Solid phase extraction of metal ions using carbon nanotubes

The sorption behaviour of carbon nanotubes (CNTs) toward some divalent metal ions such as Cu(II), Co(II), Ni(II), Zn(II), Pb(II), Mn(II) and Cd(II) has been investigated systematically. The affinity order of the metal ions towards CNTs at pH in the range of 7.0-9.0 was: Cu(II) > Pb(II) > Zn(II) > Co(II) > Ni(II) > Cd(II) > Mn(II). The experimental parameters for preconcentration of copper, which exhibits the highest affinity towards carbon nanotubes, on a microcolumn packed with CNTs prior to its determination by flame atomic absorption spectrometry have been investigated. Copper can be quantitatively retained at pH 8.2 from sample volume up to 150 mL and then eluted completely with 0.1 mol L^− 1 HNO₃. The limit of detection limit for Cu(II) determination with FAAS detection was 2.1 μg L^− 1, and the RSD was 3.5% at the 50 μg L^− 1 level. Under the optimal conditions for copper enrichment also Zn(II), Pb(II) and Ni(II) could be quantitatively preconcentrated from water samples. The method was validated using a certified reference materials BCR-610 and SRM 1640.     

Solid phase extraction of amines

The objective of this paper is to provide information about solid phase extraction (SPE) as an alternative to liquid-liquid extraction of amines from several matrices. Different sorbents ranging from non-polar phases, such as C₁₈ silica to more polar such as cyanopropylsilica (CN) have been tested for analysis of aliphatic amines as monoamines, diamines and polyamines. Phenylalkylamines such as amphetamine or methamphetamine and heterocyclic amines such as histamine or cephalosporins (which also contain a carboxylic group), have also been studied. The different steps involved in the extraction procedure have been tested (conditioning, retention, pre-concentration, washing and elution) in order to obtain extracts free of interferences and enough sensitivity. C₁₈ silica (100 mg) was selected as optimal phase with recoveries nearly of 100%. The elution of more polar amines was performed in acidic conditions while less polar amines required organic solvents. Cephalosporin retention was performed in acid condition by using disk cartridges EM C_18, which gave better selectivity. The optimised clean-up procedures have been discussed to the quantification of the corresponding amines in real samples (urine, water and beer). The accuracy and precision were outlined.     

Solid phase extraction of food contaminants using molecular imprinted polymers

Food contamination from natural or anthropogenic sources poses severe risks to human health. It is now largely accepted that continuous exposure to low doses of toxic chemicals can be related to several chronic diseases, including some type of cancer and serious hormonal dysfunctions.Contemporary analytical methods have the sensitivity required for contamination detection and quantification, but direct application of these methods on food samples can be rarely performed. In fact, the matrix introduces severe disturbances, and analysis can be performed only after some clean-up and preconcentration steps. Current sample pre-treatment methods, mostly based on the solid phase extraction technique, are very fast and inexpensive but show a lack of selectivity, while methods based on immunoaffinity extraction are very selective but expensive and not suitable for harsh environments. Thus, inexpensive, rapid and selective clean-up methods, relaying on “intelligent” materials are needed. Recent years have seen a significant increase of the “molecularly imprinted solid phase extraction” (MISPE) technique in the food contaminant analysis. In fact, this technique seems to be particularly suitable for extractive applications where analyte selectivity in the presence of very complex and structured matrices represents the main problem. In this review, several applications of MISPE in food contamination analysis will be discussed, with particular emphasis on the extraction of pesticides, drugs residua, mycotoxins and environmental contaminants.     

Electrospun nanofibers as sorbent material for solid phase extraction

Electrospinning has emerged as the most versatile technique for nanofiber fabrication. Owing to their large surface area to volume ratio, electrospun nanofibers have the potential to serve as a good sorbent material for solid phase extraction (SPE) based techniques. The ability to incorporate a variety of functionalities prior or post-electrospinning presents a platform to tune the sorbents for specific applications. It is the aim of this contribution to highlight some of the recent developments that harness the great potential of electrospun nanofibers as sorbents for SPE. The review discusses the various ways in which the electrospinning technique addresses two important parameters for sorbent material, which are sorptive capacity and selectivity. It concludes by presenting and discussing the potential for development of SPE format technology and configurations based on electrospun nanofibers.     

