Gold nanoparticles decorated carbon fiber mat as a novel sensing platform for sensitive detection of Hg(II)

The three-dimensional fibril-like carbon fiber mat electrode (CFME) decorated with Au nanoparticles (AuNPs) was employed to construct Hg(II) sensing platform for the first time. The highly porous feature of CFME combining the high affinity of AuNPs for mercury endowed the sensing platform with high sensitivity and good reproducibility. Under optimal conditions, the prepared AuNPs/CFME was capable of sensing Hg(II) with a detection limit of 0.1 μg L^− 1 (S/N = 3) using differential pulse anodic stripping voltammetry (DPASV). Finally, the AuNPs/CFME was successfully demonstrated for the determination of Hg(II) in real water samples with satisfactory results.     

Silver particle-decorated carbon paste electrode based on ionic liquid for improved determination of nitrite

A simple silver particle-modified carbon paste electrode is proposed for the determination of low concentration levels of nitrite ions. The electrode consists of a carbon powder decorated with silver sub-micrometre particles (AgPs) and a hydrophobic ionic liquid trihexyltetradecylphosphonium chloride as a binder. It has been shown that AgPs exhibit a strong electrocatalytic effect on the nitrite oxidation. For optimal electroanalytical performance the electrode was conditioned via silver oxidation/reduction cycle. The electrode revealed a linear square-wave voltammetric response in a wide examined concentration range of 0.05 to 1.0 mmol L^− 1, limit of detection (LOD) of 3 μmol L^− 1 and excellent repeatability with RSD of 0.3%.     

Green and facile electrode modification by spark discharge: Bismuth oxide-screen printed electrodes for the screening of ultra-trace Cd(II) and Pb(II)

We report that highly effective electrode modification can be achieved by sparking process between a flat electrode substrate and a tip counter electrode. The concept is introduced by the development of Bi₂O₃-modified graphite screen printed electrodes (SPEs). SPEs were sparked with a bismuth wire at 1.2 kV under atmospheric conditions. The effect of polarity on the morphology of the sensing surface, bismuth loading and the sensitivity of the resulting sensors for the simultaneous anodic stripping voltammetric determination of Cd(II) and Pb(II) was investigated. Compared with electroplated and various bismuth precursors bulk-modified SPEs, the developed sparked electrodes exhibited considerably lower limit of detection (0.2 μg L^− 1, S/N = 3) for each target ion. Therefore, sparking technique offers a facile and green approach for the development of highly sensitive bismuth-based electrodes, and a wide-scope of applicability in the development of metal-modified sensing surfaces.     

Electrochemical stripping analysis of cadmium on tantalum electrode

A tantalum electrode is reported as an alternative electrode for electrochemical stripping analysis for the first time. Several key operational parameters that influenced the electroanalytical signals were optimized, such as pH of the electrolyte, deposition potential and deposition time. The tantalum electrode yields well-defined and sharp stripping signals for trace cadmium analysis when combined with differential pulse anodic stripping voltammetry. Under the optimized condition the electrode shows good linear behavior in the examined concentration in the range of 20–200 μg L^?1 for cadmium, with a detection limit (3σ) of 0.57 μg L^?1 followed a 5-min deposition step under ? 1.3 V. It also shows good reproducibility with a relative standard deviation of 2.56% for ten consecutive measurements. The sensor was also employed for real sample determination and exhibited excellent performance compared with the result of inductively coupled plasma-mass spectrometry.     

Mesoporous silica thin films for molecular sieving and electrode surface protection against biofouling

Electrode fouling is a major challenge for the long term use of sensors in real samples as it leads to the decay of the electroanalytical signal and is often caused by the formation of an inhibiting layer formed by biomolecules. We demonstrate here that ordered and vertically aligned mesoporous silica generated at the surface of an indium tin oxide electrode by electrochemically assisted self-assembly act as a molecular sieve and a protective layer for the electrode surface. They indeed prevent the adsorption of size excluded large undesired molecules (e.g. haemoglobin) while allowing the detection of small redox active molecules likely to reach the electrode surface through the film (e.g. propranolol) with almost no loss of sensitivity. At a bare electrode, the oxidation of propranolol is completely inhibited in the presence of 5 μM haemoglobin. At a modified electrode, the sensitivity for propranolol in the absence of haemoglobin is (72.8 ± 2.9) mA mol^− 1 (R² = 0.992, N = 7) and it remains similar in the presence of 5 μM haemoglobin with a value of (67.4 ± 7.2) mA mol^− 1 (R² = 0.992, N = 7).     

