Dowex 50W-X8 Research Articles

Comparison of Ion-Exchange Resins for the Speciation Analysis of Chromium(III) and Chromium(VI) in Alkaline Solution

The retention behavior of Cr(III) and Cr(VI) in an alkaline solution (0.28 M Na2CO3/0.5 M NaOH, pH 13.5 ; US EPA Method 3060A) on four kinds of ion-exchange resins was examined. Method 3060A is an alkaline digestion procedure for extracting Cr(VI) in soils, sludges, sediments, and similar waste materials. Two commercially available ion-exchange resins were used in column operation : Dowex 50W-X8 (H+ form and Na+ form) and Dowex 1-X8 (OH− form and Cl− form). Column operation was made by pipetting a 15-mL aliquot of an original alkaline solution or a 10-fold diluted alkaline solution, spiked with Cr(III) and/or Cr(VI) to give 1 mg/mL, through a mini-column containing 2.0 g of ion-exchange resin. To compare the observed data, acidic solutions containing Cr(III) and/or Cr(VI) were also loaded. Then, the 1-mL fractions of the effluent were collected in small test tubes for both pH and flame AAS measurements, and break-through curves were illustrated and analyzed. It was found that both Cr(III) and Cr(VI) were not retained on the Na+ form cation-exchange column using both alkaline solutions. However, a selective separation of Cr(VI) from Cr(III) could be achieved by retaining Cr(III) on the H+ form cation-exchange column using a 10-fold diluted alkaline solution. Therefore, the separated Cr(VI) can be determined by a direct AAS measurement of the resulting effluent. On the OH− form and the Cl− form anion-exchange columns, both Cr(III) and Cr(VI) were retained using a 10-fold diluted alkaline solution. However, a selective separation of Cr(III) from Cr(VI) could be achieved by retaining Cr(VI) on the OH− form and the Cl− form anion-exchange columns using an original alkaline solution. Therefore, the separated Cr(III) could be determined by a direct AAS measurement of the resulting effluent.

Synthesis of peroxypropionic acid from propionic acid and hydrogen peroxide over heterogeneous catalysts

Abstract This paper proposes a study of different cation exchange resins, used as catalysts for the synthesis of peroxypropionic acid (PPA) from propionic acid and hydrogen peroxide at 40 °C, equimolar concentration of reactants and an apparent Bronsted concentration of 0.2 M. The catalytic activities of the resins are on the same scale as sulfuric acid at comparable concentration level and decrease in the order: Dowex 50Wx2 > Smopex-101 > Dowex 50Wx8 ≈ Amberlite IR-120 > Amberlyst 15. The influence of external and internal mass transfer limitation was evaluated. The experiments also demonstrated that a gelular resin with a degree of cross-linking equal to 8% and a particle size of more than 0.1 mm showed a stronger resistance to deactivation.

Selective Conversion of D-Fructose to 5-Hydroxymethylfurfural by Ion-Exchange Resin in Acetone/Dimethyl sulfoxide Solvent Mixtures

Catalytic dehydration of D-fructose to 5-Hydroxymethylfurfural (5-HMF) in acetone/dimethyl sulfoxide solvent mixtures was studied in the presence of a strong acidic cation-exchange resin catalyst (DOWEX 50WX8−100) by microwave heating. The addition of acetone to the dimethyl sulfoxide (DMSO) solvent promoted the formation of 5-HMF from D-fructose. For a D-fructose conversion of 97.9%, the 5-HMF selectivity was 91.7% for a 20-min reaction time in 70:30 (w/w) acetone/DMSO solvent mixtures. Concentrations as high as 10 wt % D-fructose were studied, for which it was found that 5-HMF yields of 82.1% for a reaction time of 10 min could be obtained. The stability of the ion-exchange resin used as the catalyst was confirmed. Compared to pure DMSO solvent, the combination of low-boiling-point acetone with DMSO used as the reaction medium not only gives highly selective 5-HMF formation, but also improves the separation efficiency and reduces environmental risk.

