Evaluation of polychlorotrifluoroethylene as sorbent material for on-line solid phase extraction systems: determination of copper and lead by flame atomic absorption spectrometry in water samples

Polychlorotrifluoroethylene (PCTFE) in the form of beads was applied, as packing material for flow injection on-line column preconcentration and separation systems coupled with flame atomic absorption spectrometry (FAAS). Its performance characteristics were evaluated for trace copper determination in environmental samples. The on-line formed complex of metal with diethyldithiophosphate (DDPA) was sorbed on the PCTFE surface. Isobutyl methyl ketone (IBMK) at a flow rate of 2.8 mL min⁻¹ was used to elute the analyte complex directly into the nebulizer-burner system of spectrophotometer. The proposed sorbent material reveal, excellent chemical and mechanical resistance, fast adsorption kinetics permitting the use of high sample flow rates up to 15 mL min⁻¹ without loss of retention efficiency. For copper determination, with 90 s preconcentration time the sample frequency was 30 h⁻¹, the enhancement factor was 250, which could be further improved by increasing the loading (preconcentration) time. The detection limit (3s) was c_L = 0.07 μg L⁻¹, and the precision (R.S.D.) was 1.8%, at the 2.0 μg L⁻¹ Cu(II) level. For lead determination, the detection limit was c_L = 2.7 μg L⁻¹, and the precision (R.S.D.) 2.2%, at the 40.0 μg L⁻¹ Pb(II) level. The accuracy of the developed method was evaluated by analyzing certified reference materials and by recovery measurements on spiked natural water samples.     

Determination of traces of palladium in stream sediment and auto catalyst by FI-ICP-OES using on-line separation and preconcentration with QuadraSil TA

A flow injection analysis (FIA) method using on-line separation and preconcentration with a novel metal scavenger beads, QuadraSil™ TA, has been developed for the ICP-OES determination of traces of palladium. QuadraSil TA contains diethylenetriamine as a functional group on spherical silica beads and shows the highest selectivity for Pd(II) at pH 1 (0.1 mol l⁻¹ hydrochloric acid) solution. An aliquot of the sample solution prepared as 0.1 mol l⁻¹ in hydrochloric acid was passed through the QuadraSil TA column. After washing the column with the carrier solution, the Pd(II) retained on the column was eluted with 0.05 mol l⁻¹ thiourea solution and the eluate was directly introduced into an ICP-OES. The proposed method was successfully applied to the determination of traces of palladium in JSd-2 stream sediment certified reference material [0.019 ± 0.001 μg g⁻¹ (n = 3); provisional value: 0.0212 μg g⁻¹] and SRM 2556 used auto catalyst certified reference material [315 ± 4 μg g⁻¹ (n = 4); certified value: 326 μg g⁻¹]. The detection limit (3σ) of 0.28 ng ml⁻¹ was obtained for 5 ml of sample solution. The sample throughputs for 5 ml and 100 μl of the sample solutions were 10 and 15 h⁻¹, respectively.     

A colloidal suspension of nanostructured poly(N-butyl benzimidazole)-graphene sheets with high oxidase yield for analytical glucose and choline detections