Flow injection analysis system with electrochemical detection for the simultaneous determination of nanomolar levels of acetaminophen and codeine

A simple, rapid and low-cost electroanalytical method is proposed for the determination of acetaminophen (ACP) and codeine (COD) at nanomolar levels in pharmaceutical and biological samples. The analytical procedure is based on a flow injection analysis system coupled to electrochemical detection, which was multiple pulse amperometry (FIA-MPA). Boron-doped diamond was used as the working electrode for electrochemical detection. The electrode was subjected to a cathodic pretreatment and was selected in this work due its good electrochemical performance. By applying the FIA-MPA method, after a number of optimization assays, the analgesics were simultaneously determined at excellent linear concentration ranges. The analytical curves ranged from 80 nmol L⁻¹ to 100 µmol L⁻¹ for ACP and from 50 nmol L⁻¹ to 10 µmol L⁻¹ for COD, and the obtained limits of detection were 30 nmol L⁻¹ and 35 nmol L⁻¹ for ACP and COD, respectively. The practical applicability of the electroanalytical method was evaluated from the ACP and COD determination in two sample matrices: commercial pharmaceutical samples and biological fluids. In the case of pharmaceutical formulation samples, the obtained results were statistically similar to those obtained using a reference chromatographic method. In addition, these drugs were simultaneously quantified in biological fluid samples of urine and human serum with excellent recovery percentages.     

Determination of lead,cadmium and mercury in blood for assessment of environmental exposure: A comparison between inductively coupled plasma–mass spectrometry and atomic absorption spectrometry

A biomonitoring method for the determination of Pb, Cd, and Hg at background levels in whole blood by inductively coupled plasma-mass spectrometry is described. While this method was optimized for assessing Pb, Cd and Hg at environmental levels, it also proved suitable for assessing concentrations associated with occupational exposure. The method requires as little as 200 μl of blood that is diluted 1 + 49 for direct analysis in the inductively coupled plasma-mass spectrometer. Method performance is compared to well-established AAS methods. Initial method validation was accomplished using National Institute of Standards and Technology (NIST) Standard Reference Material 966, Toxic Metals in Bovine Blood. Method detection limits (3s) are 0.05 μg dl^− 1 for Pb, 0.09 μg l^− 1 for Cd; and 0.17 μg l^− 1 for Hg. Repeatability ranged from 1.4% to 2.8% for Pb; 3% to 10% for Cd; and 2.6% to 8.8% for Hg. In contrast, AAS method detection limits were 1 μg dl^− 1, 0.54 μg l^− 1, and 0.6 μg l^− 1, for Pb, Cd, and Hg, respectively. Further performance assessments were conducted over a 2-year period via participation in four international External Quality Assessment Schemes (EQAS) operated specifically for toxic metals in blood. This includes schemes operated by (a) the New York State Department of Health's Wadsworth Center, Albany, NY, USA (b) L′Institut National de Santé Publique du Québec, Centre de Toxicologie du Québec, Canada, (c) Friedrich-Alexander University, Erlangen, Germany, and (d) the University of Surrey, Guildford, UK Trace Elements scheme. The EQAS data reflect analytical performance for blind samples analyzed independently by both inductively coupled plasma-mass spectrometry and AAS methods.     

