Copolymer Sorbent Research Articles

Quantitative method for analysis of hydrocodone, hydromorphone and norhydrocodone in human plasma by liquid chromatography–tandem mass spectrometry

A selective, sensitive and accurate high-performance liquid chromatography-tandem mass spectrometry (LC-MS-MS) method for the quantitation of hydrocodone, hydromorphone and norhydrocodone in human plasma was developed. The internal standard stock solution comprised of hydrocodone-d6, hydromorphone-d6 and norhydrocodone-d3 was added to 0.5 mL plasma samples. Samples were extracted using a copolymeric sorbent (mixed mode) solid phase extraction (SPE) column. Chromatographic separation was carried out using a reversed-phase C18 analytical column with a gradient mobile phase consisting of solvent A=5% acetonitrile with 0.1% formic acid and solvent B=100% acetonitrile. MS analysis was performed using positive electrospray ionization (ESI) in multiple reaction monitoring (MRM) mode. Linearity was established over the range 1-100 ng/mL with correlation coefficients ≥0.998 for all three analytes. The coefficient of variation (CV) of intra-day samples was ≤5.6% at 10 ng/mL. The precision of inter-day (6 days) samples resulted in CVs ≤8.1% at concentrations tested at 2.5, 10 and 25 ng/mL for all three analytes. The lower limit of quantification (LOQ) was 1.0 ng/mL with signal-to-noise (S/N) ratio >10, the limit of detection (LOD) was 0.25 ng/mL with S/N ratio >3 for the drug and its metabolites. Dilution effects, extraction recovery, stability, interference, carryover and ion suppression were also evaluated. This method was successfully applied to human subject plasma samples in support of a hydrocodone pharmacokinetic study.

Preparation and sorption studies of glutaraldehyde cross-linked chitosan copolymers

Chitosan–glutaraldehyde copolymer sorbents were synthesized by reacting variable weight ratios (low, medium, and high) of glutaraldehyde with fixed amounts of chitosan. Two commercially available chitosan polymers with low (L) and high (H) relative molecular weights were investigated. The chitosan–glutaraldehyde (Chi–Glu) copolymer sorbents are denoted as CPL-X or CPH-X where X denotes the incremental level (X=−1, −2, −3) of glutaraldehyde. The copolymers were characterized using FT-IR spectroscopy and TGA. The solid–solution sorption isotherms in alkaline aqueous solution for the copolymers were characterized using absorbance and emission based spectroscopic methods for p-nitrophenol (PNP) and the arsenate oxoanion HAsO42- species, respectively. The Sips isotherm model was utilized to obtain sorption parameters at pH 8.5 and 295K (i.e. sorbent surface area, sorption capacity and removal efficiency) for each copolymer sorbent. The sorbent surface areas for the low molecular weight chitosan copolymers are listed in parentheses (m2g−1), as follows: CPL-1 (124), CPL-2 (46.7) and CPL-3 (31.6). The high molecular weight chitosan copolymers are as follows: CPH-1 (79.8), CPH-2 (64.7) and CPH-3 (96.3). The removal efficiencies depend on the pH, temperature, and the relative amounts of sorbate and sorbent. The sorbent removal efficiencies for p-nitrophenol ranged between 7.1% and 49%, and the values for H2AsO42- ranged between 31% to 93% for the low and high molecular weight copolymers.

Preparation and sorption studies of β-cyclodextrin–chitosan–glutaraldehyde terpolymers

β-Cyclodextrin–chitosan–glutaraldehyde terpolymers were synthesized by reacting variable weight fractions of β-cyclodextrin (β-CD) and chitosan (Chi), with a constant amount of crosslinker (glutaraldehyde). The β-CD:Chi:Glu terpolymer sorbents were characterized by FT-IR spectroscopy and TGA. The solid-solution sorption isotherms in aqueous solution for the copolymers were characterized using two spectroscopic methods (UV–Vis and ICAP-OES) for p-nitrophenol (PNP) and the arsenate oxoanion (HAsO42-) at alkaline pH conditions. The Sips isotherm model was utilized to obtain sorption parameters at pH 8.5 and 295K (i.e. sorbent surface area, sorption capacity and removal efficiency) for each copolymer sorbent. The sorbent surface area estimates for the terpolymers at low (T1), medium (T2), and high (T3) weight fractions of β-CD are listed in parentheses (m2g−1), as follows: T1 (161), T2 (51.2) and T3 (275). The removal efficiencies are dependent on the relative weight fraction of the polysaccharide components (i.e. β-CD and Chi); whereas the removal efficiencies for p-nitrophenolate ranged between 7.3% and 28%, and H2AsO42- ranged between 23% and 55%.