A colloidal suspension of nanostructured poly(N-butyl benzimidazole)-graphene sheets (PBBIns-Gs) was used to modify a gold electrode to form a three-dimensional PBBIns-Gs/Au electrode that was sensitive to hydrogen peroxide (H₂O₂) in the presence of acetic acid (AcOH). The positively charged nanostructured poly(N-butyl benzimidazole) (PBBIns) separated the graphene sheets (Gs) and kept them suspended in an aqueous solution. Additionally, graphene sheets (Gs) formed “diaphragms” that intercalated Gs, which separated PBBIns to prevent tight packing and enhanced the surface area. The PBBIns-Gs/Au electrode exhibited superior sensitivity toward H₂O₂ relative to the PBBIns-modified Au (PBBIns/Au) electrode. Furthermore, a high yield of glucose oxidase (GOD) on the PBBIns-Gs of 52.3 mg GOD per 1 mg PBBIns-Gs was obtained from the electrostatic attraction between the positively charged PBBIns-Gs and negatively charged GOD. The non-destructive immobilization of GOD on the surface of the PBBIns-Gs (GOD-PBBIns-Gs) retained 91.5% and 39.2% of bioactivity, respectively, relative to free GOD for the colloidal suspension of the GOD-PBBIns-Gs and its modified Au (GOD-PBBIns-Gs/Au) electrode. Based on advantages including a negative working potential, high sensitivity toward H₂O₂, and non-destructive immobilization, the proposed glucose biosensor based on an GOD-PBBIns-Gs/Au electrode exhibited a fast response time (5.6 s), broad detection range (10 μM to 10 mM), high sensitivity (143.5 μA mM⁻¹ cm⁻²) and selectivity, and excellent stability. Finally, a choline biosensor was developed by dipping a PBBIns-Gs/Au electrode into a choline oxidase (ChOx) solution for enzyme loading. The choline biosensor had a linear range of 0.1 μM to 0.83 mM, sensitivity of 494.9 μA mM⁻¹ cm⁻², and detection limit of 0.02 μM. The results of glucose and choline measurement indicate that the PBBIns-Gs/Au electrode provides a useful platform for the development of oxidase-based biosensors.     

Surface plasmon resonance biosensor for enrofloxacin based on deoxyribonucleic acid

A DNA-based surface plasmon resonance biosensor for enrofloxacin was developed. Heating denatured DNA immobilized on the gold-coated glass surface was exploited. The immobilization was performed by a layer-by-layer co-deposition with a cationic polymer. The sensor performance was tested with real biological probes. Direct and simple determination of enrofloxacin in milk samples was demonstrated. The sensor response obeys Langmuir binding isotherm being almost linear until about 20 μg mL⁻¹. The detection limit in milk samples was estimated to be 3 μg mL⁻¹.     

Preparation of macroporous monoliths based on epoxy-bearing hydrophilic terpolymers and applied for affinity separations

This work reports the synthesis and characterization of poly(N-acryloyl-tris(hydroxymethyl)aminomethane-co-glycidyl methacrylate-co-N,N′-methylenebisacrylamide) [poly(NAT-GMA-BIS)] discs using different porogenic solvents. The macroporous polymer obtained with PEG 6000 as co-porogen showed the best porous properties of the series. End-point immobilization of heparin (Hep, as ligand) was then carried out on the products through reductive amination. Thus, the products were reacted with ethylenediamine (EDA) and hexamethylenediamine (HMDA) in order to introduce amine groups and to analyze the length of the spacer on the immobilization of heparin. Then, the highest value of amine groups [1.280 and 0.919 mmol amine/g dry support for poly(NAT-GMA-BIS)-EDA and poly(NAT-GMA-BIS)-HMDA, respectively] was obtained at 40 °C after 48 h of reaction. Finally, the amount of ligand coupled to discs was not influenced by the two length spacers assayed. The amount of Hep coupled on discs [591.50 and 489.90 μg Hep/g dry polymer for poly(NAT-GMA-BIS)-EDA-Hep and poly(NAT-GMA-BIS)-HMDA-Hep, respectively] was similar to that obtained using macroporous polymer beads reported by other authors. The supports yielded were used to assay the retention of antithrombin III (AT-III). The retention was greater for the EDA-containing product with a larger amount of heparin. These novel heparin-containing macroporous poly(NAT-GMA-BIS) discs could be used as potential affinity chromatography supports.     

Enatioselective quantitative separation of d- and l-thyroxine by molecularly imprinted micro-solid phase extraction silver fiber coupled with complementary molecularly imprinted polymer-sensor

Thyroxine is a known disease biomarker which demands a highly sensitive and selective technique to measure ultratrace level with enantiodifferentiation of its optical isomers (d- and l-), in real samples. In this work, an approach of hyphenation between molecularly imprinted micro-solid phase extraction and a complementary molecularly imprinted polymer-sensor was adopted for enantioseparation, preconcentration, and analysis of d- and l-thyroxine. In both techniques, the same imprinted polymer, coated on a vinyl functionalized self-assembled monolayer modified silver wire, was used as the respective extraction fiber as well as sensor material. This combination enabled enhanced preconcentration of test analyte substantially so as to achieve the stringent limit [limit of detection: 0.0084 ng mL⁻¹, RSD = 0.81%, S/N = 3 (d-thyroxine); 0.0087 ng mL⁻¹, RSD = 0.63%, S/N = 3 (l-thyroxine)] of clinical detection of thyroid-related diseases, without any problems of non-specific false-positive contribution and cross-reactivity.     

