We report on a new sorbent for preconcentration of cadmium and lead ions that is based on triazine-functionalized magnetite nanoparticles that were prepared by direct silylation of magnetic nanoparticles with 3-aminopropyltriethoxysilane-2,4-bis(3,5-dimethylpyrazol)-triazine. The sorbent was characterized by IR spectroscopy, X-ray powder diffraction, scanning electron microscopy, thermal and elemental analysis. The sorbent was applied to the preconcentration of lead and cadmium ions which then were quantified by FAAS. The effects of sample pH value, extraction time, of type, concentration and volume of eluent, and of elution time were optimized. The limits of detection are 0.7 ng mL−1 for Pb(II) ion and 0.01 ng mL−1 for Cd(II). The effects of potentially interfering ions often found in real samples on the recovery in the determination of cadmium and lead ions in real samples were also investigated. The accuracy of the method was confirmed by analyzing the certified reference materials NIST 1571 (orchard leaves) and NIST 1572 (citrus leaves). Finally, the method was successfully applied to the determination of cadmium and lead ions in some fruit samples.
We report on a new sorbent for preconcentration of cadmium and lead ions that is based on triazine-functionalized magnetite nanoparticles. After optimization of the preconcentration step the method was successfully applied to the determination of cadmium and lead ions in some fruit samples
Vortex-assisted liquid-liquid microextraction (VALLME) for the rapid extraction of trace bisphenol S (BPS) in environmental water is presented. In order to simplify the procedure, an in-house fabricated glass dropper with different internal diameters of the two ends is exploited. The solidification-melt step was cut in VALLME by means of the in-house fabricated glass dropper. After extraction with 2-ethylhexanol, BPS was detected by high performance liquid chromatography (HPLC) with ultraviolet (UV) detection. Factors such as type and volume of extraction solvent, extraction time, sample pH and ionic strength were evaluated. Under optimized conditions, the linearity range varied from 0.10 to 50 μg L−1 with a squared regression coefficient r2 of 0.9995. The relative standard deviation (RSD) is 2.3 % (n = 7). The limit of detection (LOD) and limit of quantification (LOQ) are 0.02 and 0.06 μg L−1, respectively. The presented method was employed for the determination of BPS in real water samples. The relative recoveries are 81.8–87.3 % for the two real water samples. The method is shown to be economical, fast and can be routinely performed.
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Microparticles were synthesized by suspension copolymerization of the synthetic ionic liquid (IL) 1-allyl-3-methyl-imidazolium bromide with ethylene glycol dimethacrylate. The particles have a regular spherical shape and an average diameter of 65 ± 24 μm. Their affinity for the fluoroquinolone antibiotics ofloxacin (OFL), lomefloxacin (LOM) and ciprofloxacin (CIP) is much higher than that of the blank polymer (not containing an IL), of polymers using methacrylic acid as functional monomer, of hydrophilic-lipophilic balanced sorbents, and of C18 sorbents. The microparticles were applied to the solid-phase extraction and rapid preconcentration of the fluoroquinolones from urine which then were quantified by HPLC. The calibration plot covers the 0.05 to 20 μg mL−1 concentration range, and the average recoveries at three spiking levels range from 93.6 to 103.7 %, with RSD of ≤5.7 %. The method was successfully applied to the determination of fluoroquinolones in spiked urine.
Microparticles covalently functionalized with an ionic liquid ([Amim][Br]) were synthesized by suspension copolymerization and show higher affinity for fluoroquinolones than other sorbents. The microparticles were used as a sorbent for solid-phase extraction and preconcentration of three fluoroquinolones from urine.
Double-charged diazabicyclo[2.2.2]octane (DABCO) was immobilized on the inner surface of a nanomaterial composed of the layered double hydroxides (LDHs) of Zn(II) and Cr(III). The resulting material was characterized by SEM, FT-IR and XRD techniques. This novel nanocomposite has been used as a highly porous fiber coating for solid-phase microextraction (SPME) of phenol and various chloro-, nitro- and aminophenols. The LDH nanocomposite was deposited on a stainless steel wire and then evaluated with respect to the extraction of phenolic compounds from water samples. The effects of temperature, extraction time, ionic strength, stirring rate, pH, and desorption temperature and time on the extraction were optimized. The compounds were then separated and quantified by GC-MS. Under optimum conditions, the repeatability for a single fiber (for n = 3 and expressed as the relative standard deviation) is between 2.3 and 7.2 %. The detection limits are between 0.02 and 6.3 pg mL−1. The method is simple, rapid, and inexpensive. The fiber is thermally stable and its use gives high recoveries.
