Application of multiwalled carbon nanotubes for solid-phase extraction of organophosphate pesticide

Multiwalled carbon nanotube (MWCNT) was developed as a new sorbent for solid-phase extraction (SPE) of organophosphate (OP) pesticides. A combination of SPE with square-wave voltammetric (SWV) analysis resulted in a fast, sensitive, and selective electrochemical method for determination of OP pesticide using methyl parathion (MP) as a representative. Because of the strong affinity of MWCNT for phosphoric group, nitroaromatic OP compounds can strongly bind to the MWCNT surface. The macroporosity and heterogeneity of MWCNT allow extracting a large amount of MP less than 5 min. The stripping response was highly linear over the MP range of 0.05–2.0 μg/mL, with a detection limit of 0.005 μg/mL. The determination of MP in garlic samples showed acceptable accuracy. The fast extraction ability of MWCNT makes it promising sorbent for various solid-phase extractions.     

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.     

An enzymeless organophosphate pesticide sensor using Au nanoparticle-decorated graphene hybrid nanosheet as solid-phase extraction

A sensitive enzymeless organophosphate pesticides (OPs) sensor is fabricated by using Au nanoparticles (AuNPs) decorated graphene nanosheets (GNs) modified glassy carbon electrode as solid phase extraction (SPE). Such a nanostructured composite film, combining the advantages of AuNPs with two dimensional GNs, dramatically facilitates the enrichment of nitroaromatic OPs onto the surface and realizes their stripping voltammetric detection of OPs by using methyl parathion (MP) as a model. The stripping voltammetric performances of captured MP were evaluated by cyclic voltammetric and square-wave voltammetric analysis. The combination of the nanoassembly of AuNPs-GNs, SPE, and stripping voltammetry provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. The stripping analysis is highly linear over the MP concentration ranges of 0.001-0.1and 0.2-1.0 μg mL⁻¹ with a detection limit of 0.6 ng mL⁻¹. This designed enzymeless sensor exhibits good reproducibility and acceptable stability.     

A Highly Efficient ZrO2 Nanoparticle Based Electrochemical Sensor for the Detection of Organophosphorus Pesticides

A sensitive electrochemical method for square‐wave voltammetric detection of organophosphate (OP) compounds was developed based on zirconia (ZrO₂) nanoparticles modified electrode. The electrode was fabricated using electrochemical deposition and characterized by scanning electron microscopy (SEM), which confirmed the successful formation of nanoparticles. Due to the strong affinity of ZrO₂ with the phosphoric group, nitroaromatic OPs can strongly bind to the surface of ZrO₂ nanoparticles (ZrO₂NPs). Under optimized operational conditions, SWV was employed for Omethoate (a model of OP compounds) detection with 5 min absorption, which showed a wide detection range from 98.5 pmol·L^?1 to 985 nmol·L^?1, with a detection limit as low as 52.5 pmol·L^?1. This electrochemical sensor has good selectivity, stability and reproducibility, and great potential in the detection of OP compounds in agriculture area.     

Ultra-preconcentration and determination of thirteen organophosphorus pesticides in water samples using solid-phase extraction followed by dispersive liquid–liquid microextraction and gas chromatography with flame photometric detection

An ultra-preconcentration technique composed of solid-phase extraction (SPE) and dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–flame photometric detection (GC–FPD) was used for determination of thirteen organophosphorus pesticides (OPPs) including phorate, diazinon, disolfotane, methyl parathion, sumithion, chlorpyrifos, malathion, fenthion, profenphose, ethion, phosalone, azinphose-methyl and co-ral in aqueous samples. The analytes were collected from large volumes of aqueous solutions (100 mL) into 100 mg of a SPE C₁₈ sorbent. The effective variables of SPE including type and volume of elution solvent, volume and flow rate of sample solution, and salt concentration were investigated and optimized. Acetone was selected as eluent in SPE and disperser solvent in DLLME and chlorobenzene was used as extraction solvent. Under the optimal conditions, the enrichment factors were between 15,160 and 21,000 and extraction recoveries were 75.8–105.0%. The linear range was 1–10,000 ng L^?1 and limits of detection (LODs) were between 0.2 and 1.5 ng L^?1. The relative standard deviations (RSDs) for 50 ng L^?1 of OPPs in water with and without an internal standard, were in the range of 1.4–7.9% (n = 5) and 4.0–11.6%, respectively. The relative recoveries of OPPs from well and farm water sat spiking levels of 25 and 250 ng L^?1 were 88–109%.     

