Voltammetric determination of cadmium(II) using a chemically modified electrode

An 1-(pyridylazo)-2-naphthol modified glassy carbon electrode has been investigated as sensor for the measurement of trace levels of Cd2+. Cd2+ is deposited on the surface of a PAN modified glassy carbon electrode at -1.10 V (vs. SCE) via forming Cd2+-PAN and subsequent reduction at the electrode. In the following step, Cd-PAN is oxidized, and voltammograms are recorded by scanning the potential in a positive direction. Calibration plots were found to be linear in the range 2 x 10(-8) mol/L to 8 x 10(-7) mol/L. The detection limit was 5 x 10(-10) mol/L, and the coefficient of variation, determined on one single electrode at a concentration of 5 x 10(-7) mol/L, was calculated to be 3.2% (n = 5). Using this new kind of modified electrode, trace levels of Cd(II) in water samples were determined; the average recovery was calculated to be 98.78%.     

Voltammetric determination of cadmium(II) using a chemically modified electrode

An 1-(pyridylazo)-2-naphthol modified glassy carbon electrode has been investigated as sensor for the measurement of trace levels of Cd²⁺. Cd²⁺ is deposited on the surface of a PAN modified glassy carbon electrode at –1.10 V (vs. SCE) via forming Cd²⁺–PAN and subsequent reduction at the electrode. In the following step, Cd-PAN is oxidized, and voltammograms are recorded by scanning the potential in a positive direction. Calibration plots were found to be linear in the range 2 × 10^–8 mol/L to 8 × 10^–7 mol/L. The detection limit was 5 × 10^–10 mol/L, and the coefficient of variation, determined on one single electrode at a concentration of 5 × 10^–7 mol/L, was calculated to be 3.2% (n = 5). Using this new kind of modified electrode, trace levels of Cd(II) in water samples were determined; the average recovery was calculated to be 98.78%. Received: 17 August 2000 / Revised: 19 December 2000 / Accepted: 27 December 2000     

Heterogenization of an organorhenium(VII) oxide on a modified mesoporous molecular sieve

A novel route to heterogenize an organorhenium(VII) oxide, derived from the well examined methyltrioxorhenium(VII) (MTO), on the surface of an iodosilane-modified MCM-41 is applied. The successful grafting of the -CH(2)-ReO3 moiety on the surface was evidenced by 1H CP MAS NMR, IR spectroscopy, TG-MS, and elemental analysis. XRD and TEM analyses confirm the retaining of long-range ordering throughout the grafting process. The rhenium loading of the mesoporous material after heterogenization of MTO is found to be 1.25 wt%. Despite containing formally a derivative of the very sensitive benzyltrioxorhenium(VII) the material is stable at room temperature and applicable as a heterogeneous catalyst for aldehyde olefination reactions.     

Voltammetric determination of nitrendipine on composite film modified electrode

This paper was focused on the use of electrochemical methods based on a novel composite film modified electrode for the pharmaceutical analysis. This modified electrode was fabricated by integration of room-temperature ionic liquids (1-butyl-3-methylimidazolium hexafluophosphate) and multi-walled carbon nanotubes with polymeric matrix (chitosan). This sensor showed good stability and high accumulation efficiency. Electrochemical behavior of nitrendipine at this electrode was investigated in detail. A sensitive cathodic peak was observed at −0.76 V on the modified electrode. Under the optimized conditions, the peak current was linear to nitrendipine concentration in the range of 4.0 × 10⁻⁷ ∼ 5.0 × 10⁻⁵ M, and the detection limit was estimated to be 1.0 × 10⁻⁷ M after an accumulation for 150 s on open circuit. In addition, the proposed method was applied to the determination of nitrendipine in real samples, and the recovery was from 97.6 to 102.5%.     

