Strong Anion-exchange Sorbents Research Articles

Phosphonium based anion exchange resin for enrichment of phenolic acids

The aim of this work is to investigate the efficiency of a phosphonium-based strong anion exchange sorbent for the extraction of some selected phenolic acids. The material was synthesized through chloromethylation of a porous poly(styrene-divinylbenzene) substrate with high degree of crosslinking, followed by quaternarization with tributyl phosphine. The parameters affecting the solid phase extraction of five phenolic acids, namely chlorogenic acid, caffeic acid, dihydroxybenzoic acid, ferulic acid and rosmarinic acid were optimized. The sample pH and the type, volume and concentration of the eluting solutions were investigated. The analysis of the phenolic acids after extraction was performed using HPLC with diode array detection. Limit of detection, limit of quantitation, linear range, correlation coefficient and reproducibility for the determination of the phenolic acids were estimated. The retention of the phenolic acids on the developed phase was studied using breakthrough analysis. The experimental breakthrough curves were fitted by Boltzmann's function, and the regression parameters were utilized for the determination of the breakthrough parameters. The results obtained using the developed phase were compared with those obtained by the commercially available Oasis MAX sorbent. The proposed approach was successfully applied for the extraction and pre-concentration of rosmarinic acid from rosemary leaf (Rosmarini folium) alcoholic extract.

Novel covalent organic frameworks based electrospun composite nanofiber membranes as pipette-tip strong anion exchange sorbent for determination of inorganic arsenic in rice

Novel covalent organic frameworks (COFs) based PAN@TpBD(NH2)2 electrospun composite nanofiber membranes (ECNMs) were fabricated as strong anion exchange sorbent by implementing electrospinning technology. The finished sorbent was characterized, and key parameters of pipette-tip solid phase extraction (PTSPE) procedures were investigated. Inorganic arsenic (iAs) was successfully separated from rice under the optimal precondition conditions, and quantified by hydride generation-atomic fluorescence spectrometry (HG-AFS). This PTSPE-HG-AFS methodology achieved 0.015 μg L-1 detection limit, 4.67 % relative standard deviation, and 86.48～99.11 % recoveries. In this work, preparation and characterization of this novel COFs-based anion exchange sorbent, PAN@TpBD(NH2)2 ECNMs, is described and its suitability for PTSPE applications is demonstrated.

Arsenosugar extracted from algae: Isolation by anionic exchange solid‐phase extraction

Obtaining reliable speciation data for evaluating dietary exposure, and increasing understanding of arsenic biochemistry in algae, are hindered by the availability of suitable standards of arsenosugars, the major species in these types of samples. Moreover, chemical syntheses of such compounds have been reported to be complex and tedious. The aim of this work was to investigate the feasibility of the anionic exchange SPE cartridges (SAX and WAX) as an easy and quick alternative for the isolation and preconcentration of arsenosugars. Two commercial silica-based SPE cartridges strong anion exchange sorbent (DSC-SAX) and weak anion exchange sorbent (DSC-NH2) were compared for the SPE of three arsenosugars (PO4-Sug, SO3-Sug and SO4-Sug). The effect of pH, ionic strength, type of salt and elution solvent on the elution protocols of these arsenosugars are studied. Eluted solutions from SPE were analyzed by ICP-MS for total arsenic content and IC-ICP-MS for the study of arsenic speciation.The developed SPE procedure allows to obtain a solution containing the three arsenosugars isolated from other arsenic species with recoveries over 75% for SO3-Sug and SO4-Sug, whereas for PO4-Sug were around 45%.

Solid-phase Extraction and High Performance Liquid Chromatographic Determination of Folic Acid in Fortified Foodstuffs: a Recommended Process Utilizing a New Strong Anion Exchange Sorbent

Solid-phase Extraction and High Performance Liquid Chromatographic Determination of Folic Acid in Fortified Foodstuffs: a Recommended Process Utilizing a New Strong Anion Exchange Sorbent

New generation of sequential injection chromatography: Great enhancement of capabilities of separation using flow analysis