Electrospun zirconia-embedded carbon nanofibre for high-sensitive determination of methyl parathion

Carbon nanofibers embedded with ultrafine zirconia nanoparticles (ZrO₂-CNFs) are fabricated via a new methodology. Polyvinylpyrrolidone (PVP) and polymethylmethacrylate (PMMA) binary polymers containing zirconium n-butoxide are first dissolved in dimethylformamide, and the resulting solution is electrospun and heat-treated. The tetragonal zirconia nanoparticles formed, with a size of 5 ± 2 nm in diameter, are uniformly distributed in the carbon nanofibres. Using Nafion as an additive, ZrO₂-CNFs are drop-cast onto the glassy carbon electrode (ZrO₂-CNF/GCE) and the modified electrode is then applied to detect methyl parathion (MP) using differential pulse voltammetry. Two linear relationships are found at the concentration ranges of 1 × 10^− 9–2 × 10^− 8 g/L and 2 × 10^− 8–2 × 10^− 7 g/L, with a detection limit of 3.4 × 10^− 10 g/L (S/N > 3). The electrospun-based ZrO₂-CNF is a very promising coating material for electrochemical sensing of organophosphorus compounds.     

para-Sulfonatocalix[6]arene-modified silver nanoparticles electrodeposited on glassy carbon electrode: Preparation and electrochemical sensing of methyl parathion

In this paper, a new electrochemical sensor, based on modified silver nanoparticles, was fabricated using one-step electrodeposition approach. The para-sulfonatocalix[6]arene-modified silver nanoparticles coated on glassy carbon electrode (pSC₆-Ag NPs/GCE) was characterized by attenuated total reflection IR spectroscopy (ATR-IR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), etc. The pSC₆ as the host are highly efficient to capture organophosphates (OPs), which dramatically facilitates the enrichment of nitroaromatic OPs onto the electrochemical sensor surface. The combination of the host-guest supramolecular structure and the excellent electrochemical catalytic activities of the pSC₆-Ag NPs/GCE provides a fast, simple, and sensitive electrochemical method for detecting nitroaromatic OPs. In this work, methyl parathion (MP) was used as a nitroaromatic OP model for testing the proposed sensor. In comparison with Ag NPs-modified electrode, the cathodic peak current of MP was amplified significantly. Differential pulse voltammetry was used for the simultaneous determination of MP. Under optimum conditions, the current increased linearly with the increasing concentration of MP in the range of 0.01-80 μM, with a detection limit of 4.0 nM (S/N = 3). The fabrication reproducibility and stability of the sensor is better than that of enzyme-based electrodes. The possible underlying mechanism is discussed.     

Enhancing the bioactivity of zirconium with the coating of anodized ZrO2 nanotubular arrays prepared in phosphate containing electrolyte

Bioactive zirconium oxide nanotubular arrays on zirconium alloys are prepared electrochemically in fluoride and phosphate containing electrolyte. Geometric factors of the ZrO₂ nanotubular layers, particularly the pore diameter and thickness, are affected by the electrochemical conditions, including applied potential and anodization time. Under specific sets of conditions, highly ordered ZrO₂ nanotubular arrays are formed with diameters varying from 30 nm to 75 nm and lengths varying from 2 μm to 12 μm. XPS shows that the nanotubular layer contains a significant amount of phosphate species distributed almost homogeneously over the entire tubular length. The ZrO₂ nanotubular layer formed in fluoride and phosphate containing electrolyte highly enhances the formation of bioactive hydroxyapatite coating in simulated biological fluid (SBF).     

PVP-Assisted ZrO2 coating on LiMn2O4 spinel cathode nanoparticles prepared by MnO2 nanowire templates

LiMn₂O₄ spinel nanorods prepared from nanowire MnO₂ templates were capped with polyvinyl pyrrolidone (PVP) and coated with ZrC₂O₄ precursors in aqueous solution. Upon annealing at 600 °C in air, an amorphous ZrO₂ nanoscale coating layer was obtained on the spinel nanoparticles with a particle size of <100 nm that formed from the splitting of the original spinel nanorods. The electrochemical cycling results clearly showed that nanoscale ZrO₂ coating significantly improved the rate capability and cycle life at 65 °C in spite of very high surface area of the spinel nanoparticles.     

