Hypercrosslinked strong anion-exchange polymers for selective extraction of fluoroquinolones in milk samples.

In this work, hypercrosslinked strong anion-exchange polymer resins (HXLPP-SAX) were synthesized and evaluated as solid-phase extraction (SPE) sorbents for extracting fluoroquinolones (FQs) in milk samples. These particles were prepared using a protocol that was facile and cost-effective by combining hypercrosslinking reactions and quaternisation reactions in one step. After the synthesis, the morphological properties and anion-exchange, adsorption, and selectivity performances of the HXLPP-SAX resins were characterized and evaluated. It was shown that the polymers were monodisperse microspheres, with the mean diameters of 2-4 µm, ion-exchange capacity (IEC) of 0.311 meq/g, and specific surface area more than 1000 m2/g. The resins applied as SPE sorbents possessed high selectivity in the extraction of amphoteric compounds (enoxacin and enrofloxacin as the representatives) followed by HPLC-UV analysis, as compared to commercially available strong anion-exchange sorbents (Oasis MAX). The SPE-HPLC-UV method was fully validated and exhibited good linearity (10-2000 ng/g, R2 ≥ 0.997), low limits of detection (2.8-5.1 ng/g), good recoveries (85.8%-117.9%, RSDs ≤ 7.1%) and precisions (intra-day RSDs ≤ 7.7% and inter-day RSDs ≤ 9.4%). Then the method was performed the selective enrichment of six FQs (enoxacin, norfloxacin, ciprofloxacin, lomefloxacin, enrofloxacin, and sparfloxacin) in milk samples. The present results demonstrated that the proposed resins exhibited a promising potential for the enrichment and determination of FQ residues in milk samples as well as in other samples with complex matrices.

Zeolite fillers for resin-based composites with remineralizing potential.

The objective of the study is to obtain the modified zeolite powders and to apply these materials as active fillers in the dental composites with the remineralizing potential. Three different synthesis pathways were applied to receive LTA-type (Linde A-type) zeolites. All zeolites were subjected to the ion exchange process and mineralization of surface with hydroxyapatite (HA) layer. As a result a calcium form and surface modified form of these materials were prepared. The effectiveness of each modification process was confirmed by X-ray Diffractometry, Infrared and Raman Spectroscopy. Materials were also characterized by Scanning Electron Microscopy, Energy Dispersive Spectroscopy and nitrogen adsorption/desorption measurements. The remineralizing potential was specified as an ability to release calcium ions during the incubation in saline with the use of Inductively Coupled Plasma-Mass Spectrometry. The obtained zeolite fillers were placed in the organic matrix to create photopolymerizable composites with potential dental applications. The homogeneity of the filler distribution in polymeric matrix was checked by the Raman spectra mapping. Composites containing calcium form of zeolites as well as zeolites with the HA layer proved to have the ability to release calcium ions during incubation in saline in the amount comparable to calcium phosphates-filled composites or even higher than dental glass-filled composites. The ability to release calcium ions, together with good mechanical properties and mass stability testify the suitability of prepared composites in potential dental applications.

Preparation of ion exchange resin using soluble starch and acrylamide by graft polymerization and hydrolysis.

Based on soluble starch and acrylamide by performing graft polymerization in aqueous solution and hydrolysis step, a low-cost ion exchange resin has been synthesized to remove the heavy metal ions of Cr3+ and Ni2+. The hydrolysis progresses by adding NaOH to convert -CONH2 to -COONa, and the adsorption experiments confirmed that the functional group to adsorb heavy metals is -COO-, rather than -CONH2. During the determination of heavy metal adsorption, the Na+ concentration diffused by SR-16 into the solution was also analysed to investigate the ion exchange process. The composition and morphology of SR-16 was characterized by FT-IR, SEM, elemental analyser and EDS, and the results showed that SR-16 has an excellent adsorption capacity to the removal of heavy metal pollution; the adsorption mechanism of SR-16 could be explained by ion exchange progress with -COONa attached on the network structure.

The binding of metal ions to molecularly-imprinted polymers.