PdNi- and Pd-coated electrodes prepared by electrodeposition from ionic liquid for nonenzymatic electrochemical determination of ethanol and glucose in alkaline media

Nonenzymatic electrochemical determination of ethanol and glucose was respectively achieved using PdNi- and Pd-coated electrodes prepared by electrodeposition from the novel metal-free ionic liquid (IL); N-butyl-N-methylpyrrolidinium dicyanamide (BMP-DCA). BMP-DCA provided an excellent environment and wide cathodic limit for electrodeposition of metals and alloys because many metal chlorides could dissolve in this IL where the reduction potentials of Pd(II) and Ni(II) indeed overlapped, leading to the convenience of potentiostatic codeposition. In aqueous solutions, the reduction potentials of Pd(II) and Ni(II) are considerably separated. The bimetallic PdNi coatings with atomic ratios of ∼80/20 showed the highest current for ethanol oxidation reaction (EOR). Ethanol was detected by either cyclic voltammetry (CV) or hydrodynamic amperometry (HA). Using CV, the dependence of EOR peak current on concentration was linear from 4.92 to 962 μM with a detection limit of 2.26 μM (σ = 3), and a linearity was observed from 4.92 to 988 μM using HA (detection limit 0.83 μM (σ = 3)). The Pd-coated electrodes prepared by electrodeposition from BMP-DCA showed electrocatalytic activity to glucose oxidation and CV, HA, and square-wave voltammetry (SWV) were employed to determine glucose. SWV showed the best sensitivity and linearity was observed from 2.86 μM to 107 μM, and from 2.99 mM to 10.88 mM with detection limits of 0.78 μM and 25.9 μM (σ = 3), respectively. For glucose detection, the interference produced from ascorbic acid, uric acid, and acetaminophen was significantly suppressed, compared with a regular Pt disk electrode.     

An automated system for liquid-liquid extraction based on a new micro-batch extraction chamber with on-line detection: Preconcentration and determination of copper(II)

An automated system to perform liquid-liquid extraction is proposed, in which the effective mixture (the intimate contact) between the aqueous phase and the organic phase, as well as the separation of the phases, are carried out in a micro-batch glass extraction chamber. Sample, reagents and organic solvent are introduced into the glass extraction chamber by a peristaltic pump using air as carrier. The detection of the extracted species from the aqueous phase is made in a small volume (120-150 μl) of isobutyl methyl ketone (MIBK). The system allows enrichment factors of 2-10-fold. The proposed automatic system was evaluated for Cu(II) extraction based on complex formation between copper(II) and 1-(2′-pyridylazo)naphthol (PAN) in MIBK. When a volumetric ration of 2:1 (aqueous:organic) was implemented, copper was detected in the concentration range of 100-1600 μg l⁻¹ (r = 0.9995) with a relative standard deviation of 2% (200 μg l⁻¹, n = 5) and a detection limit of 20 μg l⁻¹. The analytical curve was linear over the concentration range 25-500 μg l⁻¹ (r = 0.9994) when a volumetric ratio of 10:1 was employed. With this ratio, the detection limit was 5.0 μg l⁻¹ and the relative standard deviation was 6% (50 μg l⁻¹, n = 5).     

Electrochemical immunoassay using magnetic beads for the determination of zearalenone in baby food: An anticipated analytical tool for food safety

In this work, electrochemical immunoassay involving magnetic beads to determine zearalenone in selected food samples has been developed. The immunoassay scheme has been based on a direct competitive immunoassay method in which antibody-coated magnetic beads were employed as the immobilisation support and horseradish peroxidase (HRP) was used as enzymatic label. Amperometric detection has been achieved through the addition of hydrogen peroxide substrate and hydroquinone as mediator.Analytical performance of the electrochemical immunoassay has been evaluated by analysis of maize certified reference material (CRM) and selected baby food samples. A detection limit (LOD) of 0.011 μg L⁻¹ and EC₅₀ 0.079 μg L⁻¹ were obtained allowing the assessment of the detection of zearalenone mycotoxin. In addition, an excellent accuracy with a high recovery yield ranging between 95 and 108% has been obtained. The analytical features have shown the proposed electrochemical immunoassay to be a very powerful and timely screening tool for the food safety scene.     