Solid phase extraction of petroleum carboxylic acids using a functionalized alumina as stationary phase

Petroleum essentially consists of a mixture of organic compounds, mainly containing carbon and hydrogen, and, in minor quantities, compounds with nitrogen, sulphur, and oxygen. Some of these compounds, such as naphthenic acids, can cause corrosion in pipes and equipment used in processing plants. Considering that the methods of separation or clean up the target compounds in low concentrations and in complex matrix use large amounts of solvents or stationary phases, is necessary to study new methodologies that consume smaller amounts of solvent and stationary phases to identify the acid components present in complex matrix, such as crude oil samples. The proposed study aimed to recover acid compounds using the solid phase extraction method, employing different types of commercial stationary ion exchange phases (SAX and NH(2)) and new phase alumina functionalized with 1,4-bis(n-propyl)diazoniabicyclo[2.2.2]octane chloride silsesquioxane (Dab-Al(2)O(3)), synthesized in this work. Carboxylic acids were used as standard mixture in the solid phase extraction for further calculation of recovery yield. Then, the real sample (petroleum) was fractionated into saturates, aromatics, resins, and asphaltenes, and the resin fraction of petroleum (B1) was eluted through stationary ion exchange phases. The stationary phase synthesized in this work showed an efficiency of ion exchange comparable to that of the commercial stationary phases.     

Electrospun composite of polypyrrole-polyamide as a micro-solid phase extraction sorbent

A micro-solid phase extraction technique was developed using a novel polypyrrole-polyamide nanofiber sheet, fabricated by electrospinning method. The applicability of the new nanofiber sheet was examined as an extracting medium to isolate malathion as a model pesticide from aqueous samples. Solvent desorption was subsequently performed in a microvial, and an aliquot of extractant was injected into gas chromatography–mass spectrometry. Various parameters affecting the electrospinning process including monomer concentration, polyamide content, applied voltage, and electrospinning time were examined. After fabricating the most suitable preparation conditions, influential parameters on the extraction and desorption processes were optimized. The developed method proved to be rather convenient and offers sufficient sensitivity and good reproducibility. The limit of detection (S/N = 3) and limit of quantification (S/N = 10) of the method under optimized conditions were 50 and 100 ng L⁻¹, respectively. The relative standard deviation at concentration level of 1 ng mL⁻¹ was 2% (n = 3). The calibration curve of analyte showed linearity in the range of 0.1–1 ng mL⁻¹ (R ² = 0.9975). The developed method was successfully applied to tap and Zayanderood river water samples, while the relative recovery percentages of 98% and 96% were obtained, respectively. The whole procedure showed to be conveniently applicable and quite easy to be manipulated.     

Spectrophotometric determination of nitrite and nitrate using phosphomolybdenum blue complex

A method for spectrophotometric determination of nitrite and nitrate is described. This method is based on the reduction of phosphomolybdic acid to phosphomolybdenum blue complex by sodium sulfide. The obtained phosphomolybdenum blue complex is oxidized by the addition of nitrite and this causes a reduction in intensity of the blue color. The absolute decrease in the absorbance of the blue color or the rate of its decrease is found to be directly proportional to the amount of nitrite added. The absorbance of the phosphomolybdenum blue complex is monitored spectrophotometrically at 814 nm and related to the concentration of nitrite present. The effect of different factors such as acidity, stability of the complex, time, temperature, phosphate concentration, molybdenum concentration, sodium sulfide concentration and the tolerance amount of other ions have been reported. Maximum absorbance is at 814 nm. The range of linearity using the conventional method is 0.5-2.0 ppm with molar absorptivity of 1.1 x 10(4) l mol(-1) cm(-1). and a relative standard deviation of 2.6% for five measurements. The range of linearity using the reaction rate method is 0.2-3.6 ppm with a relative standard deviation of 2.4% for five measurements. The method is applied for determination of nitrite and nitrate in water, meat products and vegetables.     