Since its inception, sequential injection chromatography (SIC) has evolved through several stages. Key moments including introduction of the novel technique combining sequential injection analysis and monolithic column, the first generation of commercial SIC system employing robust pump, the utilization of columns packed with fused-core particles, the on-line hyphenation of extraction and separation steps in SIC, are now followed by the second generation of commercial SIC system employing stainless steel syringe pump and parts optimized for chromatographic separation. The key developments always mean acceleration of the evolution by opening new avenues and reduction of compromises in automated analytical methods based on the flow analysis. The updates, new features, and prospects of the novel instrument are described and discussed on perspective of the method developed for extraction and separation of selected phenolic acids (gallic, protocatechuic, caffeic, p-coumaric and ferulic). The method hyphenates miniaturized on-line solid phase extraction using strong anion exchange sorbent in commercial cartridge for HPLC (20 × 1 mm) and liquid chromatography using chromatographic column (C18 50 × 4.6 mm, 5 μm particles) packed with fused-core particles in the SIC manifold. The separation in gradient mode used acetonitrile: aqueous formic acid pH 2.0 mobile phase and spectrophotometric detection at 270, 300, and 320 nm. Injected sample volumes were 200 and 500 μL. The performance of the extraction step was characterized by the recovery 94.0–107.8%, enrichment factors about 20 or 50, and the separation by peak capacities 13–34, peak symmetries 1.17–1.64, and resolutions 0.82–3.75). While using a sample volume of 200 μL, our method was characterized by the following validation parameters: LODs of 0.0075–0.03 mg L−1, LOQs of 0.025–0.10 mg L−1, calibration ranges 0.025–2.50 mg L−1 (r > 0.999), repeatability of signal at 0.50 mg L−1of RSD ≤ 1.46% (n = 6), and overall time of analysis 7.1 min. The results including pilot analysis of white and red wines demonstrated the capability of novel SIC instrument to enable fast, selective, and sensitive analysis.

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.

Study of the retention of benzotriazoles, benzothiazoles and benzenesulfonamides in mixed-mode solid-phase extraction in environmental samples

In the present study, the capabilities of strong cation-exchange and strong anion-exchange sorbents for solid-phase extraction (SPE) have been evaluated for the selective retention of benzotriazoles (BTRs), benzothiazoles (BTs) and benzenesulfonamides (BSAs), which are a group of neutral analytes with interesting properties such as high polarity and the capability of delocalizing electron density. The retention of these analytes has been compared in both sorbents for the first time, using a SPE procedure specially designed to promote ionic retention of the analytes with the objective of including a washing step with an organic solvent to eliminate interferences retained by hydrophobic interactions.As a result, ionic interactions between the analytes and both sorbents were observed, which allowed the successful introduction of a washing step using methanol in the SPE procedure even when most of the analytes were in their neutral state under SPE conditions. Consequently, a method was developed and further validated for each sorbent using liquid chromatography coupled to high-resolution mass spectrometry (LC–HRMS). Apart from the development of an improved method, special attention was paid to the discussion of the interactions present between the sorbents and each group of analytes to explain how these analytes in their neutral state might develop ionic interactions with the sorbents. At the end, the use of these sorbents helped to simplify previous developed methods where hydrophobic/hydrophilic sorbents were used, obtaining enhanced results when evaluated in river water and effluent and influent wastewaters.

Comprehensive evaluation of imidazole-based polymers for the enrichment of selected non-steroidal anti-inflammatory drugs

This study reports the comparison of four manufactured imidazole-based copolymers and two commercially available hydrophilic sorbents for the solid phase extraction (SPE) of selected non-steroidal anti-inflammatory drugs (NSAID). Different hydrophilic copolymers were obtained by a suspension polymerization using a styrene-based and a methacrylate-based cross-linker and by single step modifications for enhancing the ion-exchange character. SPE protocols were optimized for both non-modified and modified sorbents and applied for the enrichment of selected NSAID using all six copolymers.Comparison and evaluation were carried out by determining recovery rates of standard mixtures at different concentration levels ranging from 0.5mgL−1 to 10mgL−1 and by the enrichment of spiked human urine at two concentration levels. In order to gain insight into the complexity of the biological sample and its reduction after solid phase extraction, UHPLC–MS analysis and following database comparison was performed for the three mixed-mode strong anion-exchange sorbents. In order to prove the applicability of the modified imidazole-based polymers for the enrichment of NSAID in surface water, river water or groundwater, solid phase extraction was performed with 10ppb of NSAID which resulted into enhanced enrichment by a hundredfold.

Determination of Polycyclic Aromatic Hydrocarbons in Coffee and Coffee Substitutes using Dispersive SPE and Gas Chromatography-Mass Spectrometry

The purpose of this study was to evaluate the application of dispersive solid-phase extraction with the use of primary secondary amine (PSA), NH2 and strong anion exchange (SAX) sorbents for polycyclic aromatic hydrocarbon (PAH) determination in samples of coffee. The final extracts were analysed by gas chromatography selected ion monitoring mass spectroscopy (GC-SIM-MS). The results indicated that cleanup with PSA and SAX sorbents followed by final solvent exchange from acetonitrile to hexane (liquid–liquid extraction, LLE) was the best variant of the method, resulting in the cleanest extracts and satisfactory compound recoveries (70–104 %) for examined compounds in coffee samples. In the study of real samples, the concentrations of PAH markers (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[a]pyrene) were higher for natural roasted coffee (7.20–68.15 μg kg−1), than for instant coffee (2.97–19.55 μg kg−1) and cereal coffee (8.15–15.35 μg kg−1), and the sum of PAHs was also higher in natural and instant coffees compared to coffee substitutes (364, 343 and 265 μg kg−1, respectively). However, in all samples of coffee, light (three-ring) PAHs dominated within the identified compounds and phenanthrene was the most abundant compound, approaching 209.67 μg kg−1 in roasted coffee.