Automatic screening method for the preconcentration and determination of N-nitrosamines in water

A screening method was developed to discriminate among water samples contaminated or uncontaminated with N-nitrosamines in order to reduce the use of expensive instruments such as chromatographs. The system is based on the preconcentration of the analytes onto a sorbent column, elution and derivatization to form nitrite, then formation of a coloured product (Griess reaction) and photometric detection. The limit of detection achieved for 100 ml of sample volume was 0.2 μg/l and the sample frequency 3 h⁻¹. The reliability of the proposed method of the N-nitrosamines was established at five concentrations (between 0.5 and 3 times the limit of detection). For a level concentration of 0.6 μg/l (three times the limit of detection), the percentage of false negatives is 0%. The method was applied to the screening of several water samples (river, pond, well, tap and waste) with a positive response only for waste water samples.     

Ultrasensitive electrochemical sensor for p-nitrophenyl organophosphates based on ordered mesoporous carbons at low potential without deoxygenization

p-Nitrophenyl organophosphates (OPs) including paraoxon, parathion and methyl parathion, etc, are highly poisonous OPs, for which sensitive and rapid detection method is most needed. In this work, an ultrasensitive electrochemical sensor for the determination of p-nitrophenyl OPs was developed based on ordered mesoporous carbons (OMCs) modified glassy carbon electrode (GCE) (OMCs/GCE). The electrochemical behavior and reaction mechanism of p-nitrophenyl OPs at OMCs/GCE was elaborated by taking paraoxon as an example. Experimental conditions such as buffer pH, preconcentration potential and time were optimized. By using differential pulse voltammetry, the current response of the sensor at −0.085 V was linear with concentration within 0.01–1.00 μM and 1.00–20 μM paraoxon. Similar linear ranges of 0.015–0.5 μM and 0.5–10 μM were found for parathion, and 0.01–0.5 μM and 0.5–10 μM for methyl parathion. The low limits of detection were evaluated to be 1.9 nM for paraoxon, 3.4 nM for parathion and 2.1 nM for methyl parathion (S/N = 3). Common interfering species had no interference to the detection of p-nitrophenyl OPs. The sensor can be applicable to real samples measurement. Therefore, a simple, sensitive, reproducible and cost-effective electrochemical sensor was proposed for the fast direct determination of trace p-nitrophenyl OPs at low potential without deoxygenization.     

Flow injection determination of choline in milk hydrolysates by an immobilized enzyme reactor coupled to a selective hydrogen peroxide amperometric sensor

A choline oxidase (ChO) immobilized enzyme reactor (IMER) prepared by glutaraldehyde coupling of the enzyme on aminopropyl modified controlled pore glass beads is described. The ChO-IMER was coupled, in a flow injection configuration system, to an interference free hydrogen peroxide amperometric sensor based on a Pt surface modified by an overoxidized polypyrrole film. The resulting analytical device responds selectively to choline and displays a sensitivity of 46.9 ± 0.2 μC mM⁻¹ and a limit of detection, calculated at a signal-to-noise ratio equal to 3, of 7 μM. Sensitivity remains constant for about 20 days and then starts to slowly deteriorate and after 2 months a 70% of the initial sensitivity was still retained. The application to choline determination in milk hydrolysates is demonstrated. Short- and long-term drift observed in the analytical response can be corrected by a bracketing technique.     