Ion exchange separation of strontium and rubidium on Dowex 50W-X8, using the complexation properties of EDTA and DCTA

A chromatographic method for separation of strontium from rubidium, using the unique alkaline-earth metal complexation ability of the carboxylic acids EDTA and DCTA is proposed. The method was developed in order to improve the effectiveness of (87)Sr/(86)Sr isotope studies with ICP-QMS. Due to the isobaric overlap of (87)Rb with (87)Sr, strontium needs to be separated from rubidium prior to sample analysis with ICP-QMS. The method involves the retention of strontium, calcium, magnesium, and rubidium on Dowex 50W-X8 resin in its NH(4)(+) form, followed by elution of the divalent cations as metal EDTA or DCTA complexes. Because divalent cations have different EDTA and DCTA complex formation constants, it is possible to separate them under the correct conditions. Neither EDTA nor DCTA form complexes with alkali metals, thus rubidium remains retained by the column and is later eluted using HNO(3). Both EDTA and DCTA elution methods were tested with different concentrations of the elements to determine the effect of increased concentration on separation efficiency. The EDTA elution procedure was proved to be effective in separating strontium from both calcium and rubidium, while the DCTA method was found to be even more effective, because strontium is separated from all the elements involved in this study.

Uptake of Iodine and Bromine by Ion-Exchange Resins in Aqueous Solution

The uptakes of molecular iodine and bromine by both strong acid cation (Dowex 50W-X4 and X8) and strong base anion (Dowex 1-X4 and X8) exchange resins have been studied in aqueous solutions at 25 degrees C. An empirical formula for the amount of solute taken up by the resin in mmol per gram of dry resin, Q, as a function of the solute concentration in M (mol dm(-3)), C, was derived. Direct proportional relationships between Q and C have been found, except for the bromine-anion exchanger system. In contrast to the cation-exchange resin, the anion exchanger exhibits extremely high affinity for I(2) and Br(2).

N-Glycans and the N Terminus of Protein C Inhibitor Affect the Cofactor-enhanced Rates of Thrombin Inhibition

Protein C inhibitor (PCI) is a serine protease inhibitor, displaying broad protease specificity, found in blood and other tissues. In blood, it is capable of inhibiting both procoagulant and anticoagulant proteases. Mechanisms that provide specificity to PCI remain largely unrevealed. In this study we have for the first time provided a full explanation for the marked size heterogeneity of blood-derived PCI and identified functional differences between naturally occurring PCI variants. The heterogeneity was caused by differences in N-glycan structures, N-glycosylation occupancy, and the presence of a Delta6-N-cleaved form. Bi-, tri-, and tetra-antennary complex N-glycans were identified. Fucose residues were identified both on the core GlcNAc and as parts of sialyl-Le(a/x) epitopes. Moreover, a glycan with a composition that implied a di-sialyl antenna was observed. PCI was N-glycosylated at all three potential N-glycosylation sites, Asn-230, Asn-243, and Asn-319, but a small fraction of PCI lacked the N-glycan at Asn-243. The overall removal of N-glycans affected the maximal heparin- and thrombomodulin-enhanced rates of thrombin inhibition differently in different solution conditions. In contrast, the Delta6-N-region increased both the heparin- and the thrombomodulin-enhanced rates of thrombin inhibition at all conditions examined. These results thus demonstrate that the N-linked glycans and the N-terminal region of blood-derived PCI in different ways affect the cofactor-enhanced rates of thrombin inhibition and provide information on the mechanisms by which this may be achieved. The findings are medically important, in view of the documented association of PCI with atherosclerotic plaques and the promising effect of PCI on reducing hypercoagulability states.

Initiation of Mammalian O-Mannosylation in Vivo Is Independent of a Consensus Sequence and Controlled by Peptide Regions within and Upstream of the α-Dystroglycan Mucin Domain

To reveal insight into the initiation of mammalian O-mannosylation in vivo, recombinant glycosylation probes containing sections of human alpha-dystroglycan (hDG) were expressed in epithelial cell lines. We demonstrate that O-mannosylation within the mucin domain of hDG occurs preferentially at Thr/Ser residues that are flanked by basic amino acids. Protein O-mannosylation is independent of a consensus sequence, but strictly dependent on a peptide region located upstream of the mucin domain. This peptide region cannot be replaced by other N-terminal peptides, however, it is not sufficient to induce O-mannosylation on a structurally distinct mucin domain in hybrid constructs. The presented in vivo evidence for a more complex regulation of mammalian O-mannosylation contrasts with a recent in vitro study of O-mannosylation in human alpha-dystroglycan peptides indicating the existence of an 18-meric consensus sequence. We demonstrate in vivo that the entire region p377-417 is necessary and sufficient for O-mannosylation initiation of hDG, but not of MUC1 tandem repeats. The feature of a doubly controlled initiation process distinguishes mammalian O-mannosylation from other types of O-glycosylation, which are largely controlled by structural properties of the substrate positions and their local peptide environment.

