Selectivity of Low- and High-Silica Clinoptilolites with Respect to Alkali and Alkaline–Earth Metal Cations

The ion-exchange equilibria involving K⁺ and Ca²⁺ cations were studied using the Na-forms of nine different clinoptilolite samples. The high-silica (in the native state, sodium–potassium form) clinoptilolites were shown to have the increased selectivity with respect to K⁺ ions, whereas the low-silica (in the native state, calcium form) clinoptilolites to Ca²⁺ ions. The phenomenon found is interpreted as a structural memory of clinoptilolites with respect to alkali and alkaline-earth metal ions which had been present during zeolite crystallization under natural conditions.     

New type of sorbents based on polyethers and some hydrophobic anions

New type of sorbent, based on the complexing properties of polyethyleneglycols, with high selectivity for Ba and Sr is described. The dependences of K_d on the initial concentration of HNO₃ for Ba, Sr, Eu, Ce, Cs and Na were studied. The capacity of two model sorbents for uptake of Cs and Sr is given. The properties of the sorbents are compared with those of the ammonium salts of heteropolyacids.     

Assessment of the sorption capacity and regeneration of carbon dioxide sorbents using thermogravimetric methods

Adsorption methods using solid sorbents are an alternative to the absorption technology in the processes of purification gases from carbon dioxide. There is a need to rapidly assess the suitability of sorbents for use it in PSA, TSA, or VPSA installations. Important parameters which determine the quality of the sorbent are the sorption capacity of sorbent, selectivity to CO₂ and the possibility of regeneration. This paper presents the results of sorption/desorption of CO₂ study on the impregnated porous materials using thermogravimetric methods. Thermogravimetry allows for rapid assessment of sorption capacity and regeneration of the sorbents. Specially selected temperature program allowed to determine the sorption capacity of sorbents depending on the concentration of CO₂ in the gas mixture and temperature. Degree of sorbent purification was determined in desorption process.     

Determination and preconcentration of natural and radio-cesium from aqueous solution

This work reports a modified atomic emission spectrometric (AES) method to determine cesium(I), based on the measurement of emission intensity at 455.5 nm with a limit of quantitation (LOQ) of 5.5 mg/l and a linear range up to 100 mg/l. In order to increase the sensitivity and lower the detection limits, potential sorbents were investigated for preconcentrating Cs from natural waters. Among the various ion-exchange materials synthesized, potassium hexanitrocobaltate (PHNCo) yielded the highest capacity for ¹³⁷Cs tagged Cs⁺ solutions as measured by gamma-spectrometry with a HPGe detector, showing the potential of a cesium preconcentration sorbent. As an alternative to AES determination, the PHNCo sorbent may be used for Cs⁺ collection from radiocesium tagged solutions and the retained activity in the dry solid exchanger be determined by gamma-spectrometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Studies on sorption of bifenthrin and diazinon insecticides on molecularly imprinted polymers

Synthesis and characterization of polymeric matrices for molecular recognition of pesticides are presented. For their preparation, methacrylic acid as a functional monomer and ethylene glycol dimethacrylate as a cross‐linking agent were used. As template molecules, diazinon and bifenthrin were applied. Syntheses were carried out in the presence of different porogens. Chemical structures were studied using FTIR‐ATR, elemental analysis, and alkacymetric titration, morphology by laser diffraction particle size analyzer and by particle size, and shape analyzer based on image analysis, whereas porous structure by nitrogen adsorption/desorption method. To study selectivity of the sorbent toward template molecule, breakthrough volumes and sorption kinetics for molecularly imprinted polymers and nonimprinted analogues were determined. Particle sizes of the studied sorbents (expressed as CE diameter) were in the range 40 to 44 μm (except sorbent obtained in the presence of hexane). The chemical composition of all obtained sorbents was close to theoretical one (60.13% C, 7.11% H, 32.77% O). The values of specific surface area of the sorbents were in the range 2 to 338 m²/g.     

Overcoming matrix interferences in ion-exchange solid phase extraction of As, Cr, Mo, Sb, Se and V species from leachates of cement-based materials using multiple extractions

