Synthesis and application of calix[4]arene based resin for the removal of azo dyes

The present study describes a novel synthetic method for the immobilization of calix[4]arene (II) onto the surface of modified Amberlite XAD-4 resin (4), which does not require the derivatization of calixarene moiety. The novel calix[4]arene based resin (C4 resin) 5 was used as sorbent for the removal of azo dyes. Batch-wise sorption study was carried out and observed that the C4 resin (5) is more effective as compared to compound II as well as pure Amberlite XAD-4 resin (1) to remove the selected dyes [i.e. Reactive Black-5 (RB-5), Reactive Red-45 (RR-45) and Congo Red (CR)]. The effect of sorbent dosage and pH on % sorption was studied. During the extraction process, various kinds of interactions such as electrostatic repulsion, deprotonation of the hydroxyl groups of C4 resin, dissociation of reactive dyes into anions/cations and structural variations were monitored and found that they are highly pH dependent.     

Thiacalix[4]arene derivatives as extractants for metal ions in aqueous solutions: Application to the selective facilitated transport of Ag(I)

The complexation abilities of different thiacalix[4]arene derivatives towards some rare earth metal ions, metallic pollutants, and noble metals have been investigated in liquid–liquid experiments. Thiacalix[4]arene dissolved in chloroform effectively extracts Pd(II) (in acidic chloride media) and also Ag(I), Cd(II), Sm(III) and Ce(III), all buffered at pH 6 or 8. The modification of this compound to form an amide derivative results in an effective extraction of noble metals, ranked according to Au(III) > Pd(II) > Pt(IV) > Ag(I). Moreover, a supported liquid membrane system for silver transport has been developed based on thiacalix[4]arene dissolved in NPOE, and parameters affecting its efficiency have been investigated, such as the stripping composition and the pH of the feed solution. Finally, the selectivity of the membrane system has been evaluated by using as feed sources mixtures of silver and other metal ions.     

Speciation of Cr(III) and Cr(VI) after column solid phase extraction on Amberlite XAD-2010

A speciation procedure for Cr(III) and Cr(VI) based on column solid phase extraction on Amberlite XAD-2010 and flame atomic absorption spectrometry combination. Cr(VI) was quantitatively recovered on Amberlite XAD-2010 resin at pH range of 2.0-3.0 as its diethyldithiocarbamate complex, while the recoveries of Cr(III) was below 5%. The influences of the various parameters including amounts of the reagents, eluent type and its volume, sample volume, etc., on the quantitative recoveries were examined. The interference of matrix and coexistent elements for method were studied. The detection limit (corresponding to three times the standard deviation of the blank) and the enrichment factor for Cr(VI) were found to be 1.28 microg/L and 25, respectively. To verify the accuracy of the method, drinking water certified reference material (CRM-TMDW-500) was analyzed and the results obtained were in good agreement with the certified value. The proposed method has been successfully applied to the speciation of Cr(III) and Cr(VI) in water samples and preconcentration of total chromium in environmental samples.     

A novel solid phase extraction procedure on Amberlite XAD-1180 for speciation of Cr(III), Cr(VI) and total chromium in environmental and pharmaceutical samples

Due to the toxicity of chromium, species depend on their chemical properties and bioavailabilities, speciation of chromium is very important in environmental samples. A speciation procedure for chromium(III), chromium(VI) and total chromium in environmental samples is presented in this work, prior to flame atomic absorption spectrometric determination of chromium. The procedure is based on the adsorption of Cr(III)-diphenylcarbazone complex on Amberlite XAD-1180 resin. After oxidation of Cr(III), the developed solid phase extraction system was applied to determinate the total chromium. Cr(III) was calculated as the difference between the total Cr content and the Cr(VI) content. The analytical conditions for the quantitative recoveries of Cr(VI) on Amberlite XAD-1180 resin were investigated. The effects of some alkaline, earth alkaline, metal ions and also some anions were also examined. Preconcentration factor was found to be 75. The detection limits (LOD) based on three times sigma of the blank (N: 21) for Cr(VI) and total chromium were 7.7 and 8.6 microg/L, respectively. Satisfactory results for the analysis of total chromium in the stream sediment (GBW7310) certified reference material for the validation of the presented method was obtained. The procedure was applied to food, water and pharmaceutical samples successfully.     