A rapid, small-scale procedure for the structural characterization of lipid A applied to Citrobacter and Bordetella strains: discovery of a new structural element

Endotoxins [lipopolysaccharides (LPSs)] are part of the outer cell membrane of Gram-negative bacteria. Their biological activities are associated mainly with the lipid component (lipid A) and even more specifically with discrete aspects of their fine structure. The need for a rapid and small-scale analysis of lipid A motivated us to develop a procedure that combines direct isolation of lipids A from bacterial cells with sequential release of their ester-linked fatty acids by a mild alkali treatment followed by MALDI-MS analysis. This method avoids the multiple-step LPS extraction procedure and lipid A isolation. The whole process can be performed in a working day and applied to lyophilized bacterial samples as small as 1 mg. We illustrate the method by applying it to the analysis of lipids A of three species of Citrobacter that were found to be identical. On the other hand, when applied to two batches of Bordetella bronchiseptica strain 4650, it highlighted the presence, in one of them, of hitherto unreported hexosamine residues substituting the lipid A phosphate groups, possibly a new camouflage opportunity to escape a host defense system.

Determination of selected elements by radionuclide X-ray fluorescence analysis after the separation on different kinds of sorption materials

This paper aimed to the evaluation of different kinds of sorbent material preparation and to the evaluation of their characteristics at different pH conditions by X-ray fluorescence analysis. This method is suitable for identification and determination of elements in samples of different character, state and origin because it is a polycomponent, non-destructive, fast and simple analytical method. Moreover, it allows time-advantageous and reliable measurements. This paper studies problems concerning the determination of some selected elements (Mn, Fe, Ni, Cu, Zn, Pb) in pharmaceutical samples of sodium chloride in the solid state as well as in its solution by sorption on chelating extraction membrane 3M Empore™ and on the strongly acidic ion-exchanger Dowex 50Wx8. Conditions for the most effective sorption of determined elements are also interpreted.

A comparative study on the separation of radiozirconium via ion-exchange and solvent extraction techniques, with particular reference to the production of 88Zr and 89Zr in proton induced reactions on yttrium

The radiochemical separation of no-carrier-added zirconium from proton irradiated yttrium was studied by two techniques, namely, ion-exchange chromatography using Dowex 50W-X8 and Dowex 21K resins, and solvent extraction using HDEHP and TPPO, the latter reagent being employed for the first time for separation of radiozirconium from bulk of yttrium. Out of all those techniques, the solvent extraction using TPPO was found to be the best: the separation yield of radiozirconium was >97%, the time of separation was short, the contamination from the long-lived 88Y activity was low (10−4%) and the final product was obtained in the form of oxalate. The production of 89Zr and 88Zr of high radionuclidic and chemical purity via irradiation of yttrium targets with protons of energies 12 and 20 MeV, respectively, is described. The experimental yields of the two radionuclides were found to be 28 MBq/μA·h and 1.63 MBq/μA·h, respectively. Each value corresponds to about 80% of the respective theoretical yield.

RECOVERY OF ZINC AND RARE EARTHS FROM ABU RUSHIED FERRUGINOUS ORE MATERIAL, SOUTH EASTERN DESERT, EGYPT

This paper is concerned with the recovery of separate Zn and REEs pure concentrates from a sulphate leach liquor of Abu Rushied ferruginous ore material. Preparation of separate Zn/REEs concentrates was carried out by either selective oxalate precipitation of the REEs or else by bulk hydroxides precipitation followed by re-dissolution of Zn as zincate. The leached REE values could also be recovered in two main steps namely; precipitation of LREEs as their double sulphate during or directly after the acid leaching while the potentiality of individual separation of the HREEs concentrate left behind was studied through the displacement technique using the cationic exchange resin Dowex 50W-X8. A tentative flowsheet for the overall treatment of Abu Rushied ore material is also presented.

Self-Cleaning Resins

This paper introduces a fundamentally new concept in adsorbents, whereby the sorption of an aqueous solute by a cross-linked polymer is controlled by a gel to liquid-crystalline phase transition. To demonstrate proof of principle, a bilayer forming surfactant, N,N-dioctadecyl,N,N-dimethylammonium bromide (DODAB) has been immobilized onto a cation exchange resin, Dowex 50WX2, and its thermotropic phase behavior and solute-adsorption properties have been investigated. Examination by a combination of differential scanning calorimetry and X-ray scattering has confirmed the retention of a gel to liquid-crystalline phase transition of the surfactant, occurring between 296 and 318 K. Adsorption measurements that were made for 4-chlorotetrahydropyran, 1,2-dichloroethane, and benzyl alcohol have also confirmed uptake by the resin in the liquid-crystalline phase and release in the gel phase.

