Effect of Surfactant Loading on the Extraction Properties of C-18 Bonded Silica used for Solid-Phase Extraction of Phenols

ABSTRACT

A solid phase extraction (SPE) system has been modified with cationic surfactants and evaluated for extraction and preconcentration of trace phenolic compounds contaminants in water at low ppb concentrations. Cationic surfactants such as cetyl trimethyl ammonium bromide (CTAB) has been steadily adsorbed on the surface of C-18 bonded silica, and the ionized functional group of the surfactant can then act as an ion–exchange site to attract the ionized phenolic compounds from water samples. The method includes enrichment of the phenolic compounds by the surfactant-loaded solid phase extraction system, followed by elution of the analyte with methylene chloride and derivatization of the phenolic compounds with acetic anhydride. Thirty-two phenolic analytes were identified and quantitatively determined by this method; identification and quantification of the compounds is performed with GC/FID using 2-bromophenol as internal standard. SPME analysis with this method was linear over 3-6 orders of magnitude, with linear correlation coefficient (R²) greater than 0.96. Experimentally determined FID detection limits ranged from ～30 ppt for methyl-substituted phenols to ～0.1ppb for phenol and chloro-substituted phenols. We tested the influence of sample pH, the loading amount of surfactant on the solid phase, and the volume and matrixes of the sample were studied. Absolute recoveries from pure water spiked with 0.2 ppb phenolic compounds were 96 – 103%. The method has been applied to analysis of various natural waters, including ground water, lake water, seawater, and wastewater. Recoveries from ground water, lake water, seawater, and wastewater were 92 – 106%, 75 – 93%, 87 – 103%, 86 – 99%, respectively. Therefore, the new technique proved to be an excellent tool for trace enrichments of phenolic compounds at low ppb concentration of these analytes, from different natural water samples.     

A poly (4‐vinylpridine‐co‐ethylene glycol dimethacrylate) monolithic concentrator for in‐line concentration‐capillary electrophoresis analysis of phenols in water samples

A poly(4‐vinylpridine‐co‐ethylene glycol dimethacrylate) monolith was synthesized in a capillary and constructed as a concentrator for the in‐line polymeric monolith microextraction coupling with capillary electrophoresis. The integrated system was then used for the simultaneous determination of five trace phenols (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2‐chlorophenol, and 2,4‐dichlorophenol) in water samples. The experimental parameters for in‐line solid‐phase extraction, such as composition and volume of the elution plug, pH of sample solution, and the time for sample loading were optimized. The sensitivity for the mixture of phenols (2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2‐chlorophenol, and 2,4‐dichlorophenol) enhanced to 615–2222 folds at the optimum condition was compared to the sensitivity for a normal hydrodynamic injection in capillary electrophoresis. Linearity ranged from concentration of 10–500 ng mL^?1(R² > 0.999) for all five phenols with the detection limits of 1.3–3.3 ng mL^?1. In tap, snow and Yangtze River water spiked with 20 ng mL^?1 and 200 ng mL^?1, respectively, the recoveries of 84–105% were obtained. It has been demonstrated that this work has great potential for the analysis of phenols in genuine water samples.     

Comparison of supercritical fluid extraction and liquid-liquid extraction for isolation of selected pesticides stored in freeze-dried water samples

Summary The stability of freeze-dried water samples spiked with eight agrochemicals (atrazine, simazine, linuron, carbaryl, propanil, fenitrothion, parathion and fenamiphos) were examined to evaluate their suitability as candidate reference materials for their determination in water samples. In addition, two different extraction procedures, liquid-liquid and supercritical fluid extraction, were compared for the isolation and trace enrichment of target analytes from freeze-dried water samples. Final analytical determinations were by gas chromatography-nitrogen phosphorus detection and electronic impact mass spectrometry, and by liquid chromatography-diode array detection. The whole methodology developed in this paper permitted the determination of pesticides spiked in water at levels varying from 0.03 to 6.9 g L^–1.     

