Efficient stripping voltammetric detection of organophosphate pesticides using NanoPt intercalated Ni/Al layered double hydroxides as solid-phase extraction

We developed a simple strategy for designing a sensitive electrochemical stripping voltammetric sensor for organophosphate pesticides (OPs) based on solid-phase extraction (SPE) using nanosized Pt intercalated Ni/Al layered double hydroxides (labeled as NanoPt-LDHs). By assembling NanoPt with LDHs together, the resulting NanoPt-LDHs are highly efficient to capture OPs. It dramatically facilitates the enrichment of OPs onto their surface and realizes the sensitive stripping voltammetric detection of methyl parathion (MP) as a model of OPs. The stripping analysis shows highly linear over MP concentration ranges of 0.001–0.15 and 0.3–1.0 μg mL^? 1 with a detection limit of 0.6 ng mL^–1 (S/N = 3). The combination of NanoPt, LDHs, SPE, and square-wave voltammetry (SWV) provides a fast, simple, and sensitive electrochemical method for OPs.     

Stripping voltammetric determination of platinum metals at a carbon paste electrode modified with cationic surfactants

In this contribution, a novel method is described for the determination of platinum metals. The procedure developed employs a carbon paste electrode modified in situ with cationic surfactants of the quaternary ammonium salt type. The pre-concentration step is based on a specific accumulation mechanism involving ion-pair formation; the detection being performed by cathodic scanning in the differential pulse voltammetric mode. Regarding the individual forms of platinum metals, the method has been found convenient for the determination of three heavy platinum metals in the form of Pt(IV), Ir(III) and Os(IV), whereas for the remaining elements (Ru, Rh, and Pd) was almost inapplicable. Platinum metals of the former group can be pre-concentrated in chloride-containing supporting media via PtCl₆²⁻, IrCl₆³⁻ and OsCl₆²⁻ complex anions, the central atom of each species being fairly reducible during the voltammetric scan. Stripping signals for both platinum and iridium were proportional to the concentration in a range of 1-10 × 10⁻⁶ M Pt(IV) and Ir(III); the response for osmium being linear within 0.1-6 × 10⁻⁷ M Os(IV) with a detection limit of about 5 × 10⁻⁹ mol l⁻¹. During optimisation, special attention was paid to the accumulation mechanism, choice of key experimental conditions, and to interference effects from foreign ions with potentially ion-pairing capabilities (AuCl₄⁻, TlCl₄⁻, CrO₄²⁻, MnO₄⁻, SCN⁻, and I⁻). The method elaborated has been tested on both model solutions and real samples of industrial waste water, showing in both cases satisfactory analytical performance.     

Determination of organophosphate pesticides using an acetylcholinesterase-based biosensor based on a boron-doped diamond electrode modified with gold nanoparticles and carbon spheres

We report on a biosensor for organophosphate pesticides (OPs) by exploiting their inhibitory effect on the activity of acetylcholinesterase (AChE). A boron-doped diamond (BDD) electrode was modified with a nanocomposite prepared from carbon spheres (CSs; with an average diameter of 500 nm) that were synthesized from resorcinol and formaldehyde, and then were coated with gold nanoparticles (AuNPs) by chemically growing them of the CSs. Compared to a bare BDD electrode, the electron transfer resistance is lower on this new electrode. Compared to an electrode without Au-NPs, the peak potential is negatively shifted by 42 mV, and the peak current is increased by 55 %. This is ascribed to the larger surface in the AuNP-CS nanocomposite which improves the adsorption of AChE, enhances its activity, and facilitates electrocatalysis. Under optimum conditions, the inhibitory effect of chlorpyrifos is linearly related to the negative log of its concentration in the 10^?11 to 10^?7 M range, with a detection limit of 1.3?×?10^?13 M. For methyl parathion, the inhibition effect is linear in the 10^?12 to 10^?6 M range, and the detection limit is 4.9?×?10^?13 M. The biosensor exhibits good precision and acceptable operational and temporal stability.

Selectivity of voltammetric determination at an ion-exchanger modified electrode

An expression of the selectivity value for the voltammetric determination of an ionic analyte in the presence of interfering component(s) at an electrode chemically modified with an ion-exchanger has been developed and applied to the analysis of a model metal-ion mixture. Using distribution coefficient values, the predicted selectivity value was calculated and compared with that obtained experimentally. The approach allows a choice of the ion-exchange resin and experimental conditions for a given analytical task.     