Determination of perfluoroalkyl carboxylic, sulfonic, and phosphonic acids in food

A sensitive and accurate method was developed and validated for simultaneous analysis of perfluoroalkyl carboxylic acids, sulfonic acids, and phosphonic acids (PFPAs) at low picograms per gram concentrations in a variety of food matrices. The method employed extraction with acetonitrile/water and cleanup on a mixed-mode co-polymeric sorbent (C8 + quaternary amine) using solid-phase extraction. High-performance liquid chromatographic separation was achieved on a C18 column using a mobile phase gradient containing 5 mM 1-methyl piperidine for optimal chromatographic resolution of PFPAs. A quadrupole time-of-flight high-resolution mass spectrometer operating in negative ion mode was used as detector. Method detection limits were in the range of 0.002 to 0.02 ng g(-1) for all analytes. Sample preparation (extraction and cleanup) recoveries at a spiking level of 0.1 ng g(-1) to a baby food composite were in the range of 59 to 98 %. A strong matrix effect was observed in the analysis of PFPAs in food extracts, which was tentatively assigned to sorption of PFPAs to the injection vial in the solvent-based calibration standard. The method was successfully applied to a range of different food matrices including duplicate diet samples, vegetables, meat, and fish samples.

Preparation and sorption studies of polyester microsphere copolymers containing β-Cyclodextrin

Polyester copolymer sorbent materials that incorporate β-Cyclodextrin (β-CD) were prepared using water-in-oil (w/o) micro-emulsion conditions at variable β-CD: cross linker mole ratios; where the cross linker units were sebacoyl chloride (SCl) and terephthaloyl chloride (TCl). The copolymers were characterized using TGA, nitrogen adsorption, and NMR/IR spectroscopy. The dye-based sorption properties of the copolymers with p-nitrophenol (PNP) in aqueous solution were evaluated at pH 4.6 and 295K using UV–Vis spectrophotometry. The uptake of PNP varied from 0.221 to 0.352mmol/g, according to the nature of the cross linker and the copolymer mole ratio. The sorption capacity of SCl-based copolymers exceed that for TCl-based copolymers, and correlate with the relative swelling properties and hydrated surface areas of the sorbent frameworks. 1H NMR spectroscopy of copolymers with low levels of linker content (i.e. SCl or TCl) indicate dual sorption sites for PNP (i.e. β-CD inclusion sites and non-inclusion (interstitial) linker domains). The existence of dual sorption sites is similarly concluded for copolymers containing higher levels of cross linker. Inclusion complexes are firstly formed between PNP and the β-CD inclusion sites of the copolymer; thereafter, PNP is adsorbed onto the linker domains of the copolymer sorbent framework.

Ionic liquids-based crosslinked copolymer sorbents for headspace solid-phase microextraction of polar alcohols

Halogen-based polymeric ionic liquid (PIL) fibers, which have proved efficient for solid-phase microextraction (SPME) of polar compounds, were with very limited fiber lifetimes. In this work, a novel crosslinked PIL sorbent with satisfactory stability and durability was prepared in situ via crosslinking polymerization processes on microstructured-silver coated stainless steel wire. 1,1′-(1,6-Hexanediyl)bis(1-vinylimidazolium) bibromide ionic liquid was synthesized and used as the crosslinking agent, with 1-vinyl-3-octylimidazolium bromide as monomer. Extraction properties of the fiber for polar alcohols in polar aqueous matrix were examined using headspace SPME (HS-SPME) coupled to gas chromatography-flame ionization detection (GC-FID). Under the optimized extraction and desorption conditions, the established method exhibited high extraction capacity. Wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9947 to 0.9999. Limits of detection were in the range of 0.5–20μgL−1. Compared with the non-crosslinked PIL fiber, the proposed crosslinked PIL fiber was with higher thermal stability and durability and longer lifetime. Four different liquor beverages were analyzed as real samples and good results were obtained.