Solid phase extraction (SPE) methods based on multiple extractions have been developed to overcome matrix interferences in the charge-based fractionation analysis of As, Cr, Mo, Sb, Se and V leached from cement-based materials. Disposable SPE tubes packed with 500 mg strong anion-exchange (SAX) or strong cation-exchange (SCX) sorbents were used to extract the anionic and cationic species of the elements, respectively. The multiple extractions were based on the percolation of a small sample volume (5.0 mL) through a series of identical ion-exchange tubes. For most of the elements, more than 90% of the anionic species were extracted from a sample containing up to 16 g L⁻¹ NO₃⁻ by passing the aliquot through five identical SAX tubes. Percolating a sample aliquot through three identical SCX cartridges gave more than 99% retention for Cr(III) from leachates containing a high concentration of interfering metal cations. The anionic and cationic analytes showed only slight non-specific adsorption on the SCX and SAX sorbents, respectively, except for V(V) on the SCX sorbent. A condition was established for the quantitative elution of the retained analytes from the ion-exchange sorbents with 1.0 mol L⁻¹ HNO₃. The multiple ion-exchange SPE procedures were validated using spike recovery tests. The methods were used to determine the anionic and cationic fractions of the target elements in concrete leachates covering a broad range of pH (3.8-13.4). The elements were found to exist predominantly as anions in the alkaline and neutral leachates. A high fraction (85%) of cationic Cr was detected in the most acidic leachate (pH 3.8).     

Hierarchically imprinted organic-inorganic hybrid sorbent for selective separation of mercury ion from aqueous solution

A new type of hierarchically organic-inorganic hybrid sorbent was prepared by a double-imprinting approach for the selective separation of Hg(II) from aqueous solution. In the imprinting process, both mercury ions and surfactant micelles (cetyltrimethylammonium bromide, CTAB) were used as templates, N-[3-(trimethoxy-silyl)propyl]ethylenediamine (TPED) as functional monomer, and tetraethoxysilane (TEOS) as cross-linking agent. The mercury ions and surfactant were removed from sorbent via acid leaching and ethanol extraction, respectively. The adsorption property and selective recognition ability of the sorbents were studied by equilibrium-adsorption method. Results showed that in the presence of Cu(II) or Cd(II) the biggest selectivity coefficient of the imprinted sorbents for Hg(II) was over 100, which is much higher than those of non-imprinted sorbents. The largest relative selectivity coefficient (k′) of the ion-imprinted functionalized sorbent between Hg(II) and Cu(II) was over 300, and between Hg(II) and Cd(II) over 200. The uptake capacities and the selectivity coefficients of the hierarchically imprinted sorbent were much higher than those of the sorbent prepared without CTAB template. Furthermore, the new imprinted sorbent possessed a fast kinetics for the removal of Hg(II) from aqueous solution with the saturation time less than 5 min, and could be used repeatedly. This sorbent has been successfully applied to the separation and determination of the trace Hg(II) in real water samples and those spiked with standards. This new sorbent can be used as an effective solid-phase extraction material for the selective preconcentration and separation of Hg(II) in environmental samples.     

Separation of 1,4-Dihydropyridine Derivative and Its Oxidized Form

Derivatives of 1,4-dihydropyridine (DHP) still play an important role in treatment of cardiovascular diseases. Typical degradation of the DHP ring is aromatization to pyridine ring which occurs both chemically and biochemically. It is, therefore, important to have a reliable and robust analytical method for separation of DHPs from their oxidized counterparts. Separation of closely-related substances possessing similar hydrophobicity, such as DHP and its oxidized form, can be challenging on conventional alkyl-bonded sorbents. In this study, an impact of reversed-phase (RP) liquid chromatography conditions on separation of the DHP/Ox pair has been investigated. Initially, a systematic study has been performed on 33 commercial RP columns with mobile phase acetonitrile/water for separation of foridone and its corresponding oxidized form. The retention and selectivity are discussed in view of the hydrophobic-subtraction model. Best separation was found replacing conventional C₁₈ sorbents with ones containing an embedded polar group due to polar interactions. Similarly, application of cyano columns resulted in efficient separation of analytes. Organic modifier of mobile phase (methanol vs. acetonitrile) contributed significantly to separation of foridone from its oxidized counterpart. Separation of six chemically diverse DHPs from corresponding oxidized forms was studied on seven RP columns (traditional C₁₈ sorbent, alkyl sorbent with polar embedded group, two different aromatic phases, pentafluorophenylpropyl sorbent and sorbent with straight chain perfluorohexyl ligand). Both acetonitrile and methanol were applied as organic modifier. It was found that application of alkyl sorbent with an embedded polar group (column Zorbax Bonus RP) or cyano sorbent (column ACE CN) yields clear separation of chemically diverse DHPs from their oxidized forms.     