Stripping voltammetric determination of mercury(II) at antimony-coated carbon paste electrode

A new procedure was elaborated to determine mercury(II) using an anodic stripping square-wave voltammetry at the antimony film carbon paste electrode (SbF-CPE). In highly acidic medium of 1 M hydrochloric acid, voltammetric measurements can be realized in a wide potential window. Presence of cadmium(II) allows to separate peaks of Hg(II) and Sb(III) and apparently catalyses reoxidation of electrolytically accumulated mercury, thus allowing its determination at ppb levels. Calibration dependence was linear up to 100 ppb Hg with a detection limit of 1.3 ppb. Applicability of the method was tested on the real river water sample.     

Electrochemical oxidation determination and voltammetric behaviour of 4-nitrophenol based on Cu2O nanoparticles modified glassy carbon electrode

Cu₂O nanoparticles (nano-Cu₂O) modified glassy carbon electrode (GCE) was fabricated and used to investigate the electrochemical behaviour of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), chronoamperometry (CA), chronocoulometry (CC) and differential pulse voltammetry (DPV). Compared with GCE, a remarkable increase in oxidation peak current was observed. It indicates that nano-Cu₂O exhibits remarkable enhancement effect on the electrochemical oxidation of 4-NP. Under the optimised experimental conditions, the oxidation peak currents were propotional to 4-NP concentration in the range from 1.0?×?10^?6 to 4.0?×?10^?4?mol?L^?1 with a detection limit of 5.0?×?10^?7?mol?L^?1 (S/N?=?3). The fabricated electrode presented good repeatability, stability and anti-interference. Finally, the proposed method was applied to determine 4-NP in water samples. The recoveries for these samples were from 94.60% to 105.5%.     

Stripping voltammetric determination of lead using a glassy-carbon electrode system

The effect of the electrochemical pretreatment of the surface of a glassy-carbon indicator electrode on the electrode response and the repeatability of measurements in the stripping voltammetric determination of lead was studied. It was shown that the analytical signal depends on the nature of an electrolyte used for the pretreatment. The electrolytes that gave the most satisfactory results in the pretreatment were proposed     

Electromembrane extraction and anodic stripping voltammetric determination of mercury(II) using a glassy carbon electrode modified with gold nanoparticles

This study presents a method for the selective determination of Hg(II) using electromembrane extraction (EME), followed by square wave anodic stripping voltammetry (SWASV), using a gold nanoparticle-modified glassy carbon electrode, (AuNP/GCE). By applying an electrical potential of typically 60 V for 12 min through a thin supported liquid membrane (1-octanol), Hg(II) ions are extracted from a donor phase (i.e., the sample solution) to an acidic acceptor solution (15 μL) placed in the lumen of a hollow fiber. The influences of experimental parameters during EME were optimized using face-centered central composite design. The calibration plot, established at a working voltage of 0.55 V (vs. Ag/AgCl), extends from 0.2 to 10 μg^.L^?1 of Hg(II). The limit of detection, at a signal to noise ratio of 3, is 0.01 μg^.L^?1 and the relative standard deviations (for 5 replicate determinations at 3 concentration levels) are between 7.5 and 8.7 %. The method was successfully applied to the determination of Hg(II) in spiked real water samples to give recoveries ranging from 89 to 97 %. The results were validated by cold vapor atomic absorption spectroscopy.

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Graphical abstract Hg(II) ions were extracted from a donor phase into an acidic acceptor phase (15 μL) placed in the lumen of a hollow fiber using electromembrane extraction. The acceptor phase was then analyzed using anodic stripping voltammetry.

     

Cathodic stripping voltammetric determination of anti-cancer medicine nitrocaphanum at nafion modified electrode

An electrochemical method for the determination of anti-cancer medicine nitrocaphanum was described. The reaction mechanism of nitrocaphanum at Nafion CME was also discussed. It was found, in pH 2.5 medium, a linear response was observed for nitrocaphanum in the concentration range of 2.2 × 10^–8 M to 1.3 × 10^–6 M. Detection limit of this method is 5 × 10^–9 M, relative standard deviation for 10 measurements is 1.7%. The results of nitrocaphanum determination in real samples were satisfactory.     

Simultaneous determination of pyrethroid,organophosphate, and organochlorine pesticides in fish tissue using tandem solid-phase extraction clean-up

A method was developed for the simultaneous analysis of pyrethroid, organophosphate, and organochlorine pesticides in fish tissue. Different extraction solvents and solid-phase extraction clean-up procedures were tested. The best approach was to extract by sonication with acetonitrile and 10%?methanol, followed by clean-up of extracts using C₁₈, Florisil and Na₂SO₄ tandem solid-phase extraction cartridges. Gas chromatography with an electron-capture detector was used for analyte determination. All 26 target pesticides were detected using the new method in a single analytical run. The method detection limits ranged from 0.13 to 1.40?µg/kg, while recoveries of the analytes ranged from 86.1 to 133.8%?with relative standard deviations?≤12.1%?at a spiked concentration of 5?µg/kg. The method was developed to assess possible pesticide contamination in fish collected from lakes at a proposed Illinois National Guard Armory site.     

