Thermal characterization of polymeric anion exchangers with a dendrimeric structure

The thermal properties of new anion exchangers prepared via the grafting process to polymeric particles having hydroxyl groups on their surface were evaluated by thermogravimetry and differential scanning calorimetry. The support microspheres were copolymers of 1,4-di(2-hydroxy-3-methacryloyloxypropoxy)benzene (1,4 DMH) and trimethylolpropane trimethacrylate (TRIM). They were coated with polymeric layers formed by condensation polymerization of primary amines with diepoxides. Synthesized copolymers of methylamine and 1,4-butanedioldiglycidyl ether have a dendrimer structure. By TG/FTIR/MS, it was observed that new dendrimeric materials exhibited one stage of mass loss with T _max1 400 °C, connected with degradation of organic layers. DSC and TG experiments showed that water molecules are absorbed on the materials surface. The synthesized anion exchangers exhibited good thermal stability, suitable for their use in chromatographic experiments carried out with higher temperatures.     

Evaluation of anion exchange resins Tulsion A-30 and Indion-930A by application of radioanalytical technique

Radioanalytical technique using ¹³¹I and ⁸²Br was employed to evaluate organic based anion exchange resins Tulsion A-30 and Indion-930A. The evaluation was based on performance of these resins during iodide and bromide ion-isotopic exchange reactions. It was observed that for iodide ion-isotopic exchange reaction by using Tulsion A-30 resin, the values of specific reaction rate (min^?1), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and logK _d were 0.238, 0.477, 0.114, and 11.0, respectively, which was higher than 0.155, 0.360, 0.056, and 7.3, respectively as that obtained by using Indion-930A resins under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resins and 0.003 M labeled iodide ion solution. Also at a constant temperature of 40.0°C, as the concentration of labeled iodide ion solution increases 0.001 to 0.004 M, for Tulsion A-30 resins the percentage of iodide ions exchanged increases from 59.0 to 65.1%, and from 46.4 to 48.8% for Indion-930A resins under identical experimental conditions. The identical trend was observed for both the resins during bromide ion-isotopic exchange reactions. The overall results indicate that under identical experimental conditions, Tulsion A-30 show superior performance over Indion-930A resins. The results of present experimental work have demonstrated that the radioanalytical technique used here can be successfully applied for characterization of different ion exchange resins so as to evaluate their performance under various process parameters.     

A radioanalytical technique for measurement of beta-glucuronidase activities

Summary Phenolphthalein-glucuronide is a commonly used glucuronide conjugate for beta-glucuronidase measurements. The quantity of phenolphthalein liberated by beta-glucuronidase is measured spectrophotometrically. The detection limit of the quantity of phenolphthalein using spectrophotometry is a few μg. In this study, a new radioanalytical technique for the measurement of beta-glucuronidase was applied which is 10⁶times more sensitive than the spectrophotometric technique. Radioiodinated phenolphthalein-glucuronide and phenyl-N-glucuronide were used in this study in which the beta-glucuronidase levels of some tissue samples were measured.     

Ion-isotopic exchange reaction kinetics using organic base anion exchange resins Indion-102 and Indion GS-400

The present study deals with the kinetic study of iodide and bromide ion-isotopic exchange reactions in organic based anion exchange resins Indion-102 (nuclear grade) and Indion GS-400 (non-nuclear grade) using radiotracer isotopes. The resins in iodide and bromide form were equilibrated respectively with iodide and bromide ion solutions which were previously spiked with ¹³¹I and ⁸²Br radiotracer isotopes. For both bromide and iodide ion-isotopic exchange reactions, it was observed that the values of specific reaction rate increase with increase in ion concentration from 0.001 to 0.004 M at a constant temperature of 40.0°C. However, at constant ion concentration of 0.003 M, the specific reaction rate was observed to decrease with rise in temperature from 30.0 to 45.0°C. Also it was observed that for iodide ion-isotopic exchange reaction by using Indion-102 resin, the values of specific reaction rate, amount of iodide ion exchanged, initial rate of iodide ion exchange and logK _d were 0.258 min^?1, 0.492 mmol, 0.127 mmol/min and 19.2, respectively, which were higher than 0.208 min^?1, 0.416 mmol, 0.087 mmol/min and 17.6, respectively, obtained by using Indion GS-400 resin under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resin and 0.003M labeled iodide ion solution. The same trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that, under identical experimental conditions, Indion-102 resin shows higher performance than Indion GS-400 resin.     

