of Japanese cedar wood powder (CWP). Convection oven and microwave heating were separately used for modification purpose and found that microwave heating is more effective over oven heating. CWP–TU was extensively studied for the adsorption of Pd(II) from nitric acid medium. The batch test showed that nitric acid concentration of 3 M or higher is favorable for Pd(II) loading. Consistent adsorption of Pd(II) under gamma irradiation condition demonstrated the feasibility of using CWP–TU in real HLW. Also, Pd(II) only adsorption from simulated HLW solution verified the palladium only selectivity of the sorbent as well as the lack of influence of coexisting metal ions on its affinity toward Pd(II). CWP–TU holds maximum Pd(II) loading capacities of 0.98 mol/kg at 30 °C and 1.04 mol/kg under gamma irradiation. A comparative study using some ion exchange resins revealed that the resins are either ineffective in nitrate medium or lack stability under irradiation.     

New hybrid chelating sorbents with grafted 3-aminopropionate groups based on mixed silicon,aluminum, titanium,or zirconium oxides

A series of new hybrid organo-inorganic sorbents with the 3-aminopropionate chelating group was synthesized. The synthesis includes the copolycondensation (sol—gel method) of tetraethoxysilane, 3-aminopropyltriethoxysilane, and several modifiers (MeSi(OEt)₃, EtSi(OEt)₃, Ti(OEt)₄, AlONO₃, ZrOCl₂) followed by carboxyethylation with acrylic acid. The obtained chelating sorbents were characterized by elemental analysis, FT-IR and ¹H NMR spectroscopy, and thermogravimetry. The N-carboxylated sorbents have a higher sorption capacity with respect to metal ions (0.5–0.9 mmol g⁻¹, pH 6.3, NH₄OAc, 20 °C) than the starting sorbents with the primary amino group (0.05–0.2 mmol g⁻¹) and manifest high selectivity for copper(II) ion extraction. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1783–1788, August, 2005.