Polymeric ionic liquid modified stainless steel wire as a novel fiber for solid‐phase microextraction

A polymeric ionic liquid modified stainless steel wire for solid‐phase microextraction was reported. Mercaptopropyl‐functionalized stainless steel wire that was formed by co‐condensation of tetramethoxysilane and 3‐mercaptopropyltrimethoxysilane via a sol‐gel process, which is followed by in situ surface radical chain‐transfer polymerization of 1‐vinyl‐3‐octylimidazolium hexafluorophosphate to result in polymeric ionic liquid modified stainless steel wire. The fiber surface was characterized by field emission scanning electron microscope equipped with energy dispersive X‐ray analysis. Coupled with GC, extraction performance of the fiber was tested with phenols and polycyclic aromatic hydrocarbons as model analytes. Effects of extraction and desorption conditions were investigated systematically in our work. RSDs for single‐fiber repeatability and fiber‐to‐fiber reproducibility were less than 7.34 and 16.82%, respectively. The calibration curves were linear in a wide range for all analytes and the detection limits were in the range of 10–60 ng L^?1. Two real water samples from the Yellow River and local waterworks were applied to test the as‐established solid‐phase microextraction–GC method with the recoveries of samples spiked at 10 μg L^?1 ranged from 83.35 to 119.24%. The fiber not only exhibited excellent extraction efficiency, but also very good rigidity, stability and durability.     

On-line packed magnetic in-tube solid phase microextraction of acidic drugs such as naproxen and indomethacin by using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript>@layered double hydroxide nanoparticles with high anion exchange capacity

The authors describe a 3-component nanoparticle system composed of a silica-coated magnetite (Fe₃O₄) core and a layered double (Cu-Cr) hydroxide nanoplatelet shell. The sorbent has a high anion exchange capacity for extraction anionic species. A simple online system, referred to as "on-line packed magnetic-in-tube solid phase microextraction" was designed. The nanoparticles were placed in a stainless steel cartridge via dry packing. The cartridge was then applied to the preconcentration acidic drugs including naproxen and indomethacin from urine and plasma. Extraction and desorption times, pH values of the sample solution and flow rates of sample solution and eluent were optimized. Analytes were then quantified by HPLC with UV detection. Under optimal conditions, the limits of detection range from 70 to 800 ng L^?1, with linear responses from 0.1–500 μg L^?1 (water samples), 0.6–500 μg L^?1 (spiked urine), and 0.9–500 μg L^?1 (spiked plasma). The inter- and intra-assay precisions (RSDs, for n?=?5) are in the range of 2.2–5.4%, 2.8–4.9%, and 2.0–5.2% at concentration levels of 5, 25 and 50 μg L^?1, respectively. The method was applied to the analysis of the drugs in spiked human urine and plasma, and good results were achieved.

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Graphical abstract Fe₃O₄@SiO₂@CuCr-LDH magnetic nanoparticles were synthesized and packed in to a stainless steel column. The column was applied to solid phase microextraction of acidic drugs from biological samples.

     

TIRF-based biosensor for sensitive detection of progesterone in milk based on ultra-sensitive progesterone detection in water

We report on recent advances of our immunoassay for the hormone progesterone in cows milk. Detection is based on total internal reflectance fluorescence (TIRF), the binding-inhibition assay with an immobilized progesterone derivative, and a commercially available monoclonal antibody to progesterone as biological recognition element. The fully automated River Analyzer (RIANA) biosensor for unattended, cost-effective, and continuous monitoring of environmental pollution therefore was adapted for sensitive determination of progesterone in milk. First, the sensitivity and robustness of the existing progesterone assay for water analysis were improved, resulting in a detection limit (LOD) of only 0.2 pg mL^–1 and a quantification limit (LOQ) of only 2.0 pg mL^–1. These extraordinary results are the lowest detection and quantification limits for progesterone determination using biosensors yet reported in the literature. Second, the accurate indicator of ovulation was calibrated and detected in three different types of milk (UHT milk, fresh milk, and raw milk). For commercial milk and randomly procured raw milk nominal levels of progesterone are typically in the range 5–15 ng mL^–1. Limits of detection (LOD) achieved for added progesterone (i.e. spiked samples) were between 45.5 and 56.1 pg mL^–1 depending on milk type. Having in mind the 1:10 dilution factor, these results are still a success. For the first time a commercially available antibody was incorporated into an immunoassay for progesterone detection in bovine milk, giving a detection limit below 1 ng mL^–1 for a fully automated biosensor. Thus the outstanding progress made with this biosensor in environmental monitoring and water analysis has now been successfully adapted to milk analysis for use in the field of reproduction management.Dedicated to the memory of Wilhelm Fresenius.     