Selectivity and efficiency of different reversed-phase and mixed-mode sorbents to preconcentrate and isolate aroma molecules

A comparison of the ability of different sorbent systems, including mixed-mode resins and reversed-phase sorbents, to extract and isolate volatile molecules from hydroalcoholic medium has been carried out by means of the determination of liquid–solid distribution coefficients. Eighteen volatile compounds covering a wide range of physicochemical properties (acids, bases and neutrals) and chemical functionalities, and thirteen different sorbents have been tested. LiChrolut EN and Isolute ENV (both polymeric with high surface area) showed the highest retention capability for nearly all analytes at all pHs tested. Exceptions were 2,3,5-trimethylpyrazine, most efficiently extracted with Strata XC at acidic pH, and indole best retained with Oasis MCX and Strata XC at any pH. Although nearly all basic compounds were most selectively extracted with cationic mixed-mode resins at acid pHs and 3-mercaptohexyl acetate and m-cresol show maxima α at pH 10 with Oasis MAX, the α values obtained have been relatively low, which suggests that retention is not particularly driven by ionic forces. The study has also shown that selectivity depends on the pH, the exact kind of mixed-mode sorbent and on the polarity of the analyte. High selectivity towards ionogenic compounds can be obtained by combining retention in mixed mode, a rinsing with a non-polar solvent and further elution with a solvent containing a neutralizing agent. However, not all the ionogenic molecules seem to be retained in ionic mode in the conditions tested and the complete elution of some analytes can be difficult, which suggests that analyte-specific isolation procedures should be analyzed case by case.     

Microcalorimetric Study of the Interaction between Water and Cation-Substituted Clinoptilolites

Heats of ion exchange and adsorption of water vapors on cation-substituted clinoptilolites are studied by microcalorimetry. Based on the results obtained, the composition of hydrates of Na⁺, Cs⁺, Co²⁺, and Ba²⁺ ions on various ion-exchange sites of clinoptilolite is determined. Their structure is identified using the combined analysis of calorimetric and X-ray diffraction data. The usefulness of energy–stoichiometry approach to the discussion of the results of adsorption calorimetry study of the interaction between water and cation-substituted clinoptilolites is demonstrated.     

双模板铅离子印迹吸附剂的制备及其应用于环境水及沉积物样品中铅的选择性吸附

利用溶胶-凝胶法制备了一种双模板介孔Pb2+印迹吸附剂(Pb-CTMAB-imp).通过平衡吸附实验,研究了Pb-CTMAB-imp的吸附性能和对Pb2+的选择识别性能.结果表明,Cd2+存在时,Pb-CTMAB-imp对Pb2+的选择系数可以达到91,远高于只用十六烷基三甲基溴化铵(CTMAB)作为模板的印迹吸附剂(...     

Hydrophobic interaction chromatography of proteins. I. Comparison of selectivity

Currently, the selection of a hydrophobic interaction chromatography (HIC) sorbent for protein separation purposes is entirely based on empirical means. An attempt was made to characterize different HIC sorbents from various manufacturers. The selectivity was determined by isocratic pulse experiments of a set of reference proteins and an algorithm was developed to classify the sorbents according to their selectivity and hydrophobicity. The obtained semi-quantitative parameters take into account the dependence of salt on adsorption. The sorbent characteristics evaluated with the model proteins were compared to the separation of a real feedstock. A good agreement was achieved between the developed evaluation procedure and the separation behaviour of the real feed stock.     

Removal of heavy metal ions from aqueous solutions using low-cost sorbents obtained from ash

This study’s main objective was the development of effective low-cost sorbents for the removal of heavy metal ions from aqueous solutions. The influence of different factors on the sorption capacity of ash and modified ash as low-cost sorbents obtained by different methods was investigated. The synthesis of new ash-based materials was carried out at ambient temperature (20°C), 70°C, and 90°C, respectively, in an alkaline medium with NaOH concentrations of 2 M and 5 M, respectively, corresponding to a mixture with solid/liquid ratios of 1: 3 and 1: 5, respectively. The prepared materials (sorbents) were characterised by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), X-ray diffraction, and BET surface measurement. Adsorption isotherms were determined using the batch equilibrium method. The results showed that these types of new materials displayed a good capacity to remove copper, nickel, and lead ions (29.97 mg of Cu²⁺ per g of sorbent, 303 mg of Ni²⁺ per g of sorbent, and 1111 mg of Pb²⁺ per g of sorbent) from aqueous solutions. The modified materials were prepared using an alkaline attack (a recognised method used in previous studies), but Romanian ash from a thermal power plant was studied for the above purpose for the first time. Hence, the factors which affect the sorption capacity of the prepared low-cost sorbents were determined and their behaviour was explained, taking into account the composition and structure of the new materials.     

Comparison of variously pretreated ion-exchange resins for131I separation from aqueous solutions

Preliminary results of experimental testing and comparison of¹³¹I separation efficiency from model solutions on ion-exchange resins pretreated in some special ways are presented. Strongly basic and strongly acidic resins were pretreated chemically and used for the separation of radioiodine by means of isotopic-exchange, ion-exchange or chemisorption and their combinations. The sorbents were tested for pI, pH, their stability during storage and selectivity of separation. From the point of view of the efficiency and selectivity of separation the sorbents based on strongly basic resins and with assumed isotopic-exchange mechanism of radioiodine separation appear to be relatively more advantegeous.     