Imprinting polymerization is a flexible method to make resins specific for different compounds. Imprinting polymerization involves the polymerization of the resin in the presence of a template, here cadmium ions or arsenate. The template is then removed by washing, leaving specific binding sites in the resin. In water treatment, the removal of toxic metal ions is difficult due to the limited affinity of these ions to ion exchange resins. Imprinting polymerization of ion-exchange resins is used to develop resins with high capacity and some selectivity for cadmium ions or arsenate for water treatment that still function as general ion-exchange resins. A minimum binding capacity of 325 meq/g was achieved for cadmium ions. Competition experiments elucidate the type of bonds present in the imprinting complex. The capacity and bond types for the cadmium ions and arsenate were contrasted. In the case of cadmium, metal-ligand bonds provide significant specificity of binding, although significant binding also occurs to non-specific surface sites. Arsenate ions are larger than cadmium ions and can only bind via ionic and hydrogen bonds, which are weaker than metal-ligand bonds. This results in lower specificity for arsenate. Additionally, diffusion into the resin is a limiting factor due to the larger size of the arsenate ion. These data elucidate the bonds formed between metal ions and the imprinting sites as well as other parameters that increase the capacity for heavy metals and arsenate.

Preparation and evaluation of a timolol maleate drug-resin ophthalmic suspension as a sustained-release formulation in vitro and in vivo.

The aim of this work was to assess the performance of resin as an ocular delivery system. Timolol maleate (TM) was chosen as the model drug and an ion exchange resin (IER) as the carrier. The drug-resin complex was prepared using an oscillation method and then characterized regarding particle size, zeta potential, morphology, and drug content. After in vitro drug release study and corneal permeation study were performed, in vivo studies were performed in New Zealand albino rabbits using a suspension with particles sized 4.8 ± 1.2 µm and drug loading at 43.00 ± 0.09%. The results indicate that drug released from the drug-resin ophthalmic suspension permeated the cornea and displayed a sustained-release behavior. Drug levels in the ocular tissues after administration of the drug-resin ophthalmic suspension were significantly higher than after treatment with an eye drop formulation but were lower in body tissues and in the plasma. In conclusion, resins have great potential as effective ocular drug delivery carriers to increase ocular bioavailability of timolol while simultaneously reducing systemic drug absorption.

Novel Pendant Benzene Disulfonic Acid Blended SPPO Membranes for Alkali Recovery: Fabrication and Properties.

To reconcile the trade-off between separation performance and availability of desired material for cation exchange membranes (CEMs), we designed and successfully prepared a novel sulfonated aromatic backbone-based cation exchange precursor named sodium 4,4'-(((((3,3'-disulfo-[1,1'-biphenyl]-4,4'-diyl)bis(oxy)) bis(4,1-phenylene))bis(azanediyl))bis(methylene))bis(benzene-1,3-disulfonate) [DSBPB] from 4,4'-bis(4-aminophenoxy)-[1,1'-biphenyl]-3,3'-disulfonic acid [BAPBDS] by a three-step procedure that included sulfonation, Michael condensation followed by reduction. Prepared DSBPB was used to blend with sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO) to get CEMs for alkali recovery via diffusion dialysis. Physiochemical properties and electrochemical performance of prepared membranes can be tuned by varying the dosage of DSBPB. All the thermo-mechanical properties like DMA and TGA were investigated along with water uptake (WR), ion exchange capacity (IEC), dimensional stability, etc. The effect of DSBPB was discussed in brief in connection with alkali recovery and ion conducting channels. The SPPO/DSBPB membranes possess both high water uptake as well as ion exchange capacity with high thermo-mechanical stability. At 25 °C the dialysis coefficients (UOH) appeared to be in the range of 0.0048-0.00814 m/h, whereas the separation factor (S) ranged from 12.61 to 36.88 when the membranes were tested for base recovery in Na2WO4/NaOH waste solution. Prepared membranes showed much improved DD performances compared to traditional SPPO membrane and possess the potentiality to be a promising candidate for alkali recovery via diffusion dialysis.

Simple and sensitive monitoring of ß2-agonist residues in meat by liquid chromatography-tandem mass spectrometry using a QuEChERS with preconcentration as the sample treatment.