Transition metal cations extraction by ester and ketone derivatives of chromogenic azocalix[4]arenes

The molecule of azocalix[n]arene is a macrocyclic used effectively in the complexation of the heavy metal pollutants (like silver and mercury). In this work, our main aim is to prepare new chromogenic azocalix[n]arene molecules to elaborate an extractant with high extractant selectivity for metal ions able to detect this type of pollutant. The solvent extraction properties of four acetyls, four methyl ketones and four benzoyls derivatives from azocalix[4]arenes which were prepared by linking 4-ethyl, 4-n-butyl, 4-acetamid anilin and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction, the alkaline earth (Sr2+) and the transition (Ag+, Hg2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+) metal cations have been determined by extraction studies with metal picrates. Both ketones are better extractants than esters, and show a strong preference for Ag+, while Cu2+ and Cr3+ are the most extracted cation with the esters. Both acetyl and benzoyl esters are good carriers for Ag+ and Hg2+.     

Pyridine appended L-methionine: a novel chelating resin for pH dependent Cr speciation with scanning electron microscopic evidence and monitoring of yeast mediated green bio-reduction of Cr(VI) to Cr(III) in environmental samples

Chemical speciation and pH dependent separation of Cr(III) and Cr(VI) species in environmental samples have been achieved by solid phase extraction using a new chelating resin containing pyridine appended L-methionine. Cr(III) is completely sorbed on the resin at pH 8.0 and Cr(VI) at pH 2.0. Hence a pH dependent separation of Cr(III) and Cr(VI) is possible with a limit of detection of 1.6 μg mL(-1) and 0.6 μg mL(-1) respectively. The sorption capacity of the resin for Cr(III) and Cr(VI) is 2.8 mmol g(-1) and 1.3 mmol g(-1) respectively. The sorption of chromium on the resin is supported by scanning electron microscopy (SEM). Complete desorption of Cr(III) and Cr(VI) from 1g of Cr loaded resin was achieved using 10 mL of 2 mol L(-1) HNO(3) and 6 mL of 3 mol L(-1) HNO(3) respectively. Quantitative recoveries of Cr(III) (pH 8.0) and Cr(VI) (pH 2.0) were found to be 96.0% and 98.0% respectively. Reduction efficiency of Rhodotornula mucilaginosa yeast from Cr(VI) to Cr(III) was monitored with this new resin. Concentrations of metal ions were measured by flame atomic absorption spectroscopy (FAAS).     

Comparative studies on the solvent extraction of transition metal cations by calixarene, phenol and ester derivatives

The ionophore solvent extraction of various alkali metal and transition metal cations from the aqueous phase to the organic phase was carried out by using diazo-coupling calix[n]arenes [p-(4-phenylazophenylazo)calix[4]arene (L1) and p-phenylazocalix[6]arene (L2)], phenol derivatives [2,6-dimethyl-3-phenylazophenol (L3), 2-(5-bromo-2-pyridylazo)-5-diethylamino phenol (L4), 2-chloro-4-nitro(phenylazo)-5-sec-butyl-2-phenol (L5) and 2-chloro-4-nitro(phenylazo)-5-tert-butyl-2-phenol (L6)], and ester derivatives [quinoline-8-benzoate (L7), phenyl-1,4-dibenzoate (L8), p-tolyltiobenzoate (L9)]. It was found that, all the compounds (L1-L9) examined showed selectivity for transition metal cations such as Ag+, Hg+ Hg2+, and poor efficiency for alkali metal cations (Na+ and K+). The best extraction efficiency was obtained with L1 and L4.     

Evaluation of the performance of calix[8]arene derivatives as liquid phase extraction material for the removal of azo dyes

This paper presents a study on the removal of azo dyes (Reactive Black 5, Trapaeolin 000, Methyl Orange and Direct Violet 51) with calix[n]arene derivatives from aqueous solution into the organic phase in order to explore the potential use of calixarenes as low-cost efficient extractants for wastewater dye removal. The carboxylic acid derivative of calix[8]arene shows highest affinity towards the azo dyes. The influence of NaCl (present in the solution) on extraction process was also studied. The extent of the dye removal increased with the addition of NaCl. The proposed extraction mechanism involves several kinds of interactions: electrostatic repulsion between carboxylic acid groups of calix[8]arenes and sulfonate groups of azo dyes, hydrogen bonding and formation of an inclusion complex due to three dimensional cavity type calix[n]arene molecules through host-guest interactions.     