On-line sorptive preconcentration platform incorporating a readily exchangeable Oasis HLB extraction micro-cartridge for trace cadmium and lead determination by flow injection-flame atomic absorption spectrometry

A simple, sensitive and inexpensive flow injection solid phase extraction (SPE) system was developed for automatic determination of trace level concentrations of metals. The potentials of this novel scheme, coupled to flame atomic absorption spectrometry (FAAS), were demonstrated for trace cadmium and lead determination in environmental water samples. The method was based on on-line chelate complex formation of target species with ammonium diethyldithiophosphate (DDTP), retention onto the surface of reversed-phase poly(divinylbenzene-N-vinylpyrrolidone) co-polymeric beads (Oasis HLB) and elution with methanol prior to atomization. A special PVC adapter was designed for easy and rapid replacement of the commercially available SPE cartridge. All main chemical and hydrodynamic parameters affecting the complex formation, sorption and elution of the analyte were optimized thoroughly. Moreover, the effect of potential interfering species occurring in environmental samples was also explored.For 90 s preconcentration time, enhancement factors of 155 and 180, detection limits (3s) of 0.09 μg L^− 1 and 0.9 μg L^− 1 and relative standard deviations (R.S.D.) of 2.9% (at 4.0 μg L^− 1) and 2.6% (at 20.0 μg L^− 1) were obtained for cadmium and lead, respectively, with a sample throughput of 24 h^− 1. The measurement trueness of the developed method was evaluated by analyzing a certified reference material and spiked environmental water samples. The proposed method is well suited to detect the target elements at concentration levels below the maximum allowed concentrations endorsed by the European Framework Directive (2008/105/EC) in inland and coastal waters.     

Solid phase extraction of Co ions using l-tyrosine immobilized on multiwall carbon nanotubes

A study was performed to assess the performance of aminoacids immobilized on carbon nanotubes (CNTs) for their employment as a sorbent for solid phase extraction systems. An immobilization method is introduced and the aminoacid l-tyrosine was chosen as a case study. A spectrophotometric study revealed the amount of aminoacid immobilizated on CNTs surface, and it turned to be of 3174 μmol of l-tyr g⁻¹. The material was tested for Co retention using a minicolumn inserted in a flow system. At pH 7.0, the amount of Co retained by the column was of 37.58 ± 3.06 μmol Co g⁻¹ of CNTs. A 10% (v/v) HNO₃ solution was chosen as eluent. The pH study revealed that Co binding increased at elevated pH values. The calculation of the mol ratio (moles of Co bound at pH 9 to moles of l-tyr) turned to be 3:1. The retention capacity was compared to other bivalent cations and showed the following tendency: Cu²⁺ > Ni²⁺ > Zn²⁺ ? Co²⁺. The analytical performance was evaluated and an enrichment factor of 180 was obtained when 10 mL of 11.37 μg L⁻¹ Co solution was loaded onto the column at pH 9.0; reaching a limit of detection (LoD) of 50 ng L⁻¹. The proposed system was successfully applied to Co determination in QC-LL2 standard reference material (metals in natural water).     

Ultrasensitive detection of pepsinogen I and pepsinogen II by a time-resolved fluoroimmunoassay and its preliminary clinical applications