Mesoporous Bimetallic PtPd Nanoflowers as a Platform to Enhance Electrocatalytic Activity of Acetylcholinesterase for Organophosphate Pesticide Detection

Mesoporous bimetallic PtPd nanoflowers (MPtPdN) were synthesized by a surfactant‐directing method. The MPtPdN was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and wide‐angle X‐ray diffraction (XRD). The use of MPtPdN as a platform for the indirect electrochemical detection of organophosphate pesticides (OPs) via enzymatic inhibition pathway was demonstrated. Due to the nanostructure of MPtPdN and the synergy effect of the noble metal nanoparticles, a novel and sensitive acetylcholinesterase (AChE) biosensor for OPs detections based on MPtPdN and enzyme inhibition was prepared. The inhibition of omethoate exhibited a linear relationship from 4.7×10⁻¹¹ to 4.7×10⁻⁸ M with a detection limit of 1.7×10⁻¹² M (S/N=3). The proposed AChE biosensor was reliable and can be used to measure the concentration of omethoate in different spiked samples with high accuracy and satisfactory recovery. The preparation of biosensors based on the MPtPdN can be further extended to construct many other important enzyme biosensors.     

Hydrogen peroxide sensor based on glassy carbon electrode modified with ��-manganese dioxide nanorods

A solid bar microextraction (SBME) method containing sorbent materials 2?mg in the lumen of a porous hollow fiber membrane 2.5?cm for the extraction of carbamazepine, diclofenac and ibuprofen from river water samples is described. The desorbed analytes were analyzed using reversed-phase high performance liquid chromatography with ultraviolet detection. In order to achieve optimum performance, several extraction parameters were optimized. Of the sorbents evaluated, LiChrosorb RP-8 was the most promising. Under the optimized conditions, limits of detection from 0.7 to 0.9???g?L^?1, precisions from 5.5 to 6.4% and a correlation coefficient of 0.999 were obtained for the target drugs over a concentration range of 1?C200???g?L^?1. In comparison with the solid phase extraction, the SBME system offers distinct advantages due to its higher enrichment factors, lower consumption of organic solvents and time saving.

Selective Electrochemical Detection of Pirarubicin by Means of DNA‐modified Graphite Biosensor

Pirarubicin (THP) is an anthracycline drug, which is mainly used in the anticancer treatment. Utilization of THP may be associated with many dangerous side effects, therefore monitoring of drug level in patients’ organism is an important aspect of chemotherapy. In our research we focused on designing of an electrochemical DNA‐based biosensor for selective detection of pirarubicin (THP). Our biosensor utilizes the ability of pirarubicin to interact with DNA double helix and the fact that THP is an electrochemically active compound. Graphite electrodes modified with DNA enable to obtain nearly three thousand times higher sensitivity (41.8⋅10³ A/M) than non‐modified sensors. Furthermore, in the case of THP detection by means of bare graphite electrodes, LOD was 43.6⋅10⁻⁹ M, whereas for developed DNA biosensors ‐112⋅10^‐12 M. A study of selectivity of DNA–modified biosensors was carried out in aqueous solutions containing interferents: acetaminophen (PCT) and ascorbic acid (AA) as well as in samples of fetal bovine serum (FBS) spiked with PCT and AA. In established measurement conditions one peak corresponding to THP reduction was observed, whereas no redox peaks assigned to interferents (PCT, AA) were present. These results indicate that developed biosensors are selective to pirarubicin.     