A novel method for speciation of Cr(III) and Cr(VI) and individual determination using Duolite C20 modified with active hydrazone

Trivalent and hexavalent chromium have been successfully separated and estimated from different solutions using 1-(3,4-dihydroxybenzaldehyde)-2-acetylpyridiniumchloride hydrazone (DAPCH) loaded on Duolite C20 in batch and column modes. The obtained modified resin [DAPCH-Duolite C20] was identified by C, H and N analyses and infrared spectra. The presence of multi-active chelating sites gives the ability for DAPCH to bind more chromium, Cr(III) by forming stable complex and chromate by forming ion pair molecule [H(2)DAPCH-Duolite C20](2+)[Cr(2)O(7)](2-) (H(2)DAPCH-Duolite C20 is the protonated form in acidic medium). The extraction isotherms were measured at different pH. The pH was found to be the backbone for the separation procedure in which the Cr(VI) and Cr(III) ions are sorbed selectively from aqueous solution at pH 2 and 6, respectively. The sorbed ions can be eluted using different concentrations of HCl. The saturation sorption capacity (41.6 and 20.05 mg g(-1)), the preconcentration factor (150 and 200) and the detection limit (13.3 and 10.0 ppb) were calculated for Cr(III) and (VI). The loaded resin can be regenerated for at least 50 cycles. The utility of the modified resin was tested in aqueous samples and shows R.S.D. value of <4% reflecting its accuracy and reproducibility.     

Use of modified sorbent for the separation and preconcentration of chromium species from industrial waste water

A simple and sensitive method based on solid phase extraction (SPE) on acetyl acetone modified XAD-16 has been established for separation of Cr (III) and Cr (VI) from and industrial water samples. Two forms of chromium showed different exchange capacities at different pH values, viz. Cr (III) selectively retained at pH 5-7 whereas Cr (VI) retained at pH 1. Hence complete separation of the two forms of chromium is possible. Retained species were eluted with 5 mL of 2 mol L(-1) HNO(3) and 2 mol L(-1) NaOH. The detection limit of 0.02 and 0.014 microg mL(-1) was achieved for Cr (III) and Cr (VI), respectively, with an enrichment factor of 100 and 140. Various kinetic and thermodynamic parameters were also determined. The metal ion concentration was measured by atomic Absorption Spectroscopy. The possible retention mechanism is also discussed. The method was successfully applied for the speciation of chromium in industrial water samples.     

An efficient calix[4]arene based silica sorbent for the removal of endosulfan from water

The present work explores sorption behavior of calix[4]arene based silica resin to remove α and β endosulfan isomers from aqueous solution. The efficiency of resin was checked through both batch and column sorption methods. In both methods, the sorption parameters, i.e. pH, equilibrium time, shaking speed and sorbent dosage were optimized as 2, 60 min, 125 rpm and 50 mg, respectively. Freundlich and Langmuir sorption isotherm models were applied to validate the sorption process. The data obtained in both models reveal that the sorption is favorable. Column sorption data were analyzed through Thomas model to calculate kinetic coefficient k(TH) and maximum sorption capacity q(o) of the resin, which were found to be 6.18 and 5.83 cm(3) mg(-1) min(-1) as well as 1.11 and 1.08 mg g(-1) for α and β endosulfan, respectively. Kinetics of sorption shows that it follows pseudo second order rate equation. The optimized method has also been applied to real water samples and the results show that calix[4]arene based silica resin is an effective sorbent to remove endosulfan from waste waters.     

Removal of lanthanum and gadolinium from nitrate medium using Aliquat-336 impregnated onto Amberlite XAD-4

Aliquat-336 in benzene was supported on Amberlite XAD-4 crosslinked polystyrene resin. The use of XAD-4 impregnated with Aliquat-336 resin for removal of lanthanum(III) and gadolinium(III) from nitrate medium was carried out using batch technique. Various parameters affecting the uptake of these metal ions such as contact time, metal ion concentrations, V/m and pH value were separately studied. Effect of temperature on the equilibrium distribution values has been studied to evaluate the changes in standard thermodynamic quantities. A comparison of kinetic models applied to the adsorption rate data was evaluated for Lagergren first order, the pseudo second order and Morris-Weber kinetic models. From the results, both pseudo second order and intraparticle diffusion models were found to best correlate the experimental rate data. The capacity of the impregnated resin for both lanthanum(III) and gadolinium(III) was found to be 4.73 and 4.44 mg/g. From the results, impregnation of Aliquat-336 onto Amberlite XAD-4 provides an efficient impregnated resin for the removal of lanthanum(III) and gadolinium(III) from 0.1M nitrate aqueous solution.     