Polymeric sorbents modified with gold and silver nanoparticles for solid-phase extraction of proteins followed by MALDI-TOF analysis

The authors describe four different kinds of sorbents for solid-phase extraction (SPE) and preconcentration of proteins from complex samples. All are based on the use of a poly(glycidyl-co-ethylene dimethacrylate) host monolith that was chemically functionalized by using two different ligands (ammonia and cysteamine). Gold nanoparticles (AuNPs) or silver NPs were then assembled to the amino or thiol groups. The resulting materials are shown to be viable stationary phases for use in SPE cartridges. The sorbents can selectively retain bovine serum albumin, and the thiol-modified sorbents containing AuNPs and AgNPs provide the highest recoveries (>90%) and satisfactory loading capacities (29.3 and 17.6 μg?mg^?1 of sorbent, respectively). The applicability of these nanosorbents was demonstrated by preconcentrating viscotoxins from mistletoe extracts. The enriched fractions were subjected to MALDI-TOF analysis to underpin their selectivity.

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Graphical abstract Hybrid materials based on methacrylate polymers modified with gold or silver nanoparticles were used as sorbents for solid phase extraction and preconcentration of bovine serum albumin and mistletoe viscotoxins, this followed by MALDI-TOF analysis.

     

Sensitive voltammetric determination of baicalein at DNA Langmuir-Blodgett film modified glassy carbon electrode

The present paper describes to modify a double stranded DNA-octadecylamine (ODA) Langmuir-Blodgett film on a glassy carbon electrode (GCE) surface to develop a voltammetric sensor for the detection of trace amounts of baicalein. The electrode was characterized by atomic force microscopy (AFM) and cyclic voltammetry (CV). Electrochemical behaviour of baicalein at the modified electrode had been investigated in pH 2.87 Britton-Robinson buffer solutions by CV and square wave voltammetry (SWV). Compared with bare GCE, the electrode presented an electrocatalytic redox for baicalein. Under the optimum conditions, the modified electrode showed a linear voltammetric response for the baicalein within a concentration range of 1.0 × 10⁻⁸-2.0 × 10⁻⁶ mol L⁻¹, and a value of 6.0 × 10⁻⁹ mol L⁻¹ was calculated for the detection limit. And the modified electrode exhibited an excellent immunity from epinephrine, dopamine, glucose and ascorbic acid interference. The method was also applied successfully to detect baicalein in the medicinal tablets and spiked human blood serum samples with satisfactory results.     

Sensitive voltammetric determination of rutin at an ionic liquid modified carbon paste electrode

An ionic liquid modified carbon paste electrode (IL/CPE) had been fabricated by using hydrophilic ionic liquid 1-amyl-3-methylimidazolium bromide ([AMIM]Br) as a modifier. The IL/CPE was characterized by scanning electron microscope and voltammetry. Electrochemical behavior of rutin at the IL/CPE had been investigated in pH 3.29 Britton-Robinson (B-R) buffer solution by cyclic voltammetry (CV) and square wave voltammetry (SWV). The experimental results suggested that the modified electrode exhibited an electrocatalytic activity toward the redox of rutin. The electron transfer coefficient (α) and the standard rate constant (k_s) of rutin at the modified electrode were calculated. Under the selected conditions, the reduction peak current was linearly dependent on the concentration of rutin in the range of 4.0 × 10⁻⁸ to 1.0 × 10⁻⁵ mol L⁻¹ (r = 0.9998), with a detection limit of 1.0 × 10⁻⁸ mol L⁻¹ (S/N = 3). The relative standard deviation (R.S.D.) for six times successful determination of 8.0 × 10⁻⁷ mol L⁻¹ rutin was 1.2%. The proposed method was applied to determine rutin in tablet and urine sample. In addition, the IL/CPE exhibited a distinct advantage of simple preparation, surface renewal, good reproducibility and good stability.     

Electrochemical behaviors of ofloxacin and its voltammetric determination at carbon nanotubes film modified electrode

A multi-wall carbon nanotubes (MWNTs)-Nafion film-coated glassy carbon electrode (GCE) was fabricated and the electrochemical behavior of ofloxacin on the MWNTs-Nafion film-coated GCE were investigated by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The oxidation peak current of ofloxacin increased significantly on the MWNTs-Nafion film modified GCE compared with that using a bare GCE. This nano-structured film electrode exhibited excellent enhancement effects on the electrochemical oxidation of ofloxacin. A well-defined oxidation peak attributed to ofloxacin was observed at 0.97 V and was applied to the determination of ofloxacin. The oxidation peak current was proportional to ofloxacin concentration in the ranges 1.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/L and 1.0 × 10⁻⁶ to 2.0 × 10⁻⁵ mol/L. A detection limit of 8.0 × 10⁻⁹ mol/L was obtained for 400 s accumulation at open circuit (S/N = 3). This method for the detection of ofloxacin in human urine was satisfactory. __________ Translated from Chinese Journal of Applied Chemistry, 2007, 24(5): 540–545 [译自: 应用化学]     