Simultaneous determination of nitrite and nitrate by normal phase ion-pair liquid chromatography

Normal phase ion-pair high performance liquid chromatography has been used for simultaneous separation of nitrite and nitrate using tetraethylammonium (TEA)(+) as ion-pairing reagent. The concentration effect of (TEA)(+), buffer salt and pH of the eluent on separation is investigated. The UV detector response at various wavelengths has been optimized. The performance of the proposed method is compared with ion chromatography for quantification of the anions in potable water, wastewater and in food samples, such as spinach and lettuce.     

Determination of traces of nitrite and nitrate in water by solid phase spectrophotometry

A simple and sensitive method for the determination of nitrite and nitrate in water using solid phase spectrophotometry is described. The method utilizes the quantitative and rapid sorption of the dye formed from nitrite, using the Griess reaction, into a thin layer of polyurethane foam (PUF) where a preconcentration factor of >140 has been achieved. Nitrate is pre-reduced using a cadmium reductor before applying the Griess reaction. The direct spectrophotometric measurement of the dye enriched in the solid foam phase has allowed the detection of as little as 5 and 40 ng ml⁻¹ nitrite and nitrate, respectively. Optimization of the parameters affecting the quantitative formation and sorption of the dye into PUF has been considered. Analysis of natural water samples has been performed.     

Solid phase extraction of trace amount of Cu(II) using functionalized-graphene

A novel and selective method for the fast determination of trace amounts of Cu(II) ions in water samples has been developed. The first organic-solution-processable functionalized-graphene (SPF-Graphene) hybrid material with porphyrins, porphyrin-graphene nanohybrid, 5-(4-aminophenyl)-10, 15, 20-triphenyl porphyrin and its photophysical properties including optical (TPP) and grapheme oxide molecules covalently bonded together via an amide bond (TPP-NHCO-SPFGraphene) were used as absorbent for extraction of Cu(II) ions by solid phase extraction method. The complexes were eluted with HNO₃ (2 M) 10% (vol/vol) methanol in acetone and determined the analyte by flame atomic absorption spectrometry. The procedure is based on the selective formation of Cu(II) at optimum pH by elution with organic eluents and determination by flame atomic absorption spectrometry. The method is based on complex formation on the surface of the ENVI-18 DISK? disks modified porphyrin-graphene nanohybrid, 5-(4-aminophenyl)-10,15,20-triphenyl porphyrin (TPP) and grapheme oxide molecules covalently bonded together via an amide bond (TPP-NHCO-SPFGraphene) followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution is efficient and quantitative. The effect of potential interfering ions, pH, TPP-NHCO-SPFGraphene, amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to about 1000 mL providing a preconcentration factor of 600. The maximum capacity of the disks was found to be 398 ± 3 μg for Cu²⁺. The limit of detection of the proposed method is 5 ng per 1000 mL. The method was applied to the extraction and recovery of copper in different water samples.     

A new sorbent for europium nitrate extraction: phosphonic acid grafted on polystyrene resin

A new chelating polymeric sorbent has been developed using polystyrene resin grafted with phosphonic acid. After characterization by FTIR and elementary analysis, the new resin has been investigated in liquid–solid extraction of europium(III). The results indicated that phosphonic resin could adsorb Eu(III) ion effectively from aqueous solution. The adsorption was strongly dependent on pH of the medium with enhanced adsorption as the pH value of 6.5. The influence of other analytical parameters including contact time, amount of resin, metal ion concentration, and ionic strength were investigated. The maximum uptake capacity of Eu(III) ions was 122.6 mg/g grafted resin at ambient temperature, at an initial pH value of 6.50. The overall adsorption process was best described by pseudo first-order kinetic. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. Furthermore, Eu(III) could be eluted by using 1.0 mol/L H₂SO₄ solution and the grafted resin could be regenerated and reused.     

The extraction of alkoxide anions by quaternary ammonium phase transfer catalysis

Only trace amounts of hydroxide ion can be extracted from aqueous solution into non-polar organic media by quaternary ammonium salts. Addition of small amounts of primary alcohols, particularly certain diols, dramatically changes the behaviour of systems, and surprising amounts of base can be found in the organic apolar phase. The competitive extraction halide/alkoxide was investigated for various ammonium salts. Quantitative measurements were carried out for the evaluation of selectivity constants for extraction of simple primary alkoxides by tetra-n-hexylammonium chloride in benzene.     