High-sensitivity determination of lead and cadmium based on the Nafion-graphene composite film

Graphene nanosheets, dispersed in Nafion (Nafion-G) solution, were used in combination with in situ plated bismuth film electrode for fabricating the enhanced electrochemical sensing platform to determine the lead (Pb²⁺) and cadmium (Cd²⁺) by differential pulse anodic stripping voltammetry (DPASV). The electrochemical properties of the composite film modified glassy carbon electrode were investigated. It is found that the prepared Nafion-G composite film not only exhibited improved sensitivity for the metal ion detections, but also alleviated the interferences due to the synergistic effect of graphene nanosheets and Nafion. The linear calibration curves ranged from 0.5 μg L⁻¹ to 50 μg L⁻¹ for Pb²⁺ and 1.5 μg L⁻¹ to 30 μg L⁻¹ for Cd²⁺, respectively. The detection limits (S/N = 3) were estimated to be around 0.02 μg L⁻¹ for Pb²⁺ and Cd²⁺. The practical application of the proposed method was verified in the water sample determination.     

Voltammetric determination of tyrosine based on an L-serine polymer film electrode

A novel film electrode for the voltammetric determination of tyrosine has been constructed based on electropolymerization of L-serine on a glassy carbon electrode. Voltammetric behaviour of tyrosine on the poly-L-serine film electrode was investigated with cyclic voltammetry and linear sweep voltammetry, and electrochemical parameters were calculated from chronocoulometry. In optimal conditions, the oxidation peak current of tyrosine on the poly-L-serine film electrode was enhanced greatly. A sensitive oxidation peak at 0.90 V was employed to determine tyrosine. A linearity between the oxidation peak current and the tyrosine concentration was obtained in the range of 3.0 x 10(-7) to 1.0 x 10(-4) mol L(-1) with a detection limit of 1.0 x 10(-7)mol L(-1). The practical application of the film electrode in the determination of tyrosine in a commercial amino acid oral solution demonstrated that it has good selectivity and high sensitivity.     

Voltammetric myoglobin sensor based on a glassy carbon electrode modified with a composite film consisting of carbon nanotubes and a molecularly imprinted polymerized ionic liquid

The ionic liquid 1-{3-[(2-aminoethyl)amino]propyl}-3-vinylimidazole bromide was synthesized and used to fabricate a molecularly imprinted film for electrochemical sensing of myoglobin (Myo). This film was deposited on a glassy carbon electrode modified with multi-walled carbon nanotubes by using the ionic liquid as the functional monomer, Myo as the template, N,N′-methylenebisacrylamide as the crosslinker, and a redox system containing ammonium persulfate and N,N,N′,N′-tetramethylethylenediamine as the initiator. The sensing performance of the modified electrode was investigated by using the hexacyanoferrate system as an electrochemical redox probe. The results demonstrated that the sensor possesses good selectivity and high sensitivity. The oxidation peak current at the potential of ~0.3 V (vs. SCE) was found linearly related to the myoglobin concentration in the range from 60.0 nM to 6.0 μM, with a 9.7 nM detection limit at an S/N ratio of 3. The sensor was applied to the determination of Myo in spiked serum samples where it showed average recoveries (for n = 5) of 96.5 %.

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Graphical abstract By using a polymerizable ionic liquid as the functional monomer, a myoglobin imprinted polymer was fabricated on a multi-walled carbon nanotube modified glassy carbon electrode. The sensing performances of the molecularly imprinted sensor towards myoglobin demonstrated good selectivity, sensitivity and accuracy.

     

Enhanced ionic conductivity of poly(ethylene oxide) (PEO) electrolyte by adding mesoporous molecular sieve LiAlSBA

Mesoporous molecular sieve LiAlSBA was prepared via an ion exchange process with mesoporous AlSBA directly, which has a regular 2D hexagonal structure with pore size about 7 nm. It was added into poly(ethylene oxide) (PEO) solid electrolyte as filler. The characteristics of the composite polymer electrolyte were determined by XRD, DSC, TGA, FTIR, PLM and electrochemical methods. Compared with bare PEO electrolyte, the adding of dispersed LiAlSBA powder improved the ionic conductivity of PEO polymer electrolyte more than three orders. The reason for it is that mesoporous LiAlSBA powder acts as crystal cores in PEO composite electrolyte and fines the crystallites, decreases the crystallinity, which provides much more continuous amorphous domain for Li⁺ moving easily in PEO electrolyte. Besides, lithium ions of the mesoporous molecular sieves can hop from one site to another along the surface of the mesoporous channels, this mechanism is absent in the case of common nano-ceramic fillers in PEO electrolyte.     