Double-charged diazabicyclo[2.2.2]octane (DABCO) was immobilized on the inner surface of a nanomaterial composed of the layered double hydroxides (LDHs) of Zn(II) and Cr(III). This novel nanocomposite has been used as a highly porous fiber coating for solid-phase microextraction (SPME) of phenol and various chloro-, nitro- and aminophenols.
We are presenting magnetic molecularly imprinted polymer nanoparticles (m-MIPs) for solid-phase extraction and sample clean-up of paracetamol. The m-MIPs were prepared from magnetite (Fe3O4) as the magnetic component, paracetamol as the template, methacrylic acid as a functional monomer, and 2-(methacrylamido) ethyl methacrylate as a cross-linker. The m-MIPs were then characterized by transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction and vibrating sample magnetometry. The m-MIPs were applied to the extraction of paracetamol from human blood plasma samples. Following its elution from the column loaded with the m-MIPs with an acetonitrile-buffer (9:1) mixture, it was submitted to HPLC analysis. Paracetamol can be quantified by this method in the 1 μg L−1 to 300 μg L−1 concentration range. The limit of detection and limit of quantification in plasma samples are 0.17 and 0.4 μg L−1. The preconcentration factor of the m-MIPs is 40. The HPLC method shows good precision (4.5 % at 50 μg L−1 levels) and recoveries (between 83 and 91 %) from spiked plasma samples.
We are presenting magnetic molecularly imprinted polymer nanoparticles (m-MIPs) for solid-phase extraction and sample clean-up of paracetamol. The m-MIPs were applied to the extraction of paracetamol from human blood plasma samples
This work describes a novel polyaniline-magnetite nanocomposite and its application to the preconcentration of Cr(VI) anions. The material was obtained by oxidative polymerization of aniline in the presence of magnetite nanoparticles. The parameters affecting preconcentration were optimized by a Box-Behnken design through response surface methodology. Extraction time, amount of magnetic sorbent and pH value were selected as the main factors affecting sorption. The sorption capacity of the sorbent for Cr(VI) is 54 mg g−1. The type, volume and concentration of the eluents, and the elution time were selected as main factors in the optimization study of the elution step. Following sorption and elution, the Cr(VI) ions were reacted with diphenylcarbazide, and the resulting dye was quantified by HPLC with optical detection at 546 nm. The limit of detection is 0.1 μg L−1, and all the relative standard deviations are <6.3 %. The nanocomposite was successfully applied to the rapid extraction and determination of trace quantities of Cr(VI) ions in spiked water samples.
A schematic procedure of magnetic solid phase extraction
We describe a near-infrared (NIR) fluorescent thrombin assay using a thrombin-binding aptamer (TBA) and Zn(II)-activated CuInS2 quantum dots (Q-dots). The fluorescence of Zn(II)-activated Q-dots is quenched by the TBA via photoinduced electron transfer, but if thrombin is added, it will bind to TBA to form G-quadruplexes and the Q-dots are released. As a result, the fluorescence intensity of the system is restored. This effect was exploited to design an assay for thrombin whose calibration plot, under optimum conditions, is linear in the 0.034 to 102 nmol L−1 concentration range, with a 12 pmol L−1 detection limit. The method is fairly simple, fast, and due to its picomolar detection limits holds great potential in the diagnosis of diseases associated with coagulation abnormalities and certain kinds of cancer.
We developed a simple near-infrared fluorescence assay using thrombin binding aptamer (TBA) and Zn(II)-activated CuInS2 quantum dots for the highly selective and sensitive detection of thrombin.
A nanoporous carbon derived from an aluminum-based metal-organic framework was deposited on stainless steel wires in a sol–gel matrix. The resulting fibers were applied to the solid-phase microextraction of the polycyclic aromatic hydrocarbons (PAHs) naphthalene, acenaphthene, fluorene, phenanthrene and anthracene from water and soil samples. The fiber was then directly inserted into the GC injector and the PAHs were quantified by GC-MS. The effects of salt addition, extraction temperature, extraction time, sample volume and desorption conditions on the extraction efficiency were optimized. A linear response to the analytes was observed in the 0.1 to 12 μg∙L−1 range for water samples, and in the 0.6 to 30 μg∙kg−1 for soil samples, with the correlation coefficients ranging from 0.9934 to 0.9985. The limits of detection ranged from 5.0 to 20 ng∙L−1 for water samples, and from 30 to 90 ng∙kg−1 for soil samples. The recoveries of spiked samples were between 72.4 and 108.0 %, and the precision, expressed as the relative standard deviations, is <12.8 %.