Solid phase DNA extraction on PDMS and direct amplification

In this paper we report an innovative use of Poly(DiMethyl)Siloxane (PDMS) to design a microfluidic device that combines, for the first time, in one single reaction chamber, DNA purification from a complex biological sample (blood) without elution and PCR without surface passivation agents. This result is achieved by exploiting the spontaneous chemical structure and nanomorphology of the material after casting. The observed surface organization leads to spontaneous DNA adsorption. This property allows on-chip complete protocols of purification of complex biological samples to be performed directly, starting from cells lysis. Amplification by PCR is performed directly on the adsorbed DNA, avoiding the elution process that is normally required by DNA purification protocols. The use of one single microfluidic volume for both DNA purification and amplification dramatically simplifies the structure of microfluidic devices for DNA preparation. X-Ray Photoelectron Spectroscopy (XPS) was used to analyze the surface chemical composition. Atomic Force Microscopy (AFM) and Field Emission Scanning Electron Microscopy (FESEM) were employed to assess the morphological nanostructure of the PDMS-chips. A confocal fluorescence analysis was utilized to check DNA distribution inside the chip.     

Micro-phase sorbent extraction for trace analysis via in situ sorbent formation: application to the spectrophotometric determination of nitrite in environmental waters.

A micro-phase sorbent in situ formation from an aqueous solution was proposed for the sensitive spectrophotometric determination of nitrite in environmental waters. Nitrite in a 10 mL sample solution was converted into a cationic azo dye by the reaction with 4-trifluoromethylanilinium ion and N-1-naphthylethylenediammonium ion in an acidic medium. Addition of dodecylbenzenesulfonate ion caused the formation of a suspension of ion associate in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase that extracted the azo dye at the bottom of the centrifuge tube. The volume of the new phase was ca. 5 microL. After the aqueous phase was discarded, the organic phase was dissolved with 1 mL of 2-methoxyethanol to measure the absorbance. Nitrogen as NO2- at concentrations from 1.5 to 30 microg L(-1) was determined with sufficient precision. When 0.2 mL of 2-methoxyethanol was applied to dissolve the organic phase, 0.3-4.8 microg NO2--N L(-1) was determined. The recovery tests for nitrite added to some river water and seawater were satisfactory. This method is very simple and rapid. It takes only 30 min from the dye formation to the measurement of the absorbance.     

槲皮素分子印迹聚合物的制备及固相萃取性能研究

采用分子印迹技术, 以槲皮素为模板分子, 丙烯酰胺为功能单体, 乙二醇二甲基丙烯酸脂为交联剂, 通过热引发聚合, 制备了槲皮素分子印迹聚合物, 并通过装入固相萃取柱试验了聚合物对槲皮素的选择性能. 结果表明, 该分子印迹聚合物对槲皮素具有高度选择性, 为从天然产物中高效分离富集黄酮活性成分槲皮素提供了一种新材料.     

Determination of nitrate and nitrite by continuous liquid-liquid extraction with a flow-injection atomic-absorption detection system

Summary A flow injection system coupled on-line with a continuous liquid-liquid extractor is used for the indirect determination of nitrate and nitrite with an atomic-absorption detection system. These anions form ion-pairs with the copper(I)-neocuproine chelate which are extracted into methyl-isobutyl-ketone, the atomic-absorption signal of copper from the organic phase being proportional to the nitrate or nitrite concentration. The methods proposed herein are suitable for determining nitrate or nitrite at the g ml^–1 level with a sampling frequency of 35 ± 5 h^–1. The methods compare favourably with their batch counterparts with regard to sensitivity, selectivity, sample volume and sampling frequency.