Comparison of sorption behavior of Th(IV) and U(VI) on modified impregnated resin containing quinizarin with that conventional prepared impregnated resin

This paper reports the results obtained by studying the ion-exchange properties of a new solvent impregnated resin (SIR), which was prepared by impregnation of quinizarin (1,4-dihydroxyanthraquinone, QNZ) on Amberlite XAD-16 after nitration of the benzene rings present in its structure. The sorption behavior of Th(IV) and U(VI) on/in the modified SIR was compared with that of the SIR prepared via the conventional method. It was observed that sorption capacity and sorption rate of the modified SIR are significantly greater than the conventional one. The modified SIR was then applied to the extraction of Th(IV) and U(VI) ions at the presence of many co-existence metal ions. The results obtained denote on successful application of this new SIR to analysis of natural water samples spiked to Th(IV) and U(VI) ions.     

Comparison of sensing characteristics of ChemFEC devices based on spin-coated thin films of calix[n]arenes

ChemFECs (chemical field effect capacitors) or EIS (Electrolyte-Insulator-Semiconductor) devices were coated with calix[n]arene macrocycles for cation sensors development. Silicon nitride surface electrodes were spin-coated with p-tert-butylcalix[n]arene molecules for n = 8, 9 and 11. Electrochemical capacitance measurements were carried out to evaluate the sensitivity of the calix[n]arene layers towards specific cations as calcium and copper ions. Sensor responses were due to the “host-guest” specific interaction between the rigid cavity of calix[n]arene receptors (ligand) and chemical ion species. The developed chemical sensors have demonstrated good analytical characteristic in terms of: stability, selectivity and lifetime. In addition, experimental results were fitted using the site binding model in order to determine complex association constants, pK (1.9 ≤ pK ≤ 6.39) and surface density of ligands, N_L (9.10¹⁴ ≤ N_L ≤ 2.10¹⁶). All results obtained in this work were compared with those obtained using silicon dioxide EIS electrodes coated with the same calix[n]arene receptors using both spin-coating and thermal evaporation deposit processes.     

Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines.

The synthesis of a propranolol amide derivative of p-allylcalix[4]arene is described, which has been designed to behave as a molecular sensor capable of distinguishing chiral amines on the basis of their shape and chirality. This molecule can discriminate between the enantiomers of phenylalaninol through the quenching of the fluorescence emission in methanol in contrast to an (S)-dinaphthylprolinol calix[4]arene derivative, which can discriminate between the enantiomers of phenylglycinol, but not phenylalaninol. The separation between the naphthyl fluorophores and the hydrogen-bonding sites within the chiral cavity can be tuned to recognize guest amines with similar separation between aryl groups and hydrogen-bonding sites. The formation of metal ion complexes of the p-allylcalix[4]arene propranolol amide derivative is shown to induce a more regular and rigid cone conformation in the calix[4]arene macrocycle, which generates a significant enhancement in the observed enantiomeric discrimination.     

Use of o-phenylene dioxydiacetic acid impregnated in Amberlite XAD resin for separation and preconcentration of uranium(VI) and thorium(IV)

The impregnation of o-phenylene dioxydiacetic acid (OPDA) into a polymeric matrix, Amberlite XAD-2000, is reported and was characterized by infrared spectroscopy. The amount of attached OPDA to the polymer resin was found to be 1.77mmolg(-1) resin. The resin was used for the sorption of U(VI) and Th(IV) from aqueous solution. This sorbent was capable of preconcentrating U(VI) and Th(IV) from weakly acidic or neutral solution. The retained metals were eluted sequentially using 0.25molL(-1) HCl for U(VI) and 1molL(-1) HCl for Th(IV) and determined spectrophotometrically using arsenazo-(III). The capacity of the resin for U(VI) and Th(IV) was found to be 0.121 and 0.113mmolg(-1), respectively. The impregnated resin exhibits a high chemical stability, reusability and fast equilibration. The method was used for the determination of U(VI) and Th(IV) in synthetic samples and rock samples.     