A liquid chromatography with tandem mass spectrometric detection (LC-MS/MS) method was established for the simultaneous determination of the levels of 10 ß2-agonists in meat. The samples were extracted using an aqueous acidic solution and cleaned up using a Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) technique utilising a DVB-NVP-SO3Na sorbent synthesised in-house. First, the ß2-agonist residues were extracted in an aqueous acidic solution, followed by matrix solid-phase dispersion for clean-up. The linearities of the method were R(2)=0.9925-0.9998, with RSDs of 2.7-15.3% and 73.7-103.5% recoveries. Very low limits of detection (LOD) and quantitation (LOQ) of 0.2-0.9 µg/kg and 0.8-3.2 µg/kg, respectively, were achieved for spiked meat. The values obtained were lower than the maximum residue limits (MRLs) established by the EU and China. These results clearly demonstrate the feasibility of the proposed approach. The evaluated method provided reliable screening, quantification and identification of 10 ß2-agonists in meat.

Nano/microstructured ion exchange resins and their applications.

Ion exchange resins, due to their specific nano/microstructures and applications, have attracted great attention in the past decades. This paper reviews the recent advances and applications of nano/microstructured ion exchange resins, with an introduction to the preparation and property of different ion exchange resins. The applications of different ion exchange resins in catalysts, medicine, metallurgical regeneration, metals, and chemicals removal are summarized and discussed. The perspectives for the future developments of ion exchange resins are also proposed.

Determination of melamine and cyromazine in milk by high performance liquid chromatography coupled with online solid-phase extraction using a novel cation-exchange restricted access material synthesized by surface initiated atom transfer radical polymerization.

A novel strong-cation-exchange restricted access material has been synthesized by atom transfer radical polymerization (ATRP). In the synthesis, poly(3-sulfopropyl methacrylate-co-ethylene dimethacrylate), [p(SPM/EDMA)] was grafted on the silica by surface-initiated ATRP first. The poly(glycerol mono-methacrylate) [pGMMA] was then immobilized on the external surface, which created a chemical diffusion barrier for protein exclusion. The resulting Sil-g-p(SPM/EDMA)-g-pGMMA has both functions of protein exclusion and cation exchange, exhibiting the property of cation-exchange restricted access material. The application of Sil-g-p(SPM/EDMA)-g-pGMMA has been studied by the determination of melamine and cyromazine in bovine milk using the online solid-phase extraction/HPLC method. In the process, the Sil-g-p(SPM/EDMA)-g-pGMMA was used for the sample pre-treatment and a HILIC column was employed as the analytical column. The method has shown good accuracy, precision and low limits of detections. The result demonstrated that the Sil-g-p(SPM/EDMA)-g-pGMMA can be used for the cation extraction from biological samples by direct HPLC injection.

Preparation of methacrylate-based anion-exchange monolithic microbore column for chromatographic separation of DNA fragments and oligonucleotides.

In this paper, we report on the preparation of a microbore-scale (1 mm i.d.) anion-exchange monolithic column suitable not only for analytical purposes but also for potentially preparative applications. In order to meet the conflicting requirements of high permeability and good mechanical strength, the following two-step procedure was applied. First, an epoxy-containing monolith was synthesized by in situ copolymerization of glycidyl methacrylate (GMA) and ethylene dimethacrylate (EDMA) within the confines of a silicosteel tubing of 1.02 mm i.d. and 1/16" o.d. in the presence of a ternary porogenic mixture of 1-propanol, 1,4-butanediol, and water. The monolithic matrix was subsequently converted into weak anion-exchanger via the ring-opening reaction of epoxy group with diethyl amine. The dynamic binding capacity was 21.4 mg mL(-1) for bovine serum albumin (BSA) at 10% breakthrough. The morphology and porous structure of this monolith were assessed by scanning electron microscope (SEM) and inverse size exclusion chromatography (ISEC). To optimize the separation efficiency, the effects of various chromatographic parameters upon the separation of DNA fragments were investigated. The resulting monolithic anion exchanger demonstrated good potential for the separation of both single- and double-stranded DNA molecules using a gradient elution with NaCl in Tris-HCl buffer (20 mM). Oligodeoxythymidylic acids (dT(12)-dT(18)) were successfully resolved at pH 8, while the fragments of 20 bp DNA ladder, 100 bp DNA ladder, and pBR322-HaeIII digest were efficiently separated at pH 9.