Control of Adsorption/Desorption of Anions Based on Redox of Solid Phase Coated with Cobalt Complexes

The adsorption-desorption behaviors of hydrophobic anion on the solid phase coated with redox-active metal complexes (ML2+/0 ; M, CoIII/II ; L−, pyridylazo compounds) were investigated. The combination of a cobalt complex of poly vinyl phenol introduced with a 2-pyridylazo group and a solid-phase extraction cartridge packed with styrene-divinyl benzene copolymer sorbent showed the highest adsorption capacity for methyl orange as a hydrophobic anion. The percentage adsorption of methyl orange (1.0 μmol) on this solid phase was more than 99%, even in the presence of a 100-fold stoichiometric excess of coexisting anions (ClO4−, Cl−). Methyl orange molecules were desorbed by reducing the cobalt complexes in the solid phase with a 1.0 × 10−2 M ascorbic acid solution.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X copolymers (< 101 m2/g), and granular activated carbon (GAC ~103 m2/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water

A trace analytical method based on high performance liquid chromatography coupled to quadrupole time-of-flight high resolution mass spectrometry was developed for simultaneous determination of perfluoroalkyl phosphonates (PFPAs, carbon chain lengths C6,8,10), perfluoroalkyl carboxylates (PFCAs, C5–12), and perfluoroalkyl sulfonates (PFSAs, C4,6,8,10) in drinking water (tap water). Analytes were enriched on a mixed mode co-polymeric sorbent (C8 + quaternary amine) using solid phase extraction. Chromatographic separation was achieved on a Zorbax Extend C18 reversed phase column using a mobile phase gradient consisting of water, methanol, and acetonitrile containing 2 mM ammonium acetate and 5 mM 1-methyl piperidine. The mass spectrometer was operated in electrospray negative ion mode. Use of 1-methyl piperidine in the mobile phase resulted in a significant increase in instrument sensitivity for PFPAs through improved chromatographic resolution, background suppression, and increased ionization efficiency. Method detection limits for extraction of 500 mL tap water were in the ranges of 0.095–0.17 ng/L, 0.027–0.17 ng/L, and 0.014–0.052 ng/L for PFPAs, PFCAs, and PFSAs, respectively. Whole method recoveries at a spiking level of 0.5 ng/L to 500 mL HPLC grade water were 40–56%, 56–97%, and 55–77% for PFPAs, PFCAs, and PFSAs, respectively. A matrix effect (signal enhancement) was observed in the detection of PFPAs in tap water extracts, leading to calculated recoveries of 249–297% at a 0.5 ng/L spiking level. This effect resulted in an additional improvement of method sensitivity for PFPAs. To compensate for the matrix effect, PFPAs in tap water were quantified using matrix-matched and extracted calibration standards. The method was successfully applied to the analysis of drinking water collected from six European countries. PFPAs were not detected except for perfluorooctyl phosphonate (PFOPA) at close to the detection limit of 0.095 ng/L in two water samples from Amsterdam, the Netherlands. Highest levels were found for perfluorobutane sulfonate (PFBS, 18.8 ng/L) and perfluorooctanoate (PFOA, 8.6 ng/L) in samples from Amsterdam as well as for perfluorooctane sulfonate (PFOS, 8.8 ng/L) in tap water from Stockholm, Sweden.