Thermodynamic and isotherm studies of the biosorption of Cu(II), Pb(II), and Zn(II) by leaves of saltbush (Atriplex canescens)

The Freundlich and Langmuir isotherms were used to describe the biosorption of Cu(II), Pb(II), and Zn(II) onto the saltbush leaves biomass at 297 K and pH 5.0. The correlation coefficients (R²) obtained from the Freundlich model were 0.9798, 0.9575, and 0.9963 for Cu, Pb, and Zn, respectively, while for the Langmuir model the R² values for the same metals were 0.0001, 0.1380, and 0.0088, respectively. This suggests that saltbush leaves biomass sorbed the three metals following the Freundlich model (R² > 0.9575). The K_F values obtained from the Freundlich model (175.5 · 10⁻², 10.5 · 10⁻², and 6.32 · 10⁻² mol · g⁻¹ for Pb, Zn, and Cu, respectively), suggest that the metal binding affinity was in the order Pb > Zn > Cu. The experimental values of the maximal adsorption capacities of saltbush leaves biomass were 0.13 · 10⁻², 0.05 · 10⁻², and 0.107 · 10⁻² mol · g⁻¹ for Pb, Zn, and Cu, respectively. The negative ΔG^∘ values for Pb and the positive values for Cu and Zn indicate that the Pb biosorption by saltbush biomass was a spontaneous process.     

Zirconium(IV) phosphosulphosalicylate-based ion selective membrane electrode for potentiometric determination of Pb(II) ions

Zirconium(IV) phosphosulphosalicylate, a cation exchanger was synthesized by mixing zirconium oxychloride to a mixture of 5-sulphosalicylic acid and phosphoric acid. The material showed good efficiency for the preparation of an ion-selective membrane electrode. The membrane was characterized affinity for Pb(II) ions. Due to its Pb(II) selective nature, the ion-exchanger was used as an electroactive by XRD and SEM analysis. The electrode responds to Pb(II) ions in a linear range from 1 × 10⁻⁵ to 1 × 10⁻¹ M with a slope of 43.8 mV per decade change in concentration with detection limit of 4.78 × 10⁻⁶ M. The life span of electrode was found to be 90 days. The proposed electrode showed satisfactory performance over a pH range of 4.0–6.5, with a fast response time of 15 s. The sensor has been applied to the determination of Pb(II) ions in water samples of different origins. It has also been used as indicator electrode in potentiometric titration of Pb(II) ion with EDTA.     

Study on the solid phase extraction and spectrophotometric determination of cobalt with 5-(2-benzothiazolylazo)-8-hydroxyquinolene

A highly sensitive, selective and rapid method for the determination of cobalt based on the rapid reaction of cobalt(II) with 5-(2-benzothiazolylazo)-8-hydroxyquinolene BTAHQ and the solid phase extraction of the Co(II)-BTAHQ complex with C18 membrane disks were developed. In the presence of pH = 6.4 buffer solution and cetylpyridenium chloride (CPC) medium, BTAHQ reacts with cobalt to form a deep violet complex with a molar ratio of 1:1 (cobalt to BTAHQ). This complex was enriched by the solid phase extraction with C18 membrane disks. An enrichment factor of 100 was obtained by elution of the complex from the disks with a minimal amount of isopentyl alcohol. In isopentyl alcohol medium, the molar absorptivity of the complex is 2.42 × 10⁵ L mol⁻¹ cm⁻¹ at 658 nm. Beer’s law is obeyed in the range of 0.01–0.38 μg mL⁻¹ in the measured solution. The relative standard deviation for 11 replicate samples of 0.20 μg mL⁻¹ level is 1.37%. The detection and quantification limits reach 3.1 and 9.7 ng mL⁻¹ in the original samples. This method was applied for the determination of cobalt in biological, water, soil and pharmaceutical preparation samples with good results.     