Neutron-activated ¹5³Sm-ion-exchange resin as a tracer for gastrointestinal scintigraphy.

Nuclear medicine techniques are well established for the investigation of gastrointestinal (GI) motility and transit. Ion-exchange resins radiolabelled with 99mTc and ¹¹¹In are widely used as nonabsorbable radiopharmaceutical markers, with ¹¹¹In being preferred for whole-gut transit studies. This radionuclide, however, is not produced in many countries and may be expensive when obtained through international shipment. This study describes the use of neutron-activated ¹5³Sm-resin as an alternative tracer for use in GI scintigraphic investigation. A measure of 50 mg of stable samarium-152 chloride (¹5²SmCl3) was incorporated into 100 mg of cation-exchange resin and irradiated in a neutron flux of 1 × 10¹³ cm⁻² s⁻¹ for 100 s to achieve an activity of 5 MBq after 66 h. Aliquots of ¹¹¹In-radiolabelled resin (5 MBq) were prepared for comparison of labelling and stability. Radiolabelling efficiencies were obtained by washing resin with distilled water, and the activity lost was measured. The radiolabelled resins were immersed in simulated gastric and intestinal fluid environments, and the retention of ¹5³Sm³âº and ¹¹¹In³âº was measured over a 24 h period. At 66 h after production, 91.15 ± 12.42% of ¹5³Sm was bound to the resin after washing in distilled water, whereas radiolabelling with ¹¹¹In achieved 99.96 ± 0.02% efficiency. Both radiolabelled resins demonstrated almost 100% stability in simulated intestinal fluid and >90% stability in artificial gastric juice over 24 h. The performance of neutron-activated ¹5³Sm-resin is similar to that of ¹¹¹In-resin and can be used as an alternative tracer for GI transit studies when In is not available.

A polar-copolymerized method to prepare silica-based anion exchanger for ion chromatography.

A novel silica-based strong anion exchanger was developed for ion chromatography by copolymerizing methyltrichlorosilane and 3-chloropropyltrichlorosilane. The method allows the column capacity to be easy control simply by adjusting the ratio of silanes. The unwanted residual silanol groups onto the surface of silica gel could also be greatly reduced by this strategy. The effective column capacity of the column used was measured to be 50.8 µequiv/column (2.03 µequiv/cm). The exchanger was characterized by solid state CP/MAS (13)C NMR and elemental analysis and its separation performance was evaluated for the separation of common inorganic anions. The results showed that the column had good separation efficiency (e.g. the plate number of nitrite is 80,000/m) and the separation mechanism was observed to be dominantly governed by ion exchange mechanism. The utility of the column was demonstrated for the determination of nitrite and nitrate in saliva sample.

[Preparation of L-phenylalanine chiral ligand-exchange chromatographic stationary phase by atom transfer radical polymerization and resolution of racemates].

A novel stationary phase was synthesized for chiral ligand-exchange chromatography via atom transfer radical polymerization (ATRP). Glycidyl methacrylate (GMA) was grafted onto the surface of the silica by ATRP using bromoisobutyryl bromide as an initiator, and the organic metal compound formed in the CuCl/2,2'-bipyridine(Bpy) system as a catalyst at room temperature. The chiral stationary phase was then synthesized by grafting L-phenylalanine on the surface of the silica. The stationary phase was characterized by means of elementary analysis and evaluated in detail to determine its separability. The amount of L-phenylalanine on the surface of silica was calculated to be 4.32 mg/m2. The results showed that the good enantioseparations of some DL-amino acids were obtained using ligand-exchange chromatography on the synthesized chiral stationary phase (50 degrees C) with 0.05 mol/L KH2PO4 and 0.1 mmol/L Cu(Ac)2 solution (pH 4.5) as the mobile phase at a flow rate of 1.0 mL/min and a wavelength of 223 nm. The influences of the mobile phase pH, concentration of Cu (II), and temperature of column on the resolution of DL-amino acids by ligand-exchange chromatography were investigated. The results showed that these conditions could affect the resolution of racemates. Compared with the column prepared by radical method using L-phenylalanine directly bonded onto the surface of the silica, the synthesized stationary phase showed a better separation ability, and the DL-aspartic acids and DL-asparagines could be separated at baseline.