A fast and highly sensitive assay for pepsinogen I (PG I) and pepsinogen II (PG II) by using time-resolved fluoroimmunoassay (TRFIA) detection technique has been developed for the determination of serum PG I and PG II against gastrointestinal diseases. On the noncompetitive assay, one monoclonal antibody (McAb) coated on wells was directed against a specific antigenic site on the PG I or PG II. The McAb, called as labelling McAb, was prepared with the europium-chelate of N-(p-isothiocyanatobenzyl)-diethylenetriamine-N,N,N,N-tetraacetic acid and directed against a different antigenic site on the PG I or PG II molecule. After bound/free separation by washing, the fluorescence counts of bound Eu³⁺-McAb were measured. The levels of PG in sera from patients or healthy volunteers were determined by PG I and PG II TRFIA using the autoDELFIA₁₂₃₅ system. The measurement ranges of PG I-TRFIA were 3.5-328.0 μg L⁻¹ and those of PG II-TRFIA were 2.0-55.0 μg L⁻¹. The within-run and between-run CVs of the PG I-TRFIA were 1.9% and 4.7%, respectively, and those of PG II-TRFIA were 2.1% and 3.8%, respectively. The recovery rates of PG I-TRFIA and PG II-TRFIA were 102.7% and 104.6%, respectively. The detection limitations of PG I and PG II were 0.05 μg L⁻¹ and 0.02 μg L⁻¹, respectively. The dilution experiments showed the percentage of expected value of PG I-TRFIA was 93.2-102.3% and of PG II-TRFIA was 97.3-110.6%. The cross-reacting rate between PG I and PG II was negligible. The linear correlation of radioimmunoassay (RIA) and TRFIA measurements resulted in a correlation coefficient as 0.926 of PG I and as 0.959 of PG II. The europium-labelling McAbs were stable for at least one year at −20 °C, and the results of the TRFIA with same reagents were reproducible over one year as well. The means of 1600 healthy volunteers were 162.4 ± 52.1 μg L⁻¹ for serum PG I, 11.7 ± 6.8 μg L⁻¹ for serum PG II, and 13.8 ± 7.4 for the PG I/PG II ratio. The normal ranges of Serum PG I levels for healthy volunteers were 58.2-266.6 μg L⁻¹, and those of serum PG II levels were less than 25.3 μg L⁻¹. The availability of a highly sensitive, reliable, and convenient PG-TRFIA method for quantifying PG will allow investigations into the possible diagnostic value of this analysis in various clinical conditions, including gastric carcinoma, duodenal ulcer, gastric ulcer and gastritis. The sensitivity and reproducibility of the assay were satisfactory for clinical applications.     

Sol-gel derived urease-based optical biosensor for the rapid determination of heavy metals

A urease optical biosensor for the determination of heavy metals based on sol-gel immobilization technique was developed. A fluorescent dye, FITC-dextran, was encapsulated and parameters including optical properties of the probe, relative enzyme activity, initial pH value and the buffer concentration for substrate preparation were investigated. In sol-gel immobilization, 1 mM Tris-HCl at pH 7.1 provided a sufficient buffer capacity for metal ion analysis as well as the enzyme activity maintenance. Also, two analytical procedures, incubated and un-incubated systems, were compared to understand the sensitivity and applicability to heavy metal analysis. The developed optical biosensor showed high reproducibility and the relative standard deviation (R.S.D.) of 5.1% (n=10) was obtained. Also, eight measurements can be completed automatically within 36 min. The biosensor has high sensitivity to Cu(II) and Cd(II) and an analytical range of 10-230 μM with a detection limit of 10 μM was achieved. Moreover, biological and environmental samples were examined to evaluate the applicability of the developed biosensor. A 19-82% of inhibition was observed when 20-45 μM metal ions were amended into tested samples, revealing that the developed system has the potential for the determination of heavy metals in real samples.     

Covalent binding of genetically engineered microorganisms to porous glass beads

Several covalent immobilization methods, which have been routinely used with proteins and antibodies, were studied for their ability to immobilize genetically engineered Escherichia coli cells to glass beads. The cells used in this study expressed a metal binding peptide that binds cadmium (Cd) and mercury (Hg). The initial work focused on a method employing 2.5% aminopropyltrimethoxy silane and 2.5% glutaraldehyde for covalent immobilization of cells onto porous glass beads. Scanning electron microscopy (SEM) demonstrated cell attachment (average of 3.0×10⁸ cells per bead) to the irregular surface. Columns containing cells immobilized with the 2.5% aminosilane and 2.5% glutaraldehyde removed more than 90% of the Cd from solutions with 50 ppb and 1 ppm levels. Following removal of the bound Cd with HCl elution and regeneration to pH 6.0, the columns were shown to effectively bind additional cadmium. Various concentrations of aminosilane and glutaraldehyde were tested for improved cell density.Glutaraldehyde is a universal and convenient cross-linker, but there are some concerns with its effects on the cells and proteins, therefore, two additional covalent techniques were examined. One method employed the aminopropyltrimethoxy silane and carbodiimide, and the other used mercaptopropyltrimethoxy silane and the heterobifunctional cross-linker GMBS. Some comparisons of these two immobilization methods to the method employing glutaraldehyde are described.     