Elution and analysis of residual chloride from anion exchangers

Summary Strong anion exchangers can be transformed to the hydroxyl forms by elution with analytical grade sodium hydroxide. The residual chloride contents remain above the 0.1% level. Such chloride amounts can rapidly and easily be determined with a radiochemical method using ^110mAg as tracer. This method was compared with neutron activation and potentiometric titration methods.

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Zusammenfassung Starke Anionenaustauscher können durch Spülen mit Natronlauge in die Hydroxylform übergeführt werden. Der Rest-Chloridgehalt bleibt jedoch immer über 0.1%. Diese Chloridgehalte können unter Zuhilfenahme des Isotopes ^110mAg mit einer radiochemischen Methode bestimmt werden. Vergleiche mit potentiometrischen Titrationen und Neutronenaktivierungsanalysen werden gegeben.

     

Synthesis and chromatographic properties of new polymer-based anion exchangers

New anion exchangers with the trimethylammonium functional group were prepared as a result of three-step synthesis involving the acylation of styrene-divinylbenzene copolymer with 25% cross-linking, the reductive amination of carbonyl groups, and subsequent methylation. Two methods of reductive amination were studied, and optimal conditions for this process were chosen. Chromatographic properties of the adsorbents were examined in a mode of ion chromatography with suppressed background conductivity and conductometric detection. The obtained anion exchangers demonstrated good selectivity, and the maximum efficiency was 30000 TP/m.     

The sorption of quercetin by high-basicity anion exchangers

The sorption of quercetin on anionites with various porosities in the OH⁻ and Cl⁻ forms was studied under static conditions. The equilibrium (distribution coefficients K _p) and kinetic (effective diffusion coefficients D _eff) parameters of quercetin sorption on AV-17-2P and AV-17-6M anionites in the Cl⁻ and OH⁻ forms were calculated. The mechanism of quercetin interactions with the anion exchangers was studied by electron microscopy and IR spectroscopy. Original Russian Text ? N.A. Udalova, S.I. Karpov, V.F. Selemenev, I.A. Sharmar, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 6, pp. 1143–1149.     

Phase transfer catalysis of modified dextran anion exchangers

Dextran anion exchangers with lipophilic substituents have been synthesized, which were found to be useful as phase transfer catalysts for displacement and hydrogenation reactions under triphase conditions.     

The nonexchange sorption of histidine by low-basicity anion exchangers

The experimental data showed that the nonexchange absorption of histidine by AN-221, AN-251, AN-31, and EDE-10P anion exchangers in the HCl form depended on the structure of the anion exchanger. The activity coefficients of the components of the sorbent phase, thermodynamic equilibrium constants, and standard Gibbs energies of nonexchange sorption of histidine by the low-basicity anion exchangers were calculated and discussed.     

Application of instrumental radioanalytical techniques to nuclear waste testing and characterization

This paper describes the validation of a multi-technique analytical methodology that uses inductively coupled plasma-mass spectrometry, α-spectrometry, and γ-spectrometry for the routine analysis of samples containing transuranic radionuclides. This methodology is capable of the determination of concentrations of both²³⁸Pu and²⁴¹Pu in the presence of²³⁸U and²⁴¹Am without the need for chemical separations. The relative merits of these three techniques were evaluated as they are applied in a nuclear waste material and spent nuclear fuel testing program by analytical (1) standards and (2) solutions prepared from the dissolution of glasses doped with²³⁷Np,²³⁹Pu, and²⁴¹Am. The uncertainty associated with technique was within ±4% for standards and ±10% for doped nuclear waste glasses. The methodology was then used to analyze three fully radioactive waste glasses.     

Investigation of the thermal behavior of new silica-polymer anion exchangers

The thermal properties of new anion exchangers consisting of silica core and organic layers grafted onto their surface were evaluated by thermogravimetry and differential scanning calorimetry. The anion exchangers were prepared by chemical modification of bare silica gel. The support was coated with polymeric layers formed by condensation polymerization of primary amines with diepoxides. Synthesized copolymers of methylamine and 1,4-butanedioldiglycidyl ether have a dendrimer structure. By TG/FTIR/MS, it was observed that silica-layered materials exhibited two stages of mass loss: first with T _max1 160 °C, connected with desorption of water molecules from the adsorbents surface, and then with T _max2 390 °C, connected with degradation of organic layers.     