Toward use of a nano layered double hydroxide/ammonium pyrrolidine dithiocarbamate in speciation analysis: One-step dispersive solid-phase extraction of chromium species in human biological samples

Chromium is a controversial element with an important essentiality and toxicity. Depending on its different species, its speciation analysis in bio-origin matrices is of utmost importance. Ammonium pyrrolidine dithiocarbamate (APDC) and layered double hydroxide (LDH) nanoparticles, with the purpose of combining their outstanding performances, were served to speciate chromium ions in human biological samples. The as-obtained sorbent (nano LDH-APDC) - after characterization by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), and scanning electron microscopy (SEM) - was used as a novel pH-sensitive adsorbent in an integrated one-step dispersive solid-phase extraction (I-OS-DSPE), which combines the benefits of the air-assisted microextraction and dispersive solid-phase extraction methods. An interesting feature of the nano LDH-APDC sorbent is that it is dissolved in an aqueous solution when the pH of the solution is lower than 4. Thus the analyte elution step, as required in most of the sorbent-based extraction methods, was obviated by dissolving the sorbent in an acidic solution after extraction and separation from the sample solution. The Cr(VI) ions were first extracted, while the Cr(III) ions remained in the aqueous solution. The extract was then directly injected into a flame atomic absorption spectrometer with a micro-sampling introduction system, and the concentration of the Cr(III) ions was calculated by its subtraction from the total chromium ions present. Several variables including the pH (5), type and amount of the nanosorbent used (30 mg of nano (Zn-Al) LDH-APDC), number of extraction cycles (15 times), and elution conditions (200 µL of 6.0 mol L⁻¹ HNO₃) were investigated to achieve the maximum extraction efficiency. Under the optimum experimental conditions, the limit of detection, linear range, consumptive index, and enrichment factor for the Cr(VI) ions were 2.4 μg L⁻¹, 8.0–640 μg L⁻¹, 0.24, and 42.5 ± 1, respectively. These findings suggested that nano (Zn-Al) LDH-APDC could be regarded as a promising adsorbent for an efficient speciation of the chromium species in the human hair, nail, saliva, plasma, and urine samples.     

Investigation of Iron-based Nanoparticles Action by Solid-phase Voltammetry

The electrochemical conversion of Fe₂O₃ nano-particles from the surface of carbon paste electrode was investigated by solid-phase voltammetry. Cyclic voltammetric curves of Fe₂O₃ nanoparticles transformations were recorded in direct current (first derivative) mode with a potential change at the speed of 80-90 mV/s in the potential range from -1.2 to +1.0 V. The dependence of the anodic peak of Fe₂O₃ nanoparticles on exposure time in a background electrolyte was researched and the method for identifying and quantification of solid-phase nanoparticles of Fe₂O₃ was developed. The results of determination were tested by a standard addition method.     

Determination of some benzimidazole fungicides in tomato puree by high performance liquid chromatography with SampliQ polymer SCX solid phase extraction

High performance liquid chromatography (HPLC) coupled with solid phase extraction (SPE) was optimized for extraction and quantification of two benzimidazoles fungicides (carbendazim and benomyl) in tomato puree. Results indicate that HPLC using an Agilent ZORBAX Eclipse plus C18 column (4.5 mm × 100 mm, 3.5 μm) and SPE using Agilent SampliQ SCX (55 mg, 3 mL) is an excellent combination for extraction and analysis of these compounds. Recoveries ranged from 90.0 to 95.5 percent with RSDs below 5 percent and limit of detections of 5 μg/kg.     

Flame atomic absorption spectrometry determination of trace amount of gold after separation and preconcentration onto ion-exchange polyethylenimine coated on Al2O3

The object of this work is to develop a simple and selective method for efficient extraction of Au(III) ions in aqueous solution using a new solid-phase extraction sorbent. Polyethylenimine (PEI) ion-exchange polymer was coated on alumina in the presence of NaNO₃. The method is based on sorption of Au³⁺ ions on 50 mg PEI/Al₂O₃. A solution of 0.5 M thiourea, then 1.0 M HCl effectively eluted the gold ion and then aspirated into flame atomic absorption spectroscopy (FAAS). The influence of flow rate of sample solution and eluent, the pH effect, eluent type and sorption capacity was investigated. The effects of various diverse ions for preconcentration and separation of the gold ion were investigated. Relative standard deviation of 4.0 μg mL⁻¹ of gold was 1.46% (n = 10). The detection limit was 26.2 ng L⁻¹ in original solution. The method has been applied successfully for the recovery of trace amount of Au(III) ions from water samples.     