Simultaneous determination of β-hydroxybutyrate and β-hydroxy-β-methylbutyrate in human whole blood using hydrophilic interaction liquid chromatography electrospray tandem mass spectrometry

ObjectivesFor the quantification of β-hydroxybutyrate (BHB) and β-hydroxy-β-methylbutyrate (HMB) in human whole blood, a method using hydrophilic interaction liquid chromatography tandem mass spectrometry (HILIC–MS/MS) was developed, which does not require chemical modification of the analytes. Design and methodsSamples were deproteinised by a mixture of methanol and acetonitrile, and the extracts were cleaned-up using both polymeric strong cation exchange and strong anion exchange sorbents. The analytes and their structural isomers were separated using a column with a zwitterionic stationary phase. Isotope dilution of both analytes was used for quantitative analysis. ResultsSeparation of BHB from isobaric interferences was achieved through chromatography. The relative intra-laboratory reproducibility standard deviations were better than 10% for blood samples at concentration levels of 10–20μM BHB and 1μM HMB and better than 5% at concentration levels 10 times higher. The mean true extraction recoveries were close to 100%. The trueness expressed as the relative bias of test results was within ±5% at concentration levels of 10–1000μM BHB and 1–20μM HMB. The lower limits of quantification were estimated to be 3μM for BHB and 0.4μM for HMB. ConclusionsA simple and highly sensitive and selective HILIC–MS/MS method was developed that is suitable for the quantification of BHB and HMB in whole blood.

Hypercrosslinked strong anion‐exchange resin for extraction of acidic pharmaceuticals from environmental water

Two novel high-specific surface area polymeric sorbents (HXLPP-SAXa and HXLPP-SAXb) were synthesised and evaluated as solid-phase extraction sorbents. The novel sorbents under study are based on hypercrosslinked polymer microspheres and designed specifically to offer ion-exchange properties; the specific polymers of interest in the current work have been chemically modified in such a way as to impart a tuneable level of strong anion-exchange character onto the sorbents. The novel sorbents were applied as strong anion-exchange sorbents in solid-phase extraction studies, with the goal being to selectively extract a group of acidic compounds from complex environmental samples in an efficient manner. Out of two HXLPP-SAX resins evaluated in this study, it was found that the sorbent with the lower ion-exchange capacity (HXLPP-SAXa) gave rise to the best overall performance characteristics and, indeed, was found to compare favourably to the solid-phase extraction performance of commercial strong anion-exchange sorbents. When the HXLPP-SAXa sorbent was applied to the solid-phase extraction of environmental water samples, the result showed quantitative and selective extraction of low levels of acidic pharmaceuticals from 500 mL of river water and 100 mL of effluent wastewater.

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

Solid phase extraction (SPE) methods based on multiple extractions have been developed to overcome matrix interferences in the charge-based fractionation analysis of As, Cr, Mo, Sb, Se and V leached from cement-based materials. Disposable SPE tubes packed with 500 mg strong anion-exchange (SAX) or strong cation-exchange (SCX) sorbents were used to extract the anionic and cationic species of the elements, respectively. The multiple extractions were based on the percolation of a small sample volume (5.0 mL) through a series of identical ion-exchange tubes. For most of the elements, more than 90% of the anionic species were extracted from a sample containing up to 16 g L −1 NO 3 − by passing the aliquot through five identical SAX tubes. Percolating a sample aliquot through three identical SCX cartridges gave more than 99% retention for Cr(III) from leachates containing a high concentration of interfering metal cations. The anionic and cationic analytes showed only slight non-specific adsorption on the SCX and SAX sorbents, respectively, except for V(V) on the SCX sorbent. A condition was established for the quantitative elution of the retained analytes from the ion-exchange sorbents with 1.0 mol L −1 HNO 3. The multiple ion-exchange SPE procedures were validated using spike recovery tests. The methods were used to determine the anionic and cationic fractions of the target elements in concrete leachates covering a broad range of pH (3.8–13.4). The elements were found to exist predominantly as anions in the alkaline and neutral leachates. A high fraction (85%) of cationic Cr was detected in the most acidic leachate (pH 3.8).