Sequestration of naphthenic acids from aqueous solution using β-cyclodextrin-based polyurethanes

The sorption characteristics of naphthenic acids (NAs) in their anion form with β-cyclodextrin (β-CD) based polyurethanes, as sorbents, from aqueous solutions that simulate the conditions of oil sands process water (OSPW) are presented. The copolymer sorbents were synthesized at various β-CD:diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and degree of unsaturation. The equilibrium sorption properties of the copolymer sorbents were characterized using sorption isotherms in aqueous solution at pH 9.00 with electrospray ionization mass spectrometry to monitor the equilibrium unbound fraction of anionic NAs in the aqueous phase. The copolymer sorbents were characterized in the solid state using (13)C CP-MAS NMR spectroscopy, IR spectroscopy and elemental analysis. The sorption results of the copolymer sorbents with anion forms of NAs in solution were compared with a commercially available carbonaceous standard: granular activated carbon (GAC). The monolayer sorption capacities of the sorbents (Q(m)) were obtained from either the Langmuir or the Sips isotherm model used to characterize the sorption characteristics of each copolymer sorbent. The estimated sorption capacity for GAC was 142 mg NAs per g sorbent whereas the polymeric materials ranged from 0-75 mg NAs per g sorbent over the experimental conditions investigated. In general, significant differences in the sorption capacities between GAC and the copolymer sorbents were related to the differences in the accessible surface areas and pore structure characteristics of the sorbents. The Sips parameter (K(eq)) for GAC and the copolymer materials reveal differences in the relative binding affinity of NAs to the sorbent framework in accordance with the synthetic ratios and the value of Q(m). The diisocyanate linker plays a secondary role in the sorption mechanism, whereas the β-CD macrocycle in the copolymer framework is the main sorption site for NAs because of the formation of inclusion complexes with β-CD.

Poly(acrylamide-co-itaconic acid) as a Potential Ion-Exchange Sorbent for Effective Removal of Antibiotic Drug-Ciprofloxacin from Aqueous Solution

This study describes equilibrium and kinetic sorption studies to remove the antibiotic drug Ciprofloxacin (CF) from aqueous solutions using poly(acrylamide-co-itaconic acid) [poly(AAm-co-IA)] as polymeric cation exchanger sorbent material. The co-polymeric sorbent was prepared by free radical induced aqueous polymerization and was characterized by FTIR spectroscopy and TGA analysis. In addition, its physicochemical parameters were also determined. The various isotherm models, when applied to equilibrium sorption data at 28°C, followed the following order: Langmuir > Temkin > Freundlich, with the fair maximum sorption capacity (Q o ) of 178.5 mg g−1. The kinetic sorption data, obtained at 28°C, was applied to kinetic models such as pseudo first order equation, pseudo second order model and a simple Elovich model. Based on regression values, the order of fitness of these models was pseudo second order > pseudo first order > simple Elovich model. The second order adsorption coefficients k2adswere found to be 58 × 10−3, 52.7 × 10−3, 34.01×10−3 g/mg min for drug solutions with initial concentrations of 10, 20 and 30 mg L−1 respectively The sorption mean free energy from the Dubinin–Raduschkevich (DR) isotherm was found to be nearly 8.839 kJ mol−1 indicating an ion-exchange mechanism for drug uptake. The optimum pH value of sorbate solution for drug uptake was found to be around 6.0. Finally, the antibacterial action of drug was investigated and it was found that after adsorption there was a decrease in bacterial growth inhibition efficiency of drug solution.

Investigation of the sorption properties of β-cyclodextrin-based polyurethanes with phenolic dyes and naphthenates