Carbon black as successful screen-printed electrode modifier for phenolic compound detection

We report a miniaturized and disposable electrochemical sensor for phenolic compound detection. The sensor was constructed by modifying the working electrode surface of screen-printed electrode (SPE) with carbon black (CB) dispersion. This new probe showed higher sensitivity and better resistance to fouling than the bare SPE, displaying the suitability of CB as an excellent nanomodifier of SPE for phenolic compound detection. Catechol, gallic acid, caffeic acid, and tyrosol were detected by square wave voltammetry with a detection limit of 0.1 μM, 1 μM, 0.8 μM, and 2 μM, respectively. The sensor was able to selectively discriminate the mono-phenols and ortho-diphenols with rapid and easy measurement, paving the way to use a cost-effective device for quality control of foods and beverages containing phenolic compounds.     

Effect of Fluoride or Chloride Ions on the Morphology of ZrO2 Thin Film Grown in Ethylene Glycol Electrolyte by Anodization

0.3 wt % ammonium fluoride (NH₄F) or ammonium chloride (NH₄Cl) was added to ethylene glycol (EG) as an active ingredient for the formation of anodic oxide comprising of ZrO₂ nanotubes (ZNTs) by anodic oxidation of zirconium (Zr) at 20 V for 10 min. It was observed that nanotubes were successfully grown in EG/NH₄F/H₂O with aspect ratio of 144.3. Shorter tubes were formed in EG/NH₄F/H₂O₂. This could be due to higher excessive chemical etching at the tip of the tubes. When fluoride was replaced by chloride in both electrolytes, multilayered oxide resembling pyramids was observed. The pyramids have width at the bottom of 3-4 μm and the top is 1-2 μm with 10.7 μm height. Oxidation of Zr in EG/NH₄Cl/H₂O₂ was rater rapid. The multilayered structure is thought to have formed due to the re-deposition of ZrO₂ or hydrated ZrO₂ on the foil inside pores formed within the oxide layer. XRD result revealed an amorphous structure for as-anodized samples regardless of the electrolytes used for this work.     

Simple strategy for the optimization of solid-phase extraction procedures through the use of solid-liquid distribution coefficients application to the determination of aliphatic lactones in wine

A practical strategy for the optimization of solid-phase extraction (SPE) systems is presented. Critical SPE volumes (sample loaded, rinsing and elution solvent) are calculated from solid–liquid extraction coefficients and from basic bed parameters determined in simple experiments, using the Lövkist Jonsson model and other expressions derived from the general theory of chromatography. The agreement between calculated and measured volumes is satisfactory, which makes it possible to consider different sorbents and rinsing and elution solvents in the SPE optimization with a relatively low experimental effort. The strategy has been successfully applied to the optimization of a SPE method directed to the selective extraction of aliphatic lactones from wine. Six different reversed-phase sorbents were studied and the one showing maximum extraction selectivity was selected. Wine (50 ml) is extracted in a 200 mg cartridge filled with Bond Elut-ENV resins. Interferences are removed with 20 ml of methanol–water (40:60) with 1% NaHCO₃. Elution is carried out with 1.8 ml of dichloromethane. The extract is concentrated to 0.15 ml and analyzed by GC–ion trap MS. Eight odor-active aliphatic γ and δ lactones (with 8–12 C atoms) from wine are recovered (R>75%) in an extract free from wine major volatiles. Detection limits are in the 40–300 ng/l range, well below the odor detection threshold of these compounds. Linearity (r²>0.996) and precision (average R.S.D. 3.5%) are satisfactory in all cases. The levels in wine of some of these lactones (γ-octa, undeca and dodecalactones) are reported by first time and results demonstrate that can be present at concentrations above or close to their corresponding odor thresholds.     