Voltammetric and flow-injection determination of carbohydrates using composite electrodes based on carbon nanotubes and Nickel(II) hexacyanoferrate

The catalytic activities of oxo and hydroxo forms of nickel(II) on the surface of a nickel deposit and an inorganic film of nickel(II) hexacyanoferrate(III) (NiHCF) electrodeposited on a glassy-carbon electrode both unmodified and modified by multi-wall or single-wall (also functionalized) carbon nanotubes in the electrooxidation of glucose, sucrose, and maltose are compared. A more pronounced catalytic effect was obtained in the electrooxidation of these carbohydrates on an electrode modified with functionalized singlewall carbon nanotubes and a NiHCF film. Methods are proposed for the voltammetric and flow-injection determination of carbohydrates on this composite electrode. A linear dependence of the analytical signal on the analyte concentration was observed in the range from 5 × 10^?7 to 5 × 10^?2 M under stationary conditions and from 0.003 to 0.3 μmol under flow conditions.     

Voltammetric sensors based on gel composites containing carbon nanotubes and an ionic liquid

Possibilities of using electrode coatings based on a gel of carboxylated multiwall carbon nanotubes (MWCNTs) in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, [BMIm]PF₆) for the creation of a voltammetric sensor with electrocatalytic properties with respect to the pharmacological group of catecholamines—levodopa, methyldopa, and carbidopa—are considered. Using cyclic voltammetry, it was found that a glassy carbon electrode coated with a thin layer of an MWCNT–[BMIm]PF₆ gel or an MWCNT–[BMIm]PF₆–Nafion gel-composite induced a decrease in overvoltage (~60 mV), improved the reversibility of the redox reaction, and increased oxidation currents of the studied substances in comparison with an unmodified glassy carbon electrode. The concentration dependence of the analytical signal was linear in the ranges of 1–250, 2–350, and 5–400 mM for carbidopa, levodopa, and methyldopa, respectively. In the determination of the specified substances in diluted urine samples and tableted drugs, the accuracy index was 98–102% and the relative standard deviation, 0.3–5% (n = 5, P = 0.95).     

Preparation, characterization, and application of a new thiol-functionalized ionic liquid for highly selective extraction of Cd(II)

A highly selective thiol-functionalized ionic liquid (thiol-FIL) was synthesized and characterized by FT-IR and ESI mass spectroscopy. The capability of thiol-FIL to extract Cd(II), Ni(II), Cr(III) and Pb(II) was evaluated. It is found that thiol-FIL possesses high selectivity for Cd(II), and this has led to a method for determination of Cd(II) by flame atomic absorption spectrometry that is free of interferences by up to a 1,000-fold excess of Na(I), Mg(II), Ca(II), Mn(II), Fe(III), Al(III), Cu(II), Zn(II), Ni(II), Cr(III), Co(II), As(III), Pb(II), and Hg(II). With extraction equilibrium time of 1 min, a good linearity (r = 0.9998) and a detection limit of 0.39 μg?L^?1 were obtained. The precision (RSD) for 11 replicate measurements of 10 μg?L^?1 Cd was 1.6%. The method was validated using certified reference materials. The recoveries of cadmium in spiked real samples ranged from 97% to 102%.     

A stannum-bismuth composite film electrode for simultaneous determination of zinc(II) and cadmium(II) using differential pulse anodic stripping voltammetry

The development and use of 'green' electrode materials is extremely attractive for the routine use of disposable metal sensors. Bismuth is an environmentally-friendly element and a bismuth film electrode was proposed as an alternative to mercury film electrodes. Compared with bismuth, stannum is a more 'environmentally friendly' material. The stannum-bismuth composite film electrode prepared by the in situ electrodeposition of stannum and bismuth on the glassy carbon substrate is reported for the first time. Compared with bismuth film and stannum film electrodes, the stannum-bismuth composite film electrode revealed better electroanalytical performance, and can be used as a possible alternative electrode for electrochemical stripping analysis of trace heavy metals.     