An electropolymerized aniline-based fiber coating for solid phase microextraction of phenols from water

An aniline-based polymer was electrochemically prepared and applied as a new fiber coating for solid phase microextraction (SPME) of some priority phenols from water samples. The polyaniline (PANI) film was directly electrodeposited on the platinum wire surface in sulfuric acid solution using cyclic voltammetry (CV) technique. The efficiency of new coating was investigated using a laboratory-made SPME device and gas chromatography with flame ionization detection for the extraction of some phenols from the headspace of aqueous samples. The scanning electron microscopy (SEM) images showed the homogeneity and the porous surface structure of the film. The results obtained proved the ability of this polymer as a suitable SPME fiber coating for trapping the selected phenols. Influential parameters affecting the extraction process were optimized and an extraction time of 50 min at 50 °C gave maximum efficiency, when the aqueous sample was saturated with NaCl and adjusted at pH 2. This new coating can be prepared easily in a reproducible manner and it is rather inexpensive and stable against most of organic solvents. The PANI thickness can be precisely controlled by the number of CV cycles. At the optimum conditions, the R.S.D. for a double distilled water spiked with phenol and chlorophenols at ppb level were 4.8-17% (n = 3) and detection limits for the studied compounds were between 0.69 and 3.7 ng ml⁻¹, except for phenol and 4-chlorophenol. The optimized method was successfully applied to some real-life water samples.     

Optimization of preconcentration and isolation for the determination of 15 phenols by supercritical-fluid extraction and gas chromatography with metallomesogenic stationary phase

Based on the merits of well-established capillary gas chromatography (GC), metallomesogenic polymer was used as the stationary phase and flame ionization detector (FID) was used as the detector, the analysis of phenolic compounds explored the possibility of application in complex matrices. We proposed the method combined supercritical-fluid extraction (SFE) of phenolic compounds, which had been enriched on the solid supports of XAD-4 resins, and then with their determinations by capillary GC-FID. The SFE parameters suitable for 15 phenols simultaneously adsorbed onto XAD-4 resins in aqueous solution were assessed by a 4⁵ factorial design method. The best results were 5 min static time, 10 min dynamic time, 0.25 ml methanol spiked, 80 °C oven temperature and 410 atm CO₂ pressure. Also, other parametric conditions for specific phenols were revealed and analyzed. In the comparison with Soxhlet extraction with regard to the recoveries and reproducibility, the developed SFE was quite superior and helped to reduce the detection limit of aqueous samples to 10⁻²-fold. Eventually, the polluted soils near a pharmaceutical factory were primarily tested and given the probable distribution.     

Magnetic solid‐phase extraction based on a polydopamine‐coated Fe3O4 nanoparticles absorbent for the determination of bisphenol A,tetrabromobisphenol A, 2,4,6‐tribromophenol,and (S)‐1,1’‐bi‐2‐naphthol in environmental waters by HPLC

Polydopamine‐coated Fe₃O₄ magnetic nanoparticles synthesized through a facile solvothermal reaction and the self‐polymerization of dopamine have been employed as a magnetic solid‐phase extraction sorbent to enrich four phenolic compounds, bisphenol A, tetrabromobisphenol A, (S)‐1,1′‐bi‐2‐naphthol and 2,4,6‐tribromophenol, from environmental waters followed by high‐performance liquid chromatographic detection. Various parameters of the extraction were optimized, including the pH of the sample matrix, the amount of polydopamine‐coated Fe₃O₄ sorbent, the adsorption time, the enrichment factor of analytes, the elution solvent, and the reusability of the nanoparticles sorbent. The recoveries of these phenols in spiked water samples were 62.0–112.0% with relative standard deviations of 0.8–7.7%, indicating the good reliability of the magnetic solid‐phase extraction with high‐performance liquid chromatography method. In addition, the extraction characteristics of the magnetic polydopamine‐coated Fe₃O₄ nanoparticles were elucidated comprehensively. It is found that there are hydrophobic, π–π stacking and hydrogen bonding interactions between phenols and more dispersible polydopamine‐coated Fe₃O₄ in water, among which hydrophobic interaction dominates the magnetic solid‐phase extraction performance.     