Study of carbon nanotubes and functionalized-carbon nanotubes as substrates for flow injection solid phase extraction associated to inductively coupled plasma with ultrasonic nebulization: Application to Cd monitoring in solid environmental samples

A research was performed to evaluate the capabilities of carbon nanotubes (CNTs) and modified CNTs to serve as sorbents for preconcentrating Cd together with on-line ultrasonic nebulization (USN)-inductively coupled plasma optical emission spectrometry (ICPOES). Three different carbon nanotubes sustrates namely, carbon nanotubes (CNTs), oxidized-carbon nanotubes (ox-CNTs) and l-alanine-carbon nanotubes (ala-CNTs) were studied systematically and the main factors influencing the preconcentration and determination of Cd were examined thoroughly. The CNTs evaluated showed dissimilar adsorption behaviors leading to increasing preconcentration factors when used in the proposed on-line solid phase extraction (SPE) system as follows: CNT < ala-CNT < ox-CNT. Aiming to achieve the best analytical performance, ox-CNTs were used as they enable quantitative retention of Cd at pH 7.0 and instantaneous elution of the analyte with 10% HNO₃. Under optimal conditions, the adsorption capacity on ox-CNTs was found to be 130 μmol g^?1 and the detection limit (3σ) achieved was 1.03 μg L^? 1. The precision of the method expressed as the relative standard deviation (RSD) turned to be 3.0%. The flow injection method involving use of ox-CNTs as sorbent and USN-ICPOES for detection was successfully applied to the determination of Cd in different kinds of environmental samples.     

Preconcentration of atrazine and simazine with multiwalled carbon nanotubes as solid-phase extraction disk

A sensitive and selective preconcentration method using solid-phase extraction (SPE) disk, namely multiwalled carbon nanotubes (MWCNTs) disk, is proposed for the determination of atrazine and simazine in water samples. Atrazine and simazine were extracted on MWCNTs disk and then determined by gas chromatography–mass spectrometry (GC/MS). Several parameters on the enrichment factor of the analytes were investigated. The experimental results showed that it was possible to obtain quantitative analysis when the solution pH was 5 using 200 mL of validation solution containing 0.1 μg of triazines and 5 mL of acetone as an eluent. The maximum enrichment factors for atrazine and simazine were 3900 ± 250 and 4000 ± 110, respectively when 200 mL of sample solution volume was used. Relative standard deviations for seven determinations were 6.9% (atrazine) and 3.0% (simazine) under optimum conditions. The linear range of calibration curves were 0.1 to 1 ng mL^− 1 for each analyte with good correlation coefficients. The detection limits (3S/N) were 2.5 and 5.0 pg mL^− 1 for atrazine and simazine, respectively. The proposed method was successfully applied to the determination of atrazine and simazine in environmental water samples with high precision and accuracy.     

Non-enzymatic detection of hydrogen peroxide using a functionalized three-dimensional graphene electrode

A novel three-dimensional (3D) electrochemical sensor was developed for highly sensitive detection of hydrogen peroxide (H₂O₂). Monolithic and macroporous graphene foam grown by chemical vapor deposition (CVD) served as the electrode scaffold. Using in-situ polymerized polydopamine as the linker, the 3D electrode was functionalized with thionine molecules which can efficiently mediate the reduction of H₂O₂ at close proximity to the electrode surface. Such stable non-enzymatic sensor is able to detect H₂O₂ with a wide linear range (0.4 to 660 μM), high sensitivity (169.7 μA mM^− 1), low detection limit (80 nM), and fast response (reaching 95% of the steady current within 3 s). Furthermore, this sensor was used for real-time detection of dynamic release of H₂O₂ from live cancer cells in response to a pro-inflammatory stimulant.     

Microwave-irradiated synthesized platinum nanoparticles/carbon nanotubes for oxidative determination of trace arsenic(III)

Platinum nanoparticles/carbon nanotubes (Pt_nano/CNTs) were rapidly synthesized by microwave radiation, and applied for the oxidative determination of arsenic(III). The transmission electron microscopy (TEM) revealed the size of synthesized Pt nanoparticles with nominal diameter of 15 ± 3 nm. Pt_nano/CNTs modified glassy carbon electrode (Pt_nano/CNTs/GCE) exhibited better performance for arsenic(III) analysis than that of Pt nanoparticles modified GCE (Pt_nano/GCE) by electrochemical deposition or Pt foil electrode. Excellent reproducibility of the Pt_nano/CNTs/GCE was obtained with the relative standard deviation (RSD) of 3.5% at 20 repeated analysis of 40 μM As(III), while the RSD was 9.8% for Pt_nano/GCE under the same conditions. The limit of determination (LOD) of the Pt_nano/CNTs/GCE was 0.12 ppb, which was 1–2 orders of magnitude lower than that of Pt_nano/GCE or Pt foil electrode.