A MOF derived nanoporous carbon coated fiber for use in solid-phase microextraction was prepared via sol–gel technology. The coated fiber has a porous, rough and wrinkled structure, and shows a high thermal stability, good extraction repeatability and long lifetime. The established HS-SPME-GC-MS method is suitable for the determination of the PAHs from water and soil samples.
We describe a single-step solvothermal method for the preparation of nanocomposites consisting of graphene oxide and Fe3O4 nanoparticles (GO/Fe3O4). This material is shown to be useful as a magnetic sorbent for the extraction of flavonoids from green tea, red wine, and urine samples. The nanocomposite is taking advantage of the high surface area of GO and the magnetic phase separation feature of the magnetic sorbent. The nanocomposite is recyclable and was applied to the extraction of flavonoids prior to their determination by HPLC. The effects of amount of surfactant, pH value of the sample solution, extraction time, and desorption condition on the extraction efficiency, and the regeneration conditions were optimized. The limits of detection for luteolin, quercetin and kaempferol range from 0.2 to 0.5 ng∙ mL−1 in urine, from 3.0 to 6.0 ng∙mL−1 in green tea, and from 1.0 to 2.5 ng∙mL−1 in red wine. The recoveries are between 82.0 and 101.4 %, with relative standard deviations of <9.3 %.
The article describes a method for magnetic solid-phase extraction (MSPE) of trace amounts of natural substances in complex samples by using graphene oxide (GO)-Fe3O4nanoparticles as the sorbent.
Magnetic Fe3O4@SiO2 core shell nanoparticles containing diphenylcarbazide in the shell were utilized for solid phase extraction of Hg(II) from aqueous solutions. The Hg(II) loaded nanoparticles were then separated by applying an external magnetic field. Adsorbed Hg(II) was desorbed and its concentration determined with a rhodamine-based fluorescent probe. The calibration graph for Hg(II) is linear in the 60 nM to 7.0 μM concentration range, and the detection limit is at 23 nM. The method was applied, with satisfying results, to the determination of Hg(II) in industrial waste water.
A simple, sensitive and accurate method was developed for solid-phase extraction and preconcentration of trace levels of gold in various samples. It is based on the adsorption of gold on modified oxidized multi-walled carbon nanotubes prior to its determination by graphite furnace atomic absorption spectrometry. The type and volume of eluent solution, sample pH value, flow rates of sample and eluent, sorption capacity and breakthrough volume were optimized. Under these conditions, the method showed linearity in the range of 0.2–6.0 ng L−1 with coefficients of determination of >0.99 in the sample. The relative standard deviation for seven replicate determinations of gold (at a level of 0.6 ng L−1) is ±3.8 %, the detection limit is 31 pg L−1 (in the initial solution and at an S/N ratio of 3; for n = 8), and the enrichment factor is 200. The sorption capacity of the modified MWCNTs for gold(III) is 4.15 mg g−1. The procedure was successfully applied to the determination of gold in (spiked) water samples, human hair, human urine and standard reference material with recoveries ranging from 97.0 to 104.2 %.
A sorbent based on modified carbon nanotubes was prepared and used to extract gold ion from various samples prior to its determination by graphite furnace atomic absorption spectrometry
The food antioxidant quercetin was used as a template in an ultrathin molecularly imprinted polymer (MIP) film prepared by photopolymerization. Indium tin oxide (ITO) plates were electrografted with aryl layers via a diazonium salt precursor bearing two terminal hydroxyethyl groups. The latter act as hydrogen donors for the photosensitizer isopropylthioxanthone and enabled the preparation of MIP grafts through radical photopolymerization of methacrylic acid (the functional monomer) and ethylene glycol dimethacrylate (the crosslinker) in the presence of quercetin (the template) on the ITO. The template was extracted, and the remaining ITO electrode used for the amperometric determination of quercetin at a working potential of 0.26 V (vs. SCE). The analytical range is from 5.10−8 to 10−4 mol L−1, and the detection limit is 5.10−8 mol L−1.
This work describes the grafting of a molecularly imprinted polymer (MIP) film by combining diazonium surface chemistry and surface-initiated photopolymerization. The MIP grafts specifically and selectively recognize quercetin in pure solution in THF and in real green tea infusion.