Single-walled carbon nanohorns immobilized on a microporous hollow polypropylene fiber as a sorbent for the extraction of volatile organic compounds from water samples

We have evaluated the behavior of single-walled carbon nanohorns as a sorbent for headspace and direct immersion (micro)solid phase extraction using volatile organic compounds (VOCs) as model analytes. The conical carbon nanohorns were first oxidized in order to increase their solubility in water and organic solvents. A microporous hollow polypropylene fiber served as a mechanical support that provides a high surface area for nanoparticle retention. The extraction unit was directly placed in the liquid sample or the headspace of an aqueous standard or a water sample to extract and preconcentrate the VOCs. The variables affecting extraction have been optimized. The VOCs were then identified and quantified by GC/MS. We conclude that direct immersion of the fiber is the most adequate method for the extraction of VOCs from both liquid samples and headspace. Detection limits range from 3.5 to 4.3 ng L^?1 (excepted for toluene with 25 ng L^?1), and the precision (expressed as relative standard deviation) is between 3.9 and 9.6 %. The method was applied to the determination of toluene, ethylbenzene, various xylene isomers and styrene in bottled, river and tap waters, and the respective average recoveries of spiked samples are 95.6, 98.2 and 86.0 %.

Preconcentration of trace aluminum (III) ion using a nanometer-sized TiO2-silica composite modified with 4-aminophenylarsonic acid, and its determination by ICP-OES

We describe a nanometer sized composite material made from titanium dioxide and silica that was chemically modified with 4-aminophenylarsonic acid and used for selective solid-phase extraction, separation and preconcentration of of aluminum(III) prior to its determination by ICP-OES. Under optimized conditions, the static adsorption capacity is 56.58?mg?g^?1, the enrichment factor is 150, the relative standard deviation is 1.6% (for n?=?11), and the detection limit (3?s) is 60?pg?mL^?1. The method was validated by analyzing the reference materials GBW 09101 (hair) and GBW 10024 (scallop) and successfully applied to the determination of trace Al(III) in spiked water samples and human urine, with recoveries ranging from 96% to 101%.

On-line trace enrichment of phenolic compounds from water using a pyrrole-based polymer as the solid-phase extraction sorbent coupled with high-performance liquid chromatography

A pyrrole-based conductive polymer was prepared and applied as new sorbent for on-line solid-phase extraction (SPE) of phenol and chlorophenols from water samples. Polypyrrole (PPy) was synthesized by chemical oxidation of the monomer in non-aqueous solution. The efficiency of this polymer for extraction of phenol and chlorophenols was evaluated using 35 mg of PPy as the sorbent in an on-line SPE system coupled to reversed-phase liquid chromatography with UV detection. The mobile phase were mixture of phosphate buffer-acetonitrile and compounds were eluted by the mobile phase using a six-port switching valve. High volumes of water, up to 160 ml, could be preconcentrated without the loss of phenols, except for the more polar ones. The R.S.D. for a river water sample spiked with phenol and chlorophenols at sub-ppb level was lower than 7% (n=5) and detection limits of 15-100 and 35-150 ng l⁻¹ for tap and river water were obtained, respectively.     

Biosensors for phenol derivatives using biochemical signal amplification

Two different approaches, both exploiting two enzymes cooperative functioning, to enhance the sensitivity of tyrosinase (PPO) based biosensor for amperometric detection of phenols have been compared. For this purpose, one monoenzyme electrode (PPO) and two bienzyme electrodes (PPO and d-glucose dehydrogenase, GDH; PPO and horseradish peroxidase, HRP) were constructed using agar-agar gel as enzyme immobilization matrix. The biosensors responses for l-tyrosine detection were recorded at −50 mV versus saturated calomel electrode (SCE). The highest sensitivity (74 mA M⁻¹) was observed for the PPO-GDH couple, while that recorded for PPO-HRP couple system was only 32 times higher than that measured for monoenzyme electrode (0.01 mA M⁻¹). The ability of the PPO-, PPO-GDH-, PPO-HRP-based biosensors to assay phenols was demonstrated by quantitative determination of phenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 2-amino-3 (4-hydroxyphenyl) propanoic acid, 2-hydroxytoluene, 3-hydroxytoluene, 4-hydroxytoluene, 4-clorophenol, 3-clorophenol, 2-clorophenol, 4-hydroxybenzoic acid.     