Molecular Baskets in Supercritical CO(2)

Calixarenes are synthetic macrocyclic compounds, described as "molecular baskets" as they possess high ionophoric selectivity and form inclusion complexes with many important ionic guests. In our initial work, hexameric and tetrameric tert-butylcalixarenes, unfunctionalized at the lower rim, are shown to be separable on a diol column using supercritical fluid chromatography with methanol/chloroform-modified CO(2) as mobile phase. The variation in capacity factors for these calixarenes was studied as a function of modifier composition. However, the solubility of these molecular baskets in unmodified supercritical CO(2) is enhanced by fluorination at the upper rim. For example, when p-allylcalix[4]arene is derivatized by a thiol-ene addition reaction with heptadecafluorodecanethiol, CF(3)(CF(2))(7)(CH(2))(2)SH, a solubility of >0.12 mol L(-)(1) in supercritical CO(2) is measured for the p-heptadecafluorodecylthio-n-propylcalix[4]arene at 60 °C and 200 atm. However, subsequent lower rim functionalization to form the tetrahydroxamate derivative, while reducing the solubility, allows supercritical fluid extraction of Fe(III) by the fluorinated calix[4]arene ligands to be studied as a function of temperature and pressure and monitored using UV/visible and atomic absorption spectrometry. In particular, the visible absorption spectra obtained for the extracted Fe(III)-calix[4]arene tetrahydroxamate complex, collected in dimethyl sulfoxide, are indicative of octahedral Fe(III) complexation in a manner similar to that displayed by water-soluble siderophores. Studies on the efficiency and selectivity of Fe(III) extraction are also reported.     

Calixarene monolayers as quartz crystal microbalance sensing elements in aqueous solution

We have examined p-tert-butylcalix[4]arenetetrathiolate (BCAT) monolayers for their potential use as molecular recognition elements for in situ aqueous chemical sensors. Spectroscopic and wetting studies of BCAT monolayers on Au{111} reveal that the calixarene molecules exist in monolayers, preferentially oriented with their phenyl rings parallel to the surface normal axis. Using quartz crystal microbalance (QCM) sensors with gold-coated electrodes, the chemical specificity of monolayers and thin films to a variety of aromatic and aliphatic analytes in aqueous solution was examined. The response of BCAT sensors was compared to the responses of p-tert-butylcalix[4]arene (BCA)- and decanethiolate (DT)-coated QCM electrodes. BCAT is very selective for alkylbenzenes, much more so than either its spray-coated thin-film analogue, BCA, or the highly ordered DT monolayer. From these measurements, the factors behind molecular differentiation in each film are explored. Drawing upon these findings, the roles of cavitation and film order in molecular recognition for calixarene films are discussed.     

Extraction of cesium and americium with <Emphasis Type="Italic">p</Emphasis>-alkylcalix[8]arenes from alkaline solutions

Previously unknown isononylcalix[8]arene was synthesized from commercially available isononylphenol. The properties of the product (solubility, extraction ability, tendency to aggregation) were compared with those of the known tert-butylcalix[8]arene. The extraction of ¹³⁷Cs, ^99mTc, and ²⁴¹Am from alkaline carbonate solutions with solutions of p-alkylcalix[8]arenes (alkyl = tert-butyl, isononyl) in tetrachloroethylene was studied. The dependence of the distribution ratios on pH of the aqueous phase in the interval from 11 to 13.9 and on the nature of functional groups in the calixarene core was determined. The composition of extractable solvates of cesium and americium with calix[8]arenes was found. Calix[8]arenes extract cesium from alkaline solutions more efficiently than p-tert-butylphenol, their nonmacrocyclic analog, does. tert-Butylcalix[8]arene exhibits the highest performance, which may be due to formation of aggregates 5.7 ± 0.8 nm in diameter in the organic phase at pH 13.5 of the aqueous phase. The isononyl derivative exists in the monomeric form (particle diameter 1.9 ± 0.5 nm).     

Removal efficiency of a calix[4]arene-based polymer for water-soluble carcinogenic direct azo dyes and aromatic amines

A Mannich base derivative of 5,11,17,23-tetrakis-[(1,4-dioxa-8-azaspiro-[4.5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene 3 was synthesized by the treatment of calix[4]arene with a cyclic secondary amine (1,4-dioxa-8-azaspiro-[4.5]decane) and formaldehyde. The compound 3 was treated with dibromoxylene to obtain a calix[4]arene-based copolymer 4. In batch sorption experiments of selected carcinogenic azo dyes and aromatic amines, the compounds 3 and 4 were found to be a better sorbent for azo dyes than for the aromatic amines. It was observed that the percentage of azo dye removal was 95-99% for compound 3 and 83-97% for 4 when the pH of the dye solution was in the range of 2.0-8.0. The sorption of azo dyes and aromatic amines by calix[4]arenes-based compounds indicates that amino groups play the major role for the formation of hydrogen bonds and electrostatic interactions.