Non-destructive spectroscopic characterization of parchment documents

Membranaceous substrates - widely found in library heritage - are truly challenging, due to the variety of manufacturing traditions, the intrinsic variability of the animal's skin and the different degradation patterns affecting documents along ageing. Moreover, when dealing with unique and delicate objects as cultural heritage specimens, sampling is never recommended and often explicitly forbidden. Aim of the research presented in this work is to achieve correct protocols for unambiguous characterization of the document's materials chemical structure and of the possible surface treatments.Experimental results allow us to evidence that the chosen non-destructive techniques (Raman, ATR-FTIR and SEM/EDS) provide a good differentiation between parchment manufacturing procedures, western with lime and eastern with enzymatic treatment. Incrustations of salts on the surface as well as superficial treatment with tannin can be clearly detected. Origin of tannin - from the surface or in ink - can also be distinguished.Choice of the better technique is sample-dependent, since preparation methods, degradation, presence of incrustations, amount of tannin, dehairing method can differently affect the spectral features. For instance, Raman appears to be the most effective molecular technique on western parchment, whereas ATR-FTIR allows distinguishing the enzymatic dehairing procedure from the chemical one.     

Separation of enantiomers on anion exchangers modified with heparin in liquid chromatography

Hepatitis B virus surface antigen (HBsAg) particles were efficiently adsorbed (retained) on a Sulfate-cellulose (S-C) bead column, and then desorbed with sodium chloride solutions (0.5-3.0 M). The HBsAg particles were not efficiently retained onto either sulfopropyl-agarose (SP-A) or quaternary amine-agarose (Q-A) at pH 4.5, 6 and 8. The size-exclusion curve showed that proteins of molecular mass higher than ca. 20,000 cannot penetrate into the pores of S-C beads. The dynamic binding capacity (DBC) values of lysozyme (ca. 7 mg/ml-gel) and of gamma-globulin (ca. 3 mg/ml gel) for S-C did not depend on the flow velocity while the DBC of gamma-globulin for SP-A decreased sharply with an increase in flow velocity. These results indicated that very large molecules are adsorbed only onto the surface of S-C, which resulted in fast adsorption-desorption rates although the equilibrium adsorption capacity is lower than conventional porous gel beads. Because of the rapid adsorption rate, the DBC values of gamma-globulin for S-C at high flow-rate regions are similar to those for SP-A. Bovine serum albumin was not adsorbed onto S-C. As this can not be explained by a simple electrostatic interaction mechanism, molecular recognition of S-C might be different from the agarose-based ion-exchange beads.     

Selection of anion exchangers for detoxification of dilute-acid hydrolysates from spruce

Six anion-exchange resins with different properties were compared with respect to detoxification of a dilute-acid hydrolysate of spruce prior to ethanolic fermentation with Saccharomyces cerevisiae. The six resins encompassed strong and weak functional groups as well as styrene-, phenol-, and acrylic-based matrices. In an analytical experimental series, fractions from columns packed with the different resins were analyzed regarding pH, glucose, furfural, hydroxymethylfurfural, phenolic compounds, levulinic acid, acetic acid, formic acid, and sulfate. An initial adsorption of glucose occurred in the strong alkaline environment and led to glucose accumulation at a later stage. Acetic and levulinic acid passed through the column before formic acid, whereas sulfate had the strongest affinity. In a preparative experimental series, one fraction from each of six columns packed with the different resins was collected for assay of the fermentability and analysis of glucose, mannose, and fermentation inhibitors. The fractions collected from strong anion-exchange resins with styrene-based matrices displayed the best fermentability: a sevenfold enhancement of ethanol productivity compared with untreated hydrolysate. Fractions from a strong anion exchanger with acrylic-based matrix and a weak exchanger with phenol-based resin displayed an intermediate improvement in fermentability, a four- to fivefold increase in ethanol productivity. The fractions from two weak exchangers with styrene- and acrylic-based matrices displayed a twofold increase in ethanol productivity. Phenolic compounds were more efficiently removed by resins with styrene-and phenol-based matrices than by resins with acrylic-based matrices.     