Magnetic solid-phase extraction of rose bengal using iron oxide nanoparticles modified with cetyltrimethylammonium bromide

Magnetic solid phase extraction (MSPE) based on cetyltrimethylammonium bromide (CTAB)-coated magnetic iron oxide nanoparticles (C-MIONPs) was investigated for the separation, preconcentration and determination of Rose Bengal (RB) in aqueous solutions. The influences of different analytical parameters such as pH, temperature, ionic strength, volume of desorbent solvent, amount of adsorbent and interfering ions in the adsorption of RB on C-MIONPs were investigated. The RB adsorption on C-MIONPs follows Langmuir isotherm. The sizes of C-MIONPs were in the range of 20–80 nm. The method was capable of determining RB concentration in the range of 0.01–1.20 μg ml^?1. The limit of detection (LOD) of RB based on three times the standard deviation of the blank (3Sb) was found to be 5.91 × 10–3 μg ml^?1 (n = 8). The relative standard deviation (RSD) for 0.3 μg ml^?1 and 0.8 μg ml^?1 of RB were 4.1% and 1.1%, respectively. The proposed method was applied to the determination of RB in Brucella Antigen solution and water samples from the Karoon River.     

Sensitive voltammetric determination of xanthinol nicotinate at a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of xanthinol nicotinate(Xan) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes(MWNTs) and room-temperature ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate(BMTMPF_6).The modified electrode exhibited good promotion to the electrochemical oxidation of Xan and an ultrasensitive electrochemical method was proposed for the determination of Xan.This method was successfully applied to the determination of...     

Sensitive voltammetric detection of clomipramine at 16-mercapto-hexadecanoic acid self-assembled monolayer modified gold electrode

Clomipramine, an effective and important antipsychotic drug with low redox activity and poor hydrophilicity, was found to effectively accumulate on hydrophobic 16-mercaptohexadecanoic acid (i.e. MHA) self-assembled monolayer (SAM) modified gold electrode (i.e. MHA/Au) and generating a sensitive anodic peak at about 0.86 V (vs. SCE) in 0.05 M Tris–HCl (pH = 8.1) buffer solution. Thus, quantitative measurement of clomipramine was established with high sensitivity under optimum conditions. The anodic peak current was linear to clomipramine concentration in the range from 1 × 10⁻⁶ to 5 × 10⁻⁵ M, with a detection limit of 6 × 10⁻⁹ M. This method was successfully applied to the detection of clomipramine in drug tablets and proved to be reliable compared to UV. The spectral features, electrochemical characteristics and wettability of MHA-SAM were also studied. Correspondence: Jilie Kong, Department of Chemistry, Fudan University, Shanghai 200433, P.R. China     

Preconcentration and voltammetric determination of trace myoglobin at a 6-mercaptopurine modified silver electrode

6-Mercaptopurine(6-MP) is covalently modified onto a silver electrode to construct a chemically modified electrode (CME). It exhibits the capability of selectively complexing myoglobin and can be applied as a selective biosensor for this compound. Myoglobin is accumulated onto the CME at 0.32 V (vs. SCE); after exchanging the medium it is determined by differential pulse stripping voltammetry. A cathodic stripping peak is obtained at 0.15 V (vs. SCE) by scanning the potential from 0.35 to –0.1 V. The peak currents are linearly proportional to the concentration of myoglobin in the range of 0.2 ～ 4 μg/mL with a relative standard deviation of 7.8%. The detection limit is about 0.1 μg/mL. The mechanism of the complexation is also discussed.     

Magnetic nanoparticles modified with polydimethylsiloxane and multi-walled carbon nanotubes for solid-phase extraction of fluoroquinolones

We have surface-functionalized magnetic particles (MPs) with polydimethylsiloxane and multi-walled carbon nanotubes in a two-step reaction. The MPs were applied to solid-phase extraction of the fluoroquinolones ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin prior to their determination by capillary liquid chromatography. The effects of sample pH, adsorption time, type of eluent, desorption time and desorption temperature were investigated. Under the optimum conditions, the extraction efficiencies are in the range from 81.5?% to 94.1?%, with relative standard deviations (RSDs) of <7.6?%. The detection limits vary from 0.24 to 0.48?ng?mL^?1. The method was applied to the analysis of spiked mineral water and honey. The recoveries for the fluoroquinolones in the real samples range from 84.0?% to 112?%, with RSDs ranging from 2.9?% to 7.8?%.