Comparison of mixed-mode anion-exchange performance ofN-vinylimidazole-divinylbenzene sorbent

A newly synthesized copolymer based on N-vinylimidazole-divinylbenzene (NVIm-DVB) was evaluated as a mixed-mode anion-exchange sorbent for SPE, since the NVIm monomer apart from its hydrophilic properties can be protonated at a certain pH, and then performs as an anion-exchanger. To investigate the behavior of the NVIm-based sorbent, the SPE performance was evaluated under reversed-phase (RP), weak anion-exchange, and strong anion-exchange conditions. The results for the NVIm-DVB sorbent were also compared to commercial reference sorbents from each group: Oasis HLB, Oasis WAX, and Oasis MAX, respectively. SPE results from this evaluation showed that NVIm-DVB can be used as an RP material, compared to Oasis HLB. It also has the potential to act as a strong anion-exchange sorbent, compared to Oasis MAX, since under the proper conditions it was able to fraction and quantitatively recover a group of selected solutes.

Determination of linear alkylbenzensulfonates in aqueous matrices by ion-pair solid-phase microextraction–in-port derivatization–gas chromatography–mass spectrometry

Trace determination (low ng/ml) of linear alkylbenzensulfonates (LASs) in water was achieved by solid-phase microextraction (SPME) of ion-pairs formed with tetrabutylammonium. This ion-pairing reagent served two purposes. First, it allowed the extraction of LAS with the polydimethylsiloxane fiber by counterion association and second, the derivatization of the formed LAS ion pairs in the GC injection port at 300 °C to form the corresponding sulfonated butyl esters. The methodology developed allows the isomer specific determination of LAS at low detection limits (0.16–0.8 ng/ml), depending on the alkyl chain lengths of LASs with RSDs of 10–12%. Furthermore, the developed methodology was applied to urban wastewater and sea water and compared with a solid-phase extraction (SPE) method (e.g. C 18 and strong anion-exchange sorbent) to obtain concordant values for urban wastewater. Moreover, the developed SPME methodology overcame the procedural blank and matrix-dependent recoveries found in the SPE methodologies at low LAS concentrations.

HPLC-fluorescence determination of equilin and equilenin in postmenopausal women's urine.

A high-performance liquid chromatographic (HPLC) method with fluorescence detection (lambda(ex) = 280 nm; lambda(em) = 410 and 312 nm) in combination with a post-column on-line photochemical derivatization is described for the determination of equilin and equilenin in urine from normal postmenopausal women after therapy with conjugated oestrogens. The column effluents were subjected on-line to UV irradiation (254 nm) and the photo-induced modifications were useful for the identification of the analytes. The conjugated (sulphate and glucuronide) forms were analysed after enzymatic or chemical hydrolysis and extracted with chloroform. Solid-phase extraction using strong anion-exchange sorbent was applied to the analysis of unconjugated oestrogen fraction to obtain a practical and reliable sample clean-up. The HPLC separations were achieved using ODS columns with a mobile phase consisting of 0.05 M triethylamine phosphate buffer (pH 4.0)-acetonitrile (64:36, v/v) at a flow rate of 1.0 mL/min. The method was accurate and reproducible; for the equilin and equilenin separation isocratic conditions were satisfactory, allowing a sensitive detection in urine samples with a detection limit of about 50 fmol for equilin (lambda(ex) = 280 nm; lambda(em) = 312 nm, after photoderivatization) and 10 fmol for equilenin (lambda(ex) = 280 nm; lambda(em) = 410 nm).

High-performance liquid chromatography of amino acids, peptides and proteins: CXI. Retention behaviour of proteins with macroporous tentacle-type anion exchangers

The chromatographic behaviour of various proteins with Fractogel-TMAE and LiChrospher-TMAE tentacle-type strong anion-exchange sorbents has been investigated. In particular, the log {ie versus log {ie (where {ie is the median capacity factor and {ie is the corresponding salt concentration) dependencies for two salt systems (NaCl and KBr) have been documented. The Fractogel-TMAE sorbent exhibited retention characteristics in terms of relative protein charge dependencies (slope Z c) and affinity values (log K c, which is log {ie at c = 10 −6 M, where c is the concentration of the displacer ion) which were similar to the more conventional anion-exchange sorbents such as the Mono-Q sorbent. However, the Z c and log K c values obtained with the LiChrospher-TMAE sorbent were significantly decreased for most proteins. Furthermore, proteins such as carbonic anhydrase and myoglobin were not retained at pH values up to 4 and 2 units above their p I values, respectively. These results illustrate the different adsorptive properties of the tentacle-type sorbents compared to other monolayer or polymer layer ion exchangers in terms of accessibility of the charged ligand and the underlying retention mechanism.