Solid phase ligand-less extraction of cadmium(II) using a silica gel modified with an amino-functionalized ionic liquid

A method was developed for the determination of cadmium(II) by ligand-less solid phase extraction that is based on the direct retention of Cd(II) in a mini-column filled with a silica gel modified with an amino-functionalized ionic liquid. The effects of pH, sample volume and its flow rate, eluent concentration and its volume, the flow rate of eluent, and of potential interferences on extraction and desorption were optimized. Following its determination by electrothermal atomic absorption spectrometry, the detection limit for Cd(II) is 8.9 ng L^?1, and the relative standard deviation is 2.3 % (at 1.0 ng mL^?1; for n?=?5). The method was applied to the analysis of Cd(II) in a certified reference material (laver; GBW10023), and the recoveries ranged from 97.0 to104.0 %

Electrochemical sensor for lead(II) ion using a carbon ionic-liquid electrode modified with a composite consisting of mesoporous carbon, an ionic liquid, and chitosan

A novel electrode was prepared that enables sensing of lead(II) ion. A suspension composed of ordered mesoporous carbon (OMC), an ionic liquid (IL), and chitosan was deposited on the highly conductive surface of a carbon ionic-liquid electrode (CILE). The surface of the sensing electrode was characterized by scanning electron microscopy and cyclic voltammetry. The new electrode can be used to determine lead(II) ion because the hydrophobic ionic liquid of the CILE can extract Pb(II), while the OMC accelerates the electron transfer rate between the electrode and Pb(II) and also strongly adsorbs Pb(II). The resulting electrode displays excellent and synergistic response to Pb(II) which is linear in the range from 0.05 to 1.4?μM, with a correlation coefficient of 0.997 and a detection limit of 25 nM.

Sensitive determination of 4-nitrophenol based on multi-walled carbon nano-tube/ionic liquid/chitosan composite film modified electrode

A composite film modified glassy carbon electrode (GCE) fabricated with spinning coating of multiwalled carbon nano-tube (MWNT) /1-butyl-3-methylimidazolium tetrafluoroborate/chitosan sol was developed for the electrochemical determination of 4-nitrophenol (4-NP). An obvious reduction peak located at about −0.688 V was observed with voltammetric measurements in the potential range from 0.200 V to −1.00 V. Compared with the bare GCE, the reduction peak potential shifted positively and the peak current increased significantly. All experimental parameters for the determination of 4-NP were optimized. It was found that the reduction peak current was proportional to 4-NP concentration in the range from 3.00 × 10⁻⁷ to 2.00 × 10⁻⁵ mol l⁻¹ with the detect limitation of 1.00 × 10⁻⁷ mol l⁻¹ (S/N = 3) after accumulation for 90 s. The proposed method was successfully applied for the determination of trace amounts of 4-NP in lake water.     

Factors affecting the reactivity of thiol-functionalized mesoporous silica adsorbents toward mercury(II)

Numerous mercaptopropyl-functionalized silica spheres have been prepared by either post-synthesis grafting of MCM-41 and MCM-48 or self-assembly co-condensation of mercaptopropyltrimethoxysilane (MPTMS) or mercaptopropyltriethoxysilane (MPTES) and tetraethoxysilane (TEOS) precursors in hydroalcoholic medium in the presence of a cationic surfactant as templating agent and ammonia as catalyst. These materials of approximately the same particle size and morphology featured different functionalization levels, various degrees of structural order, and variable distribution of thiol groups in the mesopores. Their reactivity in solution has been studied using Hg(II) as model analyte. Total accessibility (on a 1:1 S:Hg stoichiometry basis) was demonstrated and quantified for well-ordered materials whereas less open and less organized structures with high degrees of functionalization were subject to less-than-complete loadings. Capacities measured at pH 2 were lower than at pH 4 because of distinct mercury-binding mechanisms. Kinetics associated to the uptake process were studied by in situ electrochemical monitoring of Hg(II) consumption from aqueous suspensions containing the various adsorbents. They indicate only little difference between materials of the MCM-41 and MCM-48 series at similar functionalization levels, fast mass transport in well-ordered mesostructures in comparison to the poorly or non-ordered ones (except at pH 2 where charge formation induced some restriction in materials characterized by long-range structural order), and even faster processes in the wormlike frameworks (characterized by shorter range structural order). Hg(II) binding to thiol-functionalized materials obtained by post-synthesis grafting was found to occur more rapidly in the early beginning of the uptake process as a result of a higher concentration of binding sites at the pore entrance in comparison to the more homogeneous distribution of these groups in the mesochannels of materials obtained by co-condensation.     