An excellent fluoride sorption behavior of modified amberlite resin.

The article describes a convenient method for the modification of Amberlite XAD-4 resin by introducing thio-urea binding sites onto the aromatic rings. The modified (ATU) resin has been employed for the quantitative sorption of fluoride ions in batch as well as column experiments. The parameters (i.e. pH, contact time, etc.) were optimized and desorption of fluoride ions was fulfilled by using 0.01 M HCl solution. The equation isotherms such as Langmuir, Freundlich, Dubinin-Radushkevich (D-R) and Temkin were also successfully applied to model the experimental data. The sorption capacity of the ATU resin was found as 3.286 mmol g(-1). From the D-R isotherm parameters, it has been calculated that the uptake of fluoride ion by ATU resin occurs through ion exchange sorption mechanism. The study will contribute toward the remediation of fluoride polluted areas as well as in the various fields of materials science.

Development of a temperature-responsive agarose-based ion-exchange chromatographic resin.

A temperature-responsive ion-exchange resin (ItBA) has been prepared by grafting poly(N-isopropylacrylamide-co-acrylic acid-co-tert-butylacrylamide; ItBA) onto cross-linked agarose. A carboxymethylated ion exchanger (CM) of similar charge density was also prepared. Maximum adsorption capacities (B(max)) for lactoferrin at 20 degrees C and 50 degrees C were determined for both resins by batch adsorption procedures. Dynamic adsorption and desorption characteristics of the CM and ItBA with lactoferrin were established, as well as the ability of ItBA to selectively adsorb and desorb lactoferrin in the presence of other proteins. With the CM-agarose resin there was no significant difference between the B(max) values obtained at 20 degrees C and 50 degrees C. However, for the agarose-based ItBA resin the B(max) value at 50 degrees C was almost three times higher than the B(max) value at 20 degrees C. Dynamically, lactoferrin adsorbed to the ItBA packed column at 50 degrees C with a significant proportion of the adsorbed lactoferrin desorbed by reducing the temperature to 20 degrees C. In addition, anionic proteins did not adsorb to the ItBA packed column, and did not interfere with the dynamic adsorption/desorption behaviour of lactoferrin. These results indicate that this new temperature-responsive agarose-based ItBA resin has potential for the fractionation of whey proteins, with good selectivity for cationic proteins.

Ion-exchanger synthesis using reversible addition-fragmentation chain transfer polymerization.

An ion-exchanger with polyanionic molecular brushes was synthesized by a "grafting from" route based on "surface-controlled reversible addition-fragmentation chain transfer polymerization" (RAFT). The RAFT agent, PhC(S)SMgBr was covalently attached to monodisperse-porous poly(dihydroxypropyl methacrylate-co-ethylene dimethacrylate), poly(DHPM-co-EDM) particles 5.8 microm in size. The monomer, 3-sulfopropyl methacrylate (SPM), was grafted from the surface of poly(DHPM-co-EDM) particles with an immobilized chain transfer agent by the proposed RAFT protocol. The degree of polymerization of SPM (i. e. the molecular length of the polyanionic ligand) on the particles was controlled by varying the molar ratio of monomer/RAFT agent. The particles carrying polyanionic molecular brushes with different lengths were tested as packing material in the separation of proteins by ion exchange chromatography. The columns packed with the particles carrying relatively longer polyanionic ligands exhibited higher separation efficiency in the separation of four proteins. Plate heights between 130-200 microm were obtained. The ion-exchanger having poly-(SPM) ligand with lower degree of polymerization provided better peak-resolutions on applying a salt gradient with higher slope. The molecular length and the ion-exchanger group content of polyionic ligand were adjusted by controlling the degree of polymerization and the grafting density, respectively. This property allowed control of the separation performance of the ion-exchanger packing.