Characterization of synthetic macroporous ion-exchange resins in low-pressure cartridges and columns. Evaluation of the performance of Macro-Prep 50 S resin in the purification of anti-Klenow antibodies from goat serum

Three ion-exchange materials and one hydrophobic-interaction chromatography packing, based on a rigid macroporous polymer with large, relatively uniform pores, have been evaluated for low-pressure liquid chromatography of antibodies. These sorbents have high capacities for both small and large proteins and are mechanically, chemically, and thermally stable. Macro-Prep 50 S. CM and Q ion-exchange materials are strongly acidic, weakly acidic, and strongly basic, respectively. Protein binding and recovery, pressure-flow properties, and chemical and thermal stability were determined for each sorbent. A rapid, two-step method for the purification of anti-Klenow antibodies from goat serum was developed, based on the Macro-Prep 50 S strong-acid cation-exchange material and the Econo-Pac HIC prepacked hydrophobic-interaction cartridge.     

Extraction of biogenic amines using sorbent materials containing immobilized crown ethers

Three sorbent materials (A18C6-MS, DA18C6-MS and AB18C6-MS) based on the crown ether ligands, 1-aza-18-crown-6, 1,4,10,13-tetraoxa-7,16-diazacyclo octadecane and 4′-aminobenzo-18-crown-6, respectively, were prepared by the chemical immobilization of the ligand onto mesoporous silica support. The sorbents were characterized by FT-IR, scanning electron microscopy-energy dispersive X-ray microanalysis, elemental analysis and nitrogen adsorption-desorption test. The applicability of the sorbents for the extraction of biogenic amines by the batch sorption method was extensively studied and evaluated as a function of pH, biogenic amines concentration, contact time and reusability. Under the optimized conditions, all the sorbents exhibited highest selectivity toward spermidine (SPD) compared to other biogenic amines (tryptamine, putrescine, histamine and tyramine). Among the sorbents, AB18C6-MS offer the highest capacity and best selectivity towards SPD in the presence of other biogenic amines. The AB18C6-MS sorbent can be repeatedly used three times as there was no significant degradation in the extraction of the biogenic amines (%E > 85). The optimized procedure was successfully applied for the separation of SPD in food samples prior to the reversed-phase high performance liquid chromatography separation.     

Study of polymer chelating sorbents with o-aminoazo-o’-hydroxy chelating groups and their use for the preconcentration and extraction of strontium from natural, potable, and industrial waters

The physicochemical and analytical properties of some polymer chelating sorbents with the o-amino-azo-o’-hydroxy functional group were examined. The selectivity of the sorbents was studied in the determination of strontium by flame photometry. A procedure was developed for the flame-photometric determination of strontium in water with its preconcentration on the polystyrene-2-aminoazo-2’-hydroxy-5’-benzenesulfonic acid sorbent. The procedure was used for the determination of strontium in natural, potable, and industrial waters.     

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.     

Effect of the acidic treatment on the adsorption and structural properties of the natural mineral sorbent M45C20

Adsorption and structural properties of the initial natural mineral sorbent M₄₅C₂₀ and the sorbent treated with 2.33 M H₂SO₄ were studied. The sorbent mainly consists of montmorillonite and clinoptilolite. Aluminum, calcium, magnesium, sodium, and potassium ions are removed from the structure under the action of the acid. The specific surface, porosity of the sorbent, and pore size increase during this process. The sorption of ammonium ions in the natural samples predominantly follows the ion-exchange mechanism (exchange to calcium, magnesium, sodium, and potassium ions). The acid treatment changes the composition of the cation-exchange complex and results in an increase in the sorption capacity to ammonium ions by a factor of ??1.3.     

Analytical Application of Silica Gel Modified with Didecylaminoethyl-beta-Tridecylammonium Iodide

Sorption of a high molecular weight quaternary ammonium salt, didecylaminoethyl-β-tridecylammonium iodide (DDATD) on different types of sorbents was investigated. The nature of reagent adsorption on silica gel was examined by spectroscopic and computer methods. The sorption of anionic metal complexes of cobalt, copper, zinc and manganese on silica gel modified with DDATD was studied. The possibility of recovery of cobalt and copper thiocyanate complexes and their further atomic absorption determination is shown. Modified sorbent was applied to cobalt chemiluminescence and determined in natural water and a nickel preparation (detection limit, 2 μg/l.).