Manganese and zinc operational fractionation in beer by means of tandem ion exchange column assemblage and flame atomic absorption spectrometry

A straightforward method is presented for the operational fractionation of Mn and Zn in beer based on use of a tandem ion exchange column assemblage. Degassed beer samples were driven through the system comprising the weak anion exchanger Reillex 402 (first column) connected in a series with the strong cation exchanger Dowex 50Wx4 (second column). The relevant metal groupings retained on the exchangers, i.e., the fraction of the metals bound to the polyphenols, and the fraction of the cationic metal species, were determined respectively in the effluents (5-mL portions) sampled during the passage of the samples through the first column, and in the eluates obtained by the elution of Mn and Zn species (with 10 mL of 4.0 mol L−1 HCl) from the second column, after passing the samples through the tandem column system. Additionally, the effluents obtained after loading the tandem column system with the samples were also collected and taken to the analysis in order to asses the donation of the third, residual fraction. The usefulness of the fractionation scheme is illustrated by the analysis of three bottled beers produced by a local brewery. The fractionation patterns established for Mn and Zn are discussed regarding the possible associations of the metals under consideration with different endogenous beer ligands.

Acceptor Specificity of the Pasteurella Hyaluronan and Chondroitin Synthases and Production of Chimeric Glycosaminoglycans

The hyaluronan (HA) synthase, PmHAS, and the chondroitin synthase, PmCS, from the Gram-negative bacterium Pasteurella multocida polymerize the glycosaminoglycan (GAG) sugar chains HA or chondroitin, respectively. The recombinant Escherichia coli-derived enzymes were shown previously to elongate exogenously supplied oligosaccharides of their cognate GAG (e.g. HA elongated by PmHAS). Here we show that oligosaccharides and polysaccharides of certain noncognate GAGs (including sulfated and iduronic acid-containing forms) are elongated by PmHAS (e.g. chondroitin elongated by PmHAS) or PmCS. Various acceptors were tested in assays where the synthase extended the molecule with either a single monosaccharide or a long chain (approximately 10(2-4) sugars). Certain GAGs were very poor acceptors in comparison to the cognate molecules, but elongated products were detected nonetheless. Overall, these findings suggest that for the interaction between the acceptor and the enzyme (a) the orientation of the hydroxyl at the C-4 position of the hexosamine is not critical, (b) the conformation of C-5 of the hexuronic acid (glucuronic versus iduronic) is not crucial, and (c) additional negative sulfate groups are well tolerated in certain cases, such as on C-6 of the hexosamine, but others, including C-4 sulfates, were not or were poorly tolerated. In vivo, the bacterial enzymes only process unsulfated polymers; thus it is not expected that the PmCS and PmHAS catalysts would exhibit such relative relaxed sugar specificity by acting on a variety of animal-derived sulfated or epimerized GAGs. However, this feature allows the chemoenzymatic synthesis of a variety of chimeric GAG polymers, including mimics of proteoglycan complexes.

Preconcentration of total chromium on Dowex 50W-X8 resin loaded with 2-amino-benzenethiol

Application of Dowex 50W-X8 loaded with 2-amino-benzenethiol for preconcentration of total chromium (Cr(VI) and Cr(III)) in water samples and subsequent determination by inductively coupled plasma-atomic emission spectrometry was studied. The reagent 2-amino-benzenethiol loaded onto the resin effectively reduced Cr(VI) to Cr(III) and total chromium (both Cr(VI) and Cr(III)) formed chelate complex with the reagent in the Cr(III) valence state. Experimental parameters such as preconcentration time, solution flow rates, pH, and concentration of the eluent were optimized. The method has been applied for the determination of total chromium in seawater samples in the range of 0.1–200 µg L−1. A detection limit of 0.3 µg L−1 was achieved, and the relative standard deviation was about 5%.