The sorption of p-nitrophenol (PNP), phenolphthalein (phth) and naphthenates (NAs) with β-cyclodextrin (β-CD) based polyurethane sorbents from aqueous solutions are reported. The copolymer sorbents were synthesized at various β-CD/diisocyanate monomer mole ratios (e.g., 1:1, 1:2, and 1:3) with diisocyanates of variable molecular size and hydrogen deficiency. The copolymer sorbents were characterized in the solid state using 13C CP-MAS NMR spectroscopy, IR spectroscopy and elemental (C, H, N) analysis. The equilibrium sorption properties of the copolymer sorbents in aqueous solution were characterized using isotherm models at pH 4.6 and 9.0 for PNP, pH 9.0 for naphthenates and pH 10.5 for phth. UV–Vis spectroscopy was used to monitor the unbound fraction of the phenolic dyes in the aqueous phase, whereas, electrospray ionization mass spectrometry was used to monitor the unbound fraction of naphthenates. The sorption results of the copolymer sorbents were compared with a commercially available carbonaceous standard; granular activated carbon (GAC). The sorption properties and capacities of the copolymer sorbents ( Q m ) were estimated using the Sips isotherm. The sorption capacity for GAC was 2.15 mmol PNP/g, 0.0698 mmol phth/g, and 142 mg NAs/g, respectively, whereas the polymeric materials ranged from 0.471 to 1.60 mmol/g (PNP), 0.114 to 0.937 mmol/g (phth), and 0 to 75.5 mg/g (naphthenates), respectively, for the experimental conditions investigated. The observed differences in the sorption properties were attributed to the accessible surface areas and pore structure characteristics of the copolymer sorbents. The binding constant, K eq , for copolymer materials for each sorbate is of similar magnitude to the binding affinity observed for native β-CD. PNP showed significant binding onto the copolymer framework containing diisocyanate domains, whereas, negligible sorption to the sites was observed for phth and naphthenates. The β-CD inclusion sites in the copolymer framework are concluded to be the main sorption site for phth and naphthenates through the formation of well-defined inclusion complexes.

Determination of Tricyclazole in Water Using Solid Phase Extraction and Liquid Chromatography

A method for determination of tricyclazole in water using solid phase extraction and high performance liquid chromatography (HPLC) with UV detection at 230 nm and a mobile phase of acetonitrile:water (20:80, v/v) was developed. A performance comparison between two types of solid phase sorbents, the C18 sorbent of Supelclean ENVI-18 cartridge and the styrene-divinyl benzene copolymer sorbent of Sep-Pak PS2-Plus cartridge was conducted. The Sep-Pak PS2-Plus cartridges were found more suitable for extracting tricyclazole from water samples than the Supelclean ENVI-18 cartridges. For this cartridge, both methanol and ethyl acetate produced good results. The method was validated with good linearity and with a limit of detection of 0.008 µg L−1 for a 500-fold concentration through the SPE procedure. The recoveries of the method were stable at ∼80% and the precision was from 1.1 − 6.0% within the range of fortified concentrations. The validated method was also applied to measure the concentrations of tricyclazole in real paddy water.

Optimization of a Solid-Phase Extraction Method Using Copolymer Sorbents for Isolation of Phenolic Compounds in Red Wines and Quantification by HPLC

Different solid-phase extraction (SPE) cartridges for the isolation of most of the phenolic compounds present in wines in low concentration were assayed and compared with the C18 SPE sorbent, which is the most common sorbent used for the isolation of these compounds. The use of C18 cartridges has several disadvantages; therefore, a SPE method using copolymer cartridges was developed, optimized, and validated. The method proposed seems to be a good alternative to replace C18 cartridges for the isolation of wine phenolic compounds. The advantages of the proposed SPE method with the HLB cartridge are that interferences can be eliminated with water without losing the compounds of great interest; the method has very good repeatability, reproducibility, and high percentages of recovery; it has a higher sensitivity and loading capacity than silica-based C18 cartridges due to the larger surface area of this type of sorbent, and the method is not adversely affected by drying, being more reproducible than C18 cartridge.

The use of solid-phase extraction and direct injection of a copolymer sorbent as slurry into the graphite furnace prior to determination of cadmium by ETAAS

Cadmium in different certified materials was determined by direct injection of sorbent loaded with the analyte into the graphite furnace of electrothermal atomic absorption spectrophotometer. For this purpose, cadmium was collected on ethylene glycol dimethacrylatemethacrylic acid copolymer treated with ammonium pyrolidine dithiocarbamate by the batch technique. After separation of liquid phase, slurry of the sorbent was prepared for the direct injection of the sorbent into graphite furnace. Optimum conditions for quantitative sorption and those for preparing homogeneous and durable slurry were investigated. A 100-fold enrichment factor could be reached. Cadmium in certified sea water and bovine liver samples was determined within the 95% confidence limits. The proposed technique is fast and simple, and the risk of contamination is low. The calculated detection limit for cadmium using sample-matching blanks was 0.09 µg L−1 according to the 3σ concept for the described method.