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Bestimmung von nitrat und nitrit durch kontinuierliche flüssig-flüssig-extraction mit detektion durch ein fließinjektions-AAS-system

Zusammenfassung Ein Fließinjektionssytem, das on-line mit einem Flüssig-Flüssig-Extraktor gekoppelt ist, wird zur indirekten AAS-Bestimmung von Nitrat und Nitrit benutzt. Diese Anionen bilden mit Kupfer(I)-neocuproinchelat Ionenpaare, die mit Methylisobutylketon extrahiert werden. Das AAS-Signal des Kupfers aus der organischen Phase ist der Nitrat- bzw. Nitritkonzentration proportinal. Die vorgeschlagenen Verfahren eignen sich zur Nitrat- oder Nitritbestimmung im g/ml-Bereich mit einer Probenfrequenz von 35 ± 5 je Stunde. Diese Methoden sind den Batch-Verfahren in bezug auf Empfindlichkeit, Selektivität sowie Probevolumen und -frequenz überlegen.

     

Urinary hydroxylysine glycosides: Solid phase extraction and reversed phase chromatographic measurement

Summary A method is described for measurement of urinary hydroxylysine glycosides (galactosyl-hydroxylysine, or GHYL, and glucosyl-galactosyl-hydroxylysine, or GGHYL) by reversed phase chromatography after purification of the sample by solid phase extraction. Urinary levels of hydroxylysine glycosides has been correlated with collagen catabolism, and the urinary GGHYL: GHYL ratio is indicative of the metabolism of connective tissue. The GGHYL:GHYL ratio might, therefore, be a promising indicator of bone mass loss. The method described is analytically reliable and enables the measurement of a possible marker for diagnosis and follow-up of osteoporosis.     

Solid-liquid extraction and cation-exchange solid-phase extraction using a mixed-mode polymeric sorbent of Datura and related alkaloids

Tropane alkaloids solid-liquid extraction methods were developed and comprised ambient pressure ones: extraction with hot solvent, extraction at room temperature, on ultrasonic bath as well as pressurised liquid extraction (PLE) techniques. The highest yields of l-hyoscyamine in methanol PLE method (3 x 5 min, 110 degrees C) and scopolamine extracted with 1% tartaric acid in methanol (15 min, 90 degrees C) were determined. A mixed-mode reversed-phase cation-exchange solid-phase extraction (SPE) procedure was optimised for simultaneous recoveries of L-hyoscyamine, scopolamine, scopolamine-N-oxide from plant extracts as well as quaternary alkaloid representative: scopolamine-N-methyl bromide. First three alkaloids were efficiently eluted (recoveries 80-100%) from an Oasis MCX cartridge with methanol-10% ammonia (3:1, v/v) solution, whereas for the quaternary salt tetrahydrofuran-methanol-25% ammonia (6:1:3, v/v) was used with recoveries 52-6%. HPTLC-densitometric assay on silica gel plates was elaborated at 205 nm without derivatization and included: single development (over a distance 9.5 cm) with acetone-methanol-water-25% ammonia (85:5:5:8, v/v) mobile phase for L-hyoscyamine and scopolamine separation, whereas for scopolamine-N-oxide and scopolamine-N-methyl bromide a second development (to a distance 5.5 cm) with acetonitrile-methanol-85% formic acid (120:5:5, v/v) was applied. Newly elaborated RP-HPLC-diode array detection method was performed on Waters XTerra RP-18 column with gradient of acetonitrile in 15 mM ammonia solution and alkaloids were baseline separated within 20 min. Both chromatographic methods were validated and their quantitative results were compared. Good correlation between HPLC and HPTLC quantitative results was measured (correlation coefficients of mean values were 0.92086 and 0.99995 for L-hyoscyamine and scopolamine, respectively). In the RP-HPLC method, which was from 1.5- up to 7-fold more sensitive than HPTLC, limits of detection (LOD) and limits of quantitation (LOQ, in bracket) were (in ng/microl) as follows: 0.25 (0.82) for L-hyoscyamine, 0.29 (0.97) for scopolamine, 0.13 (0.45) for scopolamine-N-oxide and 0.58 (1.91) for scopolamine-N-methyl bromide. By the use of the optimised chromatographic methods, 14 various samples from the leaves and fruits of Datura sp. were screened for L-hyoscyamine and scopolamine contents and the most promising samples were established.