We describe a sensitive method for the immunochromatographic determination of aflatoxin B1. It is based on the following steps: 1) Competitive interaction between non-labeled specific primary antibodies and target antigens in a sample and in the test zone of a membrane; 2) detection of the immune complexes on the membrane by using a secondary antibodies labeled with gold nanoparticles. The method enables precise adjustment of the required quantities of specific antibodies and the colloidal (gold) marker. It was applied in a lateral flow format to the detection of aflatoxin B1 and exhibits a limit of detection (LOD) of 160 pg · mL−1 if detected visually, and of 30 pg · mL−1 via instrumental detection. This is significantly lower than the LOD of 2 ng · mL−1 achieved by conventional lateral flow analysis using the same reagents.
Immunochromatography with secondary labeled antibodies caused 10-fold decrease of detection limit
We describe a simple and efficient method for solid phase extraction and speciation of trace quantities of arsenic. It is based on the use of functionalized aluminum oxide nanoparticles and does not require any oxidation or reduction steps. The experimental parameters affecting extraction and quantitation were optimized using fractional factorial design methods. Adsorbed arsenic was eluted from the sorbent with 1 M hydrochloric acid and determined by graphite furnace atomic absorption spectrometry. Preconcentration factors up to 750 were achieved depending on the sample volume. Studies on potential interferences by various anions and cations showed the method to be highly selective. Under optimum conditions, the calibration plots are linear in the 5.0 to 280 ng L−1 and 8.0 to 260 ng L−1 concentration ranges for As(III) and total arsenic, respectively. The detection limits (calculated for S/N ratios of 3) are 1.81 and 1.97 ng L−1 for As(III) and total arsenic, respectively. The method was successfully applied to the determination and speciation of arsenic in (spiked) environmental, food and biological samples and gave good recoveries. The method was validated using a certified geological reference material.
Novel functionalized Al2O3 nanoparticles were synthesized and used for speciation and determination of arsenic in different samples. The experimental variables were optimized using fractional factorial design that can save time and operational costs.
This article describes a fluorescent molecularly imprinted polymer (MIP) capable of selective fluorescent turn-on recognition of the tumor biomarker α-fetoprotein. The technique is making use of amino-modified Mn-doped ZnS quantum dots (QDs) as solid supports, 4-vinylphenylboronic acid and methyl methacrylate as the functional monomers, γ-methacryloxypropyl trimethoxysilane as the grafting agent, and α-fetoprotein as a template. A graft imprint is created on the surface of the QDs. The functional monomers are shown to play an important role in the formation of the binding sites and in preventing nonspecific protein binding. The resulting MIP-QDs display a good linear response to α-fetoprotein in the 50 ng · L−1 to 10 μg · L−1 concentration range, and the limit of detection is 48 ng · L−1. In our perception, the method has a wide scope in that it may be adapted to various other glycoproteins.
Schematic illustration of the synthesis of the MIP-QDs composites
We report on the time-resolved detection of the three fluoroquinolone (FQs) antibiotics ciprofloxacin (CIP), enrofloxacin (ENR) and flumequine (FLU). On addition of terbium(III) ions, the terbium(III)-FQs chelates are formed in-situ in an on-capillary derivatization reaction of a microfluidic system. The laser-induced terbium(III)-sensitized luminescence of the chelates is measured at excitation/emission wavelengths of 337/545 nm. The analytes can be separated and quantified within less than 4 min. A solid phase extraction step for analyte preconcentration can be included prior to chelation and microchip capillary electrophoresis. The analytical ranges of the calibration graphs for CIP, ENR and FLU are from 10.6 to 60.0, 10.3 to 51.0, and 11.5 to 58.8 ng mL−1, respectively, and the detection limits are 3.2, 3.1 and 3.6 ng mL−1, respectively. The precision was established at two concentration levels of each analyte and revealed relative standard deviations in the range from 3.0 to 10.2 %. The method was applied to the analysis of FQ-spiked water samples.
We report on the time-resolved detection of the three fluoroquinolone antibiotics. The analytes can be separated and quantified within less than 4 min. A solid phase extraction step for analyte preconcentration can be included prior to chelation and microchip capillary electrophoresis.