Fractionation analysis of manganese and zinc in tea infusions by two-column solid phase extraction and flame atomic absorption spectrometry

The fractionation pattern of Mn and Zn in the infusions of black and green teas was studied using the Amberlite XAD7 and the Dowex 50Wx4 sorbents connected in a series, after the thorough examination of the sorption and the desorption characteristics of the resins applied. Under the optimized conditions, the one step two column approach developed enabled to distinguish three different operationally defined classes of the metal species, namely the polyphenolic, the cationic and the residual metal fractions. The results indicate that Mn and Zn in tea infusions are predominantly present in the form of the cationic species (up to 80% or more, especially in the green teas). Both metals are also attached to the polyphenolic compounds and possibly to other macromolecules.

Fractionation analysis of manganese and zinc in beers by means of two sorbent column system and flame atomic absorption spectrometry

In the present article, a method of operational fractionation of Mn and Zn in beer using flame atomic absorption spectrometry was developed. The proposed fractionation scheme was based on use of a hydrophobic adsorbing resin Amberlite XAD7 (first column, 2 g resin bed) connected in a series with a strong cation exchanger Dowex 50Wx4 (second column, 1 g resin bed). After passing the samples of beers through the columns, distinct groupings of Mn and Zn species retained on the sorbents, i.e., hydrophobic fraction of polyphenols bound metal species and cationic metal species fraction, respectively, were determined in respective eluates obtained after complete recovery of Mn and Zn species with 10 ml of 2.0 mol l −1 HNO 3 (first column) and 10 ml of 4.0 mol l −1 HCl (second column). In addition, the effluents collected were analyzed prior to the evaluation of the third, residual fraction, presumably attributed to any hydrophilic anionic and inert metal species. The established fractionation patterns for Mn and Zn were discussed in reference to likely associations of metals with endogenous food bioligands and possible availability of the distinguished metal species classes. The quality of the results was proved by the recovery experiments.

Determination of Ca, Mg, Fe and Zn partitioning in UHT cow milks by two-column ion exchange and flame atomic absorption spectrometry detection

An operationally defined fractionation protocol was developed to study the partitioning of Ca, Mg, Fe and Zn in UHT cow milks. The method was based on sorption of distinct metal species by two ion exchange columns, namely strong cation exchanger Dowex 50Wx4 and strong anion exchanger Dowex 1x4, connected in a series. The evaluation of the donation of metal species classes distinguished, that is cationic and anionic fractions, was made after splitting the columns and elution of metal groupings with a 2.0 mol l −1 HCl solution, followed by the determination of metal concentrations in the resulting eluates. The amount of third, inert fraction was assessed by measuring metal contents in the effluents obtained after passage of the samples through the columns. The results achieved utilizing two-column ion exchange based procedure were compared with those obtained for the approach in which the columns were considered separately. The fractionation pattern for each metal studied was thoroughly discussed in light of available knowledge relating to the composition of milk.

Uptake of Benzene and Alkylbenzenes by Cation- and Anion-Exchange Resins from Aqueous Solutions

Uptakes of benzene and 12 alkylbenzenes (from toluene to n-pentylbenzene including xylene and trimethylbenzene isomers) by both strong acid cation (Dowex 50W-X4 and X8) and strong base anion (Dowex 1-X4 and X8) exchange resins have been studied in aqueous solutions at 25 degrees C; their distribution constants (K) have been determined. The relationship between the octanol-water partition coefficient (K(ow)) and the resin affinity for solutes has been analyzed. The K values of benzene and alkylbenzenes were larger than the K values of aliphatic hydrocarbons expected from the K(ow) values. While the K value was increased with the alkyl chain length, no further increase in the K value was observed for n-butylbenzene and n-pentylbenzene.

Simple and versatile operational fractionation of Fe and Zn in dietary products by solid phase extraction on ion exchange resins

A simple and versatile protocol, based on use of solid phase extraction on strong ion exchangers and off-line detection by flame atomic absorption spectrometry, was devised to fractionate iron and zinc in common dietary food and beverages products, i.e., bee honeys, fruit juices and tea infusions. In the procedure proposed, cation exchanger Dowex 50Wx4 and anion exchanger Dowex 1x4 were used separately for distinguishing broadly meant the cationic metal fraction and the fraction of stable anionic metal complexes, respectively, after retention of metal species and their exhaustive elution by means of a 4.0 mol l −1 HCl solution. The third fraction, referred to the residual metal species, was retrieved by difference between total soluble metal contents and sum of metal quantities in separated cationic and anionic fractions. The fractionation pattern observed for both metals was described and discussed.