Ultrasensitive and simultaneous detection of heavy metal ions based on three-dimensional graphene-carbon nanotubes hybrid electrode materials

A green and facile method was developed to prepare a novel hybrid nanocomposite that consisted of one-dimensional multi-walled carbon nanotubes (MWCNTs) and two-dimensional graphene oxide (GO) sheets. The as-prepared three-dimensional GO–MWCNTs hybrid nanocomposites exhibit excellent water-solubility owing to the high hydrophilicity of GO components; meanwhile, a certain amount of MWCNTs loaded on the surface of GO sheets through π–π interaction seem to be “dissolved” in water. Moreover, the graphene(G)-MWCNTs nanocomposites with excellent conductivity were obtained conveniently by the direct electrochemical reduction of GO–MWCNTs nanocomposites. Seeing that there is a good synergistic effect between MWCNTs and graphene components in enhancing preconcentration efficiency of metal ions and accelerating electron transfer rate at G-MWCNTs/electrolyte interface, the G-MWCNTs nanocomposites possess fast, simultaneous and sensitive detection performance for trace amounts of heavy metal ions. The electrochemical results demonstrate that the G-MWCNTs nanocomposites can act as a kind of practical sensing material to simultaneously determine Pb²⁺ and Cd²⁺ ions in terms of anodic stripping voltammetry (ASV). The linear calibration plots for Pb²⁺ and Cd²⁺ ranged from 0.5 μg L⁻¹ to 30 μg L⁻¹. The detection limits were determined to be 0.2 μg L⁻¹ (S/N = 3) for Pb²⁺ and 0.1 μg L⁻¹ (S/N = 3) for Cd²⁺ in the case of a deposition time of 180 s. It is worth mentioning that the G-MWCNTs modified electrodes were successfully applied to the simultaneous detection of Cd²⁺ and Pb²⁺ ions in real electroplating effluent samples containing lots of surface active impurities, showing a good application prospect in the determination of trace amounts of heavy metals.     

Magnetic molecularly imprinted polymer beads prepared by microwave heating for selective enrichment of β-agonists in pork and pig liver samples

Novel magnetic molecularly imprinted polymer (MIP) beads using ractopamine as template for use in extraction was developed by microwave heating initiated suspension polymerization. Microwave heating, as an alternative heating source, significantly accelerate the polymerization process. By incorporating magnetic iron oxide, superparamagnetic composite MIP beads with average diameter of 80 μm were obtained. The imprinted beads were then characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and vibrating sample magnetometer. Highly cross-linked porous surface and good magnetic property were observed. The adsorption isotherm modeling was performed by fitting the data to Freundlich isotherm model. The binding sites measured were 3.24 μmol g⁻¹ and 1.17 μmol g⁻¹ for the magnetic MIP beads and the corresponding non-imprinted magnetic beads, respectively. Cross-selectivity experiments showed the recognition ability of the magnetic MIP beads to analytes is relative to degree of molecular analogy to the template. Finally, this magnetic MIP bead was successfully used for enrichment of ractopamine, isoxsuprine and fenoterol from ultrasonically extracted solution of pork and pig liver followed by high performance chromatography with fluorescence detection. The proposed method presented good linearity and the detection limits was 0.52-1.04 ng mL⁻¹.The recoveries were from 82.0% to 90.0% and from 80.4% to 86.8% for the spiked pork and pig liver, respectively, with the RSDs of 5.8-10.0%. Combination of the specific adsorption property of the MIP material and the magnetic separation provided a powerful analytical tool of simplicity, flexibility, and selectivity.     

Factorial design for multivariate optimization of preconcentration system for spectrophotometric phosphorus determination

The present paper proposes a preconcentration procedure for phosphorus determination by using ultraviolet-visible spectrophotometer. It is based on the formation of phosphomolybdate and its reduction to molybdenum blue. Phosphorus extraction as phosphomolybdenum blue complex was performed onto Amberlite XAD-4. The optimization step was carried out using two-level full factorial design. Three variables (resin amount, sample volume, flow rate) were regarded as factors in the optimization. The relative standard deviation was 2% at 0.08 μg mL⁻¹. The limit of detection was found to be 2.23 μg L⁻¹ (N = 15). The proposed solid-phase extraction procedure was applied to phosphorus in some fruit leaves, natural waters, and a standard reference material (SRM 1515 apple leaves).