Catalytic properties of Pd-containing systems based on SBA-15 molecular sieve modified with imidazolium ionic liquid

Palladium(II) ions were incorporated in SBA-15 molecular sieve modified with imidazolium-based ionic liquids. The synthesized materials were characterized using differential thermic analysis, low-temperature nitrogen adsorption, transmission electron spectroscopy and elemental analysis. The materials obtained basing on a grafted ion liquid, in 1-hexene hydrogenetion were shown to exhibit the catalytic activity significanly higher than those prepared via ion liquid adsorption on supports.     

Synchronous determination of mercury (II) and copper (II) based on quantum dots-multilayer film

A sensitive sensor for mercury (II) and copper (II) synchronous detection was established via the changed photoluminescence of CdTe quantum dots (QDs) multilayer films in this work. QDs were deposited on the quartz slides to form QDs-multilayer films by electrostatic interactions with poly(dimethyldiallyl ammonium chloride) (PDDA). Hg²⁺ or Cu²⁺ could quench the photoluminescence of the QDs-multilayer films, and glutathione (GSH) was used to remove Hg²⁺ or Cu²⁺ from QDs-multilayer films due to strong affinity of GSH-metal ions, which resulted in the recovered photoluminescence of QDs-multilayer films. There are good linear relationships between the metal ions concentration and the photoluminescence intensity of QDs in the quenched and recovered process. It was found that the Stern–Volmer constants for Hg²⁺ are higher than that for Cu²⁺. Based on different quenching and recovery constant between Hg²⁺ and Cu²⁺, the synchronous detection of Hg²⁺ and Cu²⁺ can be achieved. The linear ranges of this assay were obtained from 0.005 to 0.5 μM for Hg²⁺ and from 0.01 to 1 μM for Cu²⁺, respectively. And the artificial water samples were determined by this method with satisfactory results, the recoveries for Hg²⁺ and Cu²⁺ ions were found in the range of 90.4–106.4%. To the best of our knowledge, it is the first report about the synchronous detection of Hg²⁺ and Cu²⁺ by using quenched and recovered photoluminescence of quantum dots multilayer films.     

Electroanalytical determination of cadmium(II) and lead(II) using an in-situ bismuth film modified edge plane pyrolytic graphite electrode.

A highly sensitive and simple electroanalytical methodology is presented using an in-situ bismuth film modified edge plane pyrolytic graphite electrode (BiF-EPPGE) which is exemplified with the simultaneous determination of cadmium(II) and lead(II). Square-wave anodic stripping voltammetry is utilised with the effects of several experimental variables studied. Simultaneous additions of cadmium(II) and lead(II) were investigated where two linear ranges between 0.1-100 and 0.1-300 microg/L and also detection limits of 0.062 and 0.084 microg/L were obtained, respectively. The method was then successfully applied to the simultaneous determination of cadmium(II) and lead(II) in spiked river water, where recoveries of 100.5 and 98% were obtained, respectively. This electroanalytical protocol using edge plane pyrolytic graphite electrodes is one of the simplest methodologies to date using non-mercury based electrodes and is simpler and cheaper than alternatives such as carbon nanotube electrode arrays, suggesting the use of edge plane pyrolytic graphite electrode for routine sensing.     

Hg(II)-imprinted thiol-functionalized mesoporous sorbent micro-column preconcentration of trace mercury and determination by inductively coupled plasma optical emission spectrometry

Hg(II)-imprinting thiol-functionalized mesoporous sorbent was prepared by a sol–gel method and characterized by X-ray diffraction (XRD), FT-IR spectroscopy and nitrogen gas adsorption–desorption. The static adsorption capacity of the Hg(II)-imprinted and non-imprinted sorbent was 78.5 and 26.6 mg g⁻¹, respectively. The breakthrough capacity was 4.46 mg g⁻¹, and the relative selectivity coefficient for Hg(II) in the presence of Cd and Pb was 3.3 and 3.9, respectively. A new method using a micro-column packed with Hg(II)-imprinting thiol-functionalized mesoporous sorbent has been developed for preconcentration of trace mercury prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analyte have been investigated. The limit of detection was 0.39 ng ml⁻¹ with a concentration factor of 150 times. The developed method has been applied to the determination of trace mercury in some biological and environmental samples with satisfactory results. The accuracy was assessed through recovery experiments and analysis of certified reference material.