We describe the preparation of nanoporous carbon using a metal-organic framework (MOF) as a template and furfuryl alcohol as the source for carbon. The MOF consists of a zeolitic framework (ZIF-8) that was obtained from 2-methylimidazole and Zn(II) ions. ZIF-8 was soaked with furfuryl alcohol which then was carbonized at 900 °C. The resulting nanoporous carbon (MOF-C) exhibits a high specific surface area and a large pore volume. It was used as a dispersive solid-phase adsorbent for the preconcentration of the benzoylurea insecticides diflubenzuron, triflumuron, hexaflumuron and teflubenzuron from water and tangerine samples. Under optimized conditions, the methods exhibits excellent extraction performance. The insecticides can be quantified via HPLC with UV detection in the 0.5 to 100 ng mL−1 concentration range in case of spiked tap water, and in the 2.0 to 200 ng g−1 concentration range in case of tangerines. The limits of detection range from 0.10 to 0.23 ng mL−1 in case of water samples, and from 0.34 to 0.71 ng g−1 for tangerine sample (at an S/N ratio of 3). Mean recoveries range from 91.7 to 107.9 %, with relative standard deviations of <7.1 %. The results indicate that the method was efficient for the preconcentration of trace levels of benzoylurea insecticides from water and tangerine samples. Conceivably, this new adsorbent has a large potential with respect to the enrichment of other organic pollutants from various kinds of samples.
Nanoporous carbon was prepared using metal-organic framework (zeolitic imidazolate framework, ZIF-8) as template with furfuryl alcohol as carbon precursor, and was used as dispersive solid phase extraction adsorbent for the enrichment of some benzoylurea insecticides from water and tangerine samples.
A label-free and single-step method is reported for rapid and highly sensitive detection of bisphenol A (BPA) in aqueous samples. It utilizes an aptamer acting as a probe molecule immobilized on a commercially available array of interdigitated aluminum microelectrodes. BPA was quantified by measuring the interfacial capacitance change rate caused by the specific binding between bisphenol A and the immobilized aptamer. The AC signal also induces an AC electrokinetic effect to generate microfluidic motion for enhanced binding. The capacitive aptasensor achieves a limit of detection as low as 10 fM(2.8 fg ⋅ mL − 1) with a 20 s response time. The method is inexpensive, highly sensitive, rapid and therefore provides a promising technology for on-site detection of BPA in food and water samples.
A. AC electrokinetics effect plays a vital role in BPA detection by introducing microfluidic movement to accelerate the molecular transport to the electrode surface.
B. The ACEK capacitive aptasensor has a limit of detection as low as 10 fM (2.8 fg ⋅ mL − 1) with a 20-s response time.
We describe a molecularly imprinted polymer (MIP) for the solid-phase extraction of the skin protectant allantoin. The MIP was deposited on the surface of monodisperse silica microspheres possessing acroyl groups on the surface (MH-SiO2). The resulting MIP microspheres (MH-SiO2@MIP) showed a 3.4-fold higher adsorption capacity and a 1.9-fold better selectivity for allantoin than the respective non-imprinted polymer (MH-SiO2@NIP). The monolayer adsorption capacities of the MH-SiO2@MIP and the MH-SiO2@NIP were calculated with the help of the Langmuir model and found to be 6.8 and 1.9 mg•g−1, respectively. Adsorption kinetics fit a pseudo-second order rate mechanism, with an initial adsorption rate of 1.44 for the MH-SiO2@MIP, and of 0.07 mg•g−1•min−1 for the MH-SiO2@NIP. The material can be regenerated, and its adsorption capacity for allantoin remains stable for at least five regeneration cycles. It was successfully used as a sorbent for the selective solid-phase extraction of allantoin from Rhizoma dioscoreae.
A molecularly imprinted polymer for the selective separation of allantoin was developed. It was successfully used as a sorbent for the selective solid-phase extraction of allantoin from Rhizoma dioscoreae.
A fluorescent probe for the sensitive and selective determination of sulfide ions is presented. It is based on the use of graphene quantum dots (GQDs) which emit strong and stable blue fluorescence even at high ionic strength. Copper(II) ions cause aggregation of the GQDs and thereby quench fluorescence. The GQDs-Cu(II) aggregates can be dissociated by adding sulfide ions, and this results in fluorescence turn on. The change of fluorescence intensity is proportional to the concentration of sulfide ions. Under optimal conditions, the increase in fluorescence intensity on addition of sulfide ions is linearly related (r 2 = 0.9943) to the concentration of sulfide ions in the range from 0.20 to 20 μM, and the limit of detection is 0.10 μM (at 3 σ/s). The fluorescent probe is highly selective for sulfide ions over some potentially interfering ions. The method was successfully applied to the determination of sulfide ions in real water samples and gave recoveries between 103.0 and 113.0 %.
Graphene quantum dots (GQDs) emit strong blue fluorescence which, however, is quenched by copper(II) ions due to the formation of GQDs-Cu(II) aggregates. Fluorescence is recovered by sulfide ions due to the dissociation of GQDs-Cu(II) aggregates.