Preparation and characterization of zirconium (IV) molybdo tungsto vanado silicate as a novel inorganic ion exchanger in sorption of radionuclides.

A new mixed metal heteropoly anion-based cation exchanger Zr(IV) molybdo tungsto vanado silicate (ZMTVS) was prepared under varying conditions. The material was characterized by FTIR, X-ray diffraction, TGA-DTA and SEM techniques. Its ion exchange capacity (IEC) for K(+) was found to be 0.86 meq g(-1). Distribution coefficients (K(d)) values for 10 metal ions and three radioisotopes were determined. On the basis of K(d) values, two important and analytically difficult quantitative binary separations viz. Ni(II)-Co(II) and Ni(II)-Pb(II) were achieved on its column. Decontamination of aqueous nuclear waste solution was also studied.

Studies on the adsorption behavior of trace amounts of 90Sr2+, 140La3+, 60Co2+, Ni2+ and Zr4+ cations on synthesized inorganic ion exchangers.

Three inorganic ion exchangers namely potassium zinc hexacyanoferrate(II) (PZF), magnesium oxide-polyacrylonitrile composite (MgO-PAN) and ammonium molybdophosphate (AMP) were synthesized. The physicochemical properties of these ion exchangers were determined using different techniques including inductively coupled plasma (ICP), CHNSO elemental analysis, infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric (TGA) and pH - titration curve analysis. The solubility of the synthesized ion exchangers in different acidic and alkaline media, their thermal stability and the effect of gamma irradiation were investigated. It was observed that the exchange capacity of the ion exchangers depend upon the pH value of the solution used. Furthermore, the adsorption of (90)Sr(2+), (140)La(3+), (60)Co(2+) and the distribution coefficient of these ion exchangers for Ni(2+)and Zr(4+) were studied. The effect of parameters such as pH and contact time on the adsorption was also investigated and the optimum conditions for separation of these ions were determined.

Synthesis of high capacity cation exchangers from a low-grade Chinese natural zeolite.

The Chinese natural zeolite, in which clinoptilolite coexists with quartz was treated hydrothermally with NaOH solutions, either with or without fusion with NaOH powder as pretreatment. Zeolite Na-P, Na-Y and analcime were identified as the reacted products, depending on the reaction conditions such as NaOH concentration, reaction time and hydrothermal temperature. The products were identified by X-ray diffraction, and characterized by Fourier transform IR and ICP. With hydrothermal treatment after fusion of natural zeolite with NaOH, high purity of zeolite Na-Y and Na-P can be selectively formed, their cation exchange capacity (CEC) are 275 and 355 meq/100g respectively, which are greatly higher than that of the natural zeolite (97 meq/100g). Furthermore, the ammonium removal by the synthetic zeolite Na-P in aqueous solution was also studied. The equilibrium isotherms have been got and the influence of other cations present in water upon the ammonia uptake suggested an order of preference Ca(2+)>K(+)>Mg(2+).

Automated pretreatment system for the speciation of Cr(III) and Cr(VI) using dual mini-columns packed with newly synthesized chitosan resin and ME-03 resin.

Chitosan resin possessing the 4-hydroxyphthalic acid moiety (CCTS-HPA resin) was synthesized. This resin could adsorb chromium(VI) at pH 3 to 5, whereas chromium(III) could not be retained in the acidic region. The CCTS-HPA resin was used for collecting chromium(VI), and ME-03 resin was used for collecting chromium(III) before their measurement by ICP-AES measurement. Both resins were packed in mini-columns and installed serially in a laboratory-assembled automated pretreatment system (Auto-Pret System). The system provides a highly sensitive and fully automated procedure for the speciation of chromium(III) and chromium(VI). The proposed system was successfully applied to speciation of chromium(III) and chromium(VI) using 5 ml of water samples. The detection limits (S/N = 3) of chromium(III) and chromium(VI) were 0.06 and 0.04 microg l(-1), respectively, along with an analysis time of 7 min 45 s for both chromium species. The lowest determinable concentrations for both chromium species were about 0.5 microg l(-1), which was enough for the speciation of chromium in water samples.