Rapid Ultrasound-Assisted Emulsification Microextraction Combined with COU-2 Dispersive Micro-solid Phase Extraction for the Determination of Azole Antifungals in Milk Samples by HPLC-DAD

A rapid, simple, and efficient method using ultrasound-assisted emulsification microextraction combined with dispersive micro-solid phase extraction (USAE-D-µ-SPE) was developed for detection and quantification of three azole antifungals in milk samples by high-performance liquid chromatography diode array detector. In this study, mesoporous carbon, COU-2, was used as sorbent in USAE-D-µ-SPE for the extraction and preconcentration of analytes. Several important experimental parameters, including type of deproteinized solvents, desorption time, type of extraction solvents, volume of extraction solvent, extraction time, emulsification time, sample pH, salt addition, and mass of COU-2 sorbent, were optimized using spiked milk samples. Under the optimum extraction and detection conditions, three azole antifungals, namely ketoconazole, clotrimazole, and miconazole, were determined within 20 min, with good linearity of matrix-matched calibration in the range of 0.5–5000.0 µg L^?1 with coefficient of determination, r ² ≥ 0.9943. The method showed limits of detection and limits of quantification of all analytes in the range of 0.15–3.0 and 0.5–10.0 µg L^?1, respectively. Good repeatability with RSDs <15% (n = 3) and satisfactory relative recoveries (83.3–111.1%) were obtained for spiked azole antifungal drugs in milk. The results reveal that the developed USAE-D-µ-SPE method was a simple, rapid, efficient, environmentally friendly, and practicable method for the determination of azole antifungals in milk samples.     

DNA-based biosensors with external Nafion and chitosan membranes for the evaluation of the antioxidant activity of beer,coffee, and tea

Novel electrochemical DNA-based biosensors with outer-sphere Nafion and chitosan protective membranes were prepared for the evaluation of antioxidant properties of beverages (beer, coffee, and black tea) against prooxidant hydroxyl radicals. A carbon working electrode of a screen-printed three-electrode assembly was modified using a layer-by-layer deposition technique with low molecular weight double-stranded DNA and a Nafion or chitosan film. The membrane-covered DNA biosensors were initially tested with respect to their voltammetric and impedimetric response after the incubation of the beverage and the medium exchange for the solution of the redox indicator [Fe(CN)₆]^3?/4?. While the Nafion-protected biosensor proved to be suitable for beer and black tea extracts, the chitosan-protected biosensor was successfully used in a coffee extract. Afterwards, the applicability was successfully verified for these biosensors for the detection of a deep degradation of the surface-attached DNA at the incubation in the cleavage agent (hydroxyl radicals generated via Fenton reaction) and for the evaluation of antioxidant properties of coffee and black tea extracts against prooxidant hydroxyl radicals. The investigation of the novel biosensors with a protective membrane represents a significant contribution to the field of electrochemical DNA biosensors utilization.      

Extraction of endocrine disrupting phenols with iron-ferric oxide core-shell nanowires on graphene oxide nanosheets,followed by their determination by HPLC

We describe a novel magnetic nanosorbent that consists of nanowires consisting of a core of metallic iron and an iron (III) oxide shell. These nanowires were then deposited on graphene oxide to form a composite of the type Fe@Fe₂O₃/GO. Specifically, the magnetic composite is formed via electrostatic interaction between negatively charged GO nanosheets and positively charged Fe@Fe₂O₃ nanowires in aqueous solution. The material was successfully applied to the extraction of the endocrine-disrupting phenols bisphenol A, triclosan and 2,4-dichlorophenol from water samples. Compared to neat graphene oxide, the composite material exhibits improved properties in terms of microextraction where both the hydrophilic graphene oxide and the Fe@Fe₂O₃ nanowires participate in the adsorption of the hydrophilic analytes. The amount of adsorbent, pH of water sample, extraction time and desorption time, type and volume of desorption solution were optimized. Following extraction for the absorbent, the phenols were quantified by HPLC. The three phenols can be determined in 0.5 to 100 ng∙mL⁻¹ concentration range, with limits of detection (at an S/N ratio of 3) ranging from 0.08 to 0.10 ng∙mL⁻¹. The repeatability was investigated by evaluating the intra- and inter-day precisions with relative standard deviations of lower than 7.5 % (n = 5). The recoveries from spiked real water samples were in the range from 84.8 to 92.0 %. The results indicate that the novel material can be successfully applied to the extraction and analysis of phenols from water samples.

Scheme 1 procedure for the synthesis of Fe@Fe₂0₃/G0