Sorption of aldonic acids from ethyl alcohol-water solutions on anion exchangers

Aldonic acids can be retained quantitatively from ethyl alcohol-water solutions by means of anion exchangers in the sulfate form. After the sorption step the aldonic acids can be easily displaced by washing with water. The sorption is explained by a partition mechanism of the same type as demonstrated in earlier work with strongly polar non-electrolytes. Precautions have to be taken to prevent uptake by means of an ion exchange mechanism. The method permits a separation from exchangeable anions and from non-adsorbable solutes.     

Non-destructive evaluation of concrete samples using PGNAA technique

Non-destructive evaluation of concrete is an important task of quality control in building construction industry. The quality evaluation of concrete samples was carried out using prompt gamma ray activation analysis (PGNAA) technique. In this study calcium and silicon contents of six concrete samples were determined through yield of 1.94 MeV gamma-rays from calcium and 3.54 MeV gamma-rays from silicon. The concrete samples were prepared by mixing cement, coarse and fine aggregates in different proportions. A linear correlation has been observed between the experimental yield of the prompt gamma rays and the actual calcium and silicon concentration in the concrete samples. Results of this study have demonstrated successful use of an accelerator-based PGNAA setup in non-destructive analysis of the concrete samples.     

Determination of the degree of palladium reduction in supported catalysts based on anion exchangers

A procedure is suggested for determining the degree of palladium reduction in fibrous anion exchangers from data on the quantitative recovery of Pd(II) from samples with a hydrochloric acid solution of thiourea before and after the reduction stage.     

Rapid high-performance liquid chromatography of nucleic acids with polystyrene-based micropellicular anion exchangers

Nucleic acids were separated by ion-exchange chromatography on 30 x 4.6 and 100 x 4.6 mm columns packed with a micropellicular anion exchanger made of 3-microns rigid polystyrene-based non-porous microspheres with a covalently bound hydrophilic layer and DEAE functional groups at the surface. The stationary phase particles showed negligible swelling in methanol according to permeability measurements with water and methanol. Nucleic acids and their fragments including synthetic single-stranded oligonucleotides, linear, nicked and supercoiled DNAs as well as DNA restriction fragments were separated in less than 5 min, a time scale that is much smaller than that of conventional high-performance liquid chromatographic analysis for such samples. When only buffer and sodium chloride were used in the eluent for the separation of double-stranded DNA restriction fragments pGEM-3Z/Taq I, electrophoretic analysis of the effluent revealed the presence of smaller fragments in the bands of the larger ones. Upon addition of ethylenediaminetetraacetic (EDTA) salt to the eluent, however, such contamination by shorter fragments was no longer observed. In the absence of EDTA, magnesium chloride in the eluent at a concentration of 1 mM precluded the separation of the restriction fragments under otherwise identical chromatographic conditions.     

Ionic polymers VI. Chemical stability of strong base anion exchangers in aggressive media

The chemical stability in aggressive media of two types of strong base anion exchangers was studied. The anion exchangers were a commercial Amberlite IRA-400 with a styrene structure and an unconventional resin obtained by the quaternization of a 4-vinylpyridine: 8% divinylbenzene copolymer with methylchloride. The presence of the quaternary nitrogen atoms in or out of the aromatic ring had a great influence on the chemical stability of the ion exchangers.     

Sorption of levulinic acid onto weakly basic anion exchangers: equilibrium and kinetic studies

The equilibrium and dynamics of levulinic acid sorption on two weakly basic anion exchangers, in free base form, in single-component aqueous solutions were investigated. Adsorption isotherms such as Langmuir, Sips, Radke-Prausnitz, and Toth were applied to correlate the experimental data in the temperature range 285-315 K. Modeling results showed that the Toth model is the best one to correlate the sorption isotherms. The resulting Toth equations were used with the Clausius-Clapeyron equation to determine the isosteric heat of sorption. The sorption kinetics was experimentally measured via a completely stirred finite-bath batch experiment under different initial concentrations and at varying solution temperatures. The pseudo-second-order kinetic model and the Elovich equation were used to represent the kinetic data and the equation parameter values were also evaluated. The pseudo-second-order equation cannot simulate the experimental kinetic data, while the Elovich equation fitted the sorption dynamic data very well under all the operating conditions studied. Finally, the apparent activation energy of sorption was also determined.