Application of solid-phase extraction coupled with freezing-lipid filtration clean-up for the determination of endocrine-disrupting phenols in fish

An analytical method has been developed for the determination of endocrine-disrupting phenols (eight alkylphenols and bisphenol A) in fish samples. The extraction of nine phenols from fish samples was carried out by ultrasonification. After the extraction, high levels of lipids were removed by freezing-lipid filtration instead of the traditional methods of column chromatography or saponification. During freezing-lipid filtration, about 90% of the lipids were eliminated without any significant loss of phenolic compounds. For further purification, hydrophilic–lipophilic balanced copolymer (HLB) sorbent with a poly(divinylbenzene-co- N-vinylpyrrolidone) phase and Florisil-solid-phase extraction (SPE) cartridges were used to eliminate the remaining interferences. Silyl-derivatization, with N, N′-methyl-( tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA), was applied to enhance the sensitivity of detection of phenolic compounds. Quantification was performed by gas chromatography/mass spectrometry (GC/MS)-selected ion monitoring (SIM) mode, using deuterium-labeled internal standards. Spiking experiments were carried out to determine the recovery, precision and detection limit of the method. The overall recoveries ranged between 70 and 120%, with relative standard deviations of 3–17% for the entire procedure. The detection limits of the method for the nine phenols ranged from 0.02 to 0.41 ng g −1. The method provided simultaneous screening and accurate confirmation of each phenol when applied to biological samples.

Removal of Cr(VI) Oxy‐anions from Aqueous Solution by Sorption into Poly(Acrylamide‐Co‐Maleic Acid) Hydrogels

The dynamic removal of hexavalent chromiuim by poly(acrylamide‐co‐maleic acid) hydrogels was studied by a batch equilibrium technique at 35°C. Various kinetic and adsorption parameters such as rate constant for sorption, intraparticle diffusion rate constant, Langmuir constant, and adsorption capacity have been evaluated. The sorption process follows the Langmuir‐type behavior and extent of sorption of Cr(VI) ions depends upon the composition of co‐polymeric gels, presence of other ions in the solution, and temperature of the system. Relatively higher temperature favors the sorption process. The activation energy was found to be −20.369 kJ mol−1. Finally, various thermodynamic parameters have also been calculated to elucidate the mechanism involved in the sorption process. The positive enthalpy change indicates the endothermic nature of the process. The presence of fluoride ions causes a decrease in the degree of sorption of Cr(VI). Finally, the sorption of Cr(VI) into the copolymeric sorbent has been explained on the basis of coordination between electron rich O and N atoms of sorbent molecules and the Cr(III) molecules. Moreover, H‐bonding interactions also seem to contribute to the sorption process.

Calibration of a passive sampling device for time‐integrated sampling of hydrophilic herbicides in aquatic environments

Two types of solid-phase materials, a styrenedivinylbenzene copolymer sorbent (embedded in a SDB-XC Empore disk) and a styrenedivinylbenzene copolymer sorbent modified with sulfonic acid functional groups (embedded in a SDB-RPS Empore disk), were compared as a receiving phase in a passive sampling device for monitoring polar pesticides. The SDB-XC Empore disk was selected for further evaluation, overlayed with either a polysulfone or a polyethersulfone diffusion membrane. The target herbicides included five nonionized herbicides (simazine, atrazine, diuron, clomazone, and metolachlor) and four phenoxy acid herbicides (dicamba, (2,4-dichlorophenoxy)acetic acid [2,4-D], (4-chloro-2-methylphenoxy)acetic acid [MCPA], and triclopyr) with log octanol/water partition coefficient (log K(OW)) values of less than three in water. Uptake of these herbicides generally was higher into a device constructed of a SDB-XC Empore disk as a receiving phase covered with a polyethersulfone membrane compared to a similar device covered with a polysulfone membrane. Using the device with a SDB-XC Empore disk covered with a polyethersulfone membrane, linear uptake of simazine, atrazine, diuron, clomazone, and metolachlor was observed for up to 21 d, and daily sampling rates of the herbicides from water in a laboratory flow-through system were determined. The uptake rate of each nonionized herbicide by the Empore disk-based passive sampler was linearly proportional to its concentration in the water, and the sampling rate was independent of the water concentrations over the 21-d period. Uptake of the phenoxy acid herbicides (2,4-D, MCPA, and triclopyr) obeyed first-order kinetics and rapidly reached equilibrium in the passive sampler after approximately 12 d of exposure. The Empore disk-based passive sampler displayed isotropic kinetics, with a release half-life for triclopyr of approximately 6 d.

On-line coupling of sequential injection extraction with restricted-access materials and post-column derivatization for sample clean-up and determination of propranolol in human plasma

The presented paper deals with a new methodology for direct determination of propranolol in human plasma. The methodology described is based on sequential injection analysis technique (SIA) coupled with solid phase extraction (SPE) column based on restricted access materials (RAM). Special RAM column containing 30 μm polymeric material— N-vinylacetamide copolymer was integrated into the sequential injection manifold. SIA–RAM system was used for selective retention of propranolol, while the plasma matrix components were eluted with two weak organic solutions to waste. Due to the acid–basic and polarity properties of propranolol molecule and principles of reversed-phase chromatography, it was possible to retain propranolol on the N-vinylacetamide copolymer sorbent (Shodex MSpak PK-2A 30 μm (2 mm × 10 mm)). Centrifuged plasma samples were aspirated into the system and loaded onto the column using acetonitrile–water (5:95, v/v), pH 11.00, adjusted by triethylamine. The analyte was retained on the column while proteins contained in the sample were removed to waste. Interfering endogenous substances complicating detection were washed out by acetonitrile–water (15:85), pH 11.00 in the next step. The extracted analyte was eluted by means of tetrahydrofuran–water (25:75), pH 11.00 to the fluorescence detector (emission filter 385 nm). The whole procedure comprising sample pre-treatment, analyte detection and column reconditioning took about 15 min. The recoveries of propranolol from undiluted plasma were in the range 96.2–97.8% for three concentration levels of analyte. The proposed SIA–RAM method has been applied for direct determination of propranolol in human plasma.

Multi-syringe flow injection solid-phase extraction system for on-line simultaneous spectrophotometric determination of nitro-substituted phenol isomers

In this paper, a time-based multi-syringe flow injection (MSFI) approach is proposed for automated disk-based sorbent extraction of three nitro-substituted phenol isomers (2-, 3-, and 4-nitrophenol) followed by on-line simultaneous determination of individual species by diode-array spectrophotometry. The method involves the on-line enrichment of the targeted analytes from an acidic medium containing 0.1 mol L −1 HCl onto a co-polymeric sorbent material, and the concurrent removal of potentially interfering matrix components. The nitrophenol isomers are subsequently eluted with an alkaline solution (0.7 mol L −1 NaOH), whereupon the eluate is delivered to a diode-array spectrophotometer for recording of the spectral data in the UV–vis region. Deconvolution of strongly overlapped spectra was conducted with multivariate regression models based on multiple linear regression calibration. The analytical performance of the chemometric algorithm was characterized by relative prediction errors and recoveries. The MSFI manifold was coupled to a multiposition selection valve to set a rugged analyzer that ensures minimum operational maintenance via exploitation of membrane switching protocols. As compared with earlier methods for isolation/pre-concentration of nitro-substituted phenols based on liquid–liquid extraction, the proposed flow-through disk-based system should be regarded as an environmentally friendly approach because the use of harmful organic solvents is circumvented. Under the optimized chemical and physical variables, the 3 σ blank detection limits for 2-, 3-, and 4-nitrophenol were 1.2, 3.2 and 0.3 μmol L −1 for a sample loading volume of 1.5 mL, and the relative standard deviations were ≤5.0%. The flowing system, which is able to handle up to 135 samples automatically, was proven suitable for monitoring trace levels of the target isomers in mineral, tap, and seawater.