Gold nanoparticles/tetraaminophenyl porphyrin functionalized multiwalled carbon nanotubes nanocomposites modified glassy carbon electrode for the simultaneous determination of p-acetaminophen and p-aminophenol

A novel electrochemical platform was designed and prepared for simultaneous determination of p-acetaminophen (AMP) and p-aminophenol (AP) by combining the excellent conductivity and electrocatalytic activities of tetraaminophenyl porphyrin functionalized multi-walled carbon nanotubes (CNTs-CONH-TAPP) and gold nanoparticles (AuNPs). The as-synthesized CNTs-CONH-TAPP composites were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscope. The incisive oxidation current responses of AMP and AP at the modified electrode promised a sensitive and selective simultaneous determination of AMP and AP. Under optimized conditions, the peak currents were directly proportional to the concentrations of AMP and AP over the ranges of 4.5–500 μmol L⁻¹ and 0.08–60 μmol L⁻¹, respectively, and the limits of detection were 0.44 μmol L⁻¹ for AMP and 0.025 μmol L⁻¹ for AP(S/N = 3) respectively. The proposed modified electrode showed excellent selectivity, reproducibility and long-term stability and could be applied in simultaneous determination of p-acetaminophen and p-aminophenol in real samples.     

Simultaneous determination of ascorbic acid,epinephrine, and uric acid by differential pulse voltammetry using poly(p-xylenolsulfonephthalein) modified glassy carbon electrode

A novel poly(p-xylenolsulfonephthalein) modified glassy carbon electrode was prepared for the simultaneous determination of ascorbic acid (AA), epinephrine (EP) and uric acid (UA). Cyclic voltammetric, chronoamperometric, and differential pulse voltammetric methods were used to investigate the modified electrode for the electrocatalytic oxidation of EP, AA, and UA in aqueous solutions. The separation of the oxidation peak potentials for AA–EP and EP–UA was about 200 and 130 mV, respectively. The calibration curves obtained for AA, EP, and UA were in the ranges of 10–1343, 2–390, and 0.1–560 μmol L⁻¹, respectively. The detection limits (S/N = 3) were 4, 0.1, and 0.08 μmol L⁻¹ for AA, EP and UA, respectively. The diffusion coefficient and the catalytic rate constant for the oxidation of EP at the modified electrode were calculated as 1.40(±0.10) × 10⁻⁴ cm² s⁻¹ and 1.06 × 10³ mol⁻¹ L s⁻¹, respectively. The present method was applied to the determination of EP in pharmaceutical and urine samples, AA in commercially available vitamin C tablet, and EP plus UA in urine samples.     

Dual-signal anodic stripping voltammetric determination of trace arsenic(III) at a glassy carbon electrode modified with internal-electrolysis deposited gold nanoparticles

A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPs_ied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPs_ied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl₄ and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H₂SO₄, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L^− 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L^− 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.     

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent — Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (II) was then eluted with 10% HNO₃ and subsequently reduced by NaBH₄ to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min^− 1 sample loading rate. The detection limit was 0.2 ng L^− 1 and much lower than that of conventional method (around 15.8 ng L^− 1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L^− 1 of Hg and the linear working curve is from 20 to 2000 ng L^− 1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.     

Development of a headspace-gas chromatography (HS-GC-PID-FID) method for the determination of VOCs in environmental aqueous matrices: Optimization,verification and elimination of matrix effect and VOC distribution on the Fortaleza Coast,Brazil

An analytical protocol combining a headspace technique with gas chromatography and detection by photoionization detector and flame ionization detector (HS-GC-PID-FID) was developed. This procedure was used to measure volatile organic compounds (VOCs) in environmental aqueous matrices and was applied in determination of VOCs on the coast of Fortaleza, Brazil. At optimum operating conditions, analytical figures of merit such as linearity (R ranged from 0.9983 to 0.9993), repeatability (5.62 to 9.63% and 0.02 to 0.19% for the quantitative and qualitative analyses, respectively), detection limits (0.22 to 7.48 μg L⁻¹) and sensibility were estimated. This protocol favors a fast sampling/sample preparation (in situ), minimizes the use of laboratory material, eliminates the matrix effect from environmental samples, and can be applied to river, estuarine and oceanic waters. The advantage of detectors in series is that a low sensitivity in detection in one is compensated by the other. Toluene was the most abundant VOC in the studied area, with an average concentration of 1.63 μg L⁻¹. It was followed by o-xylene (1.15 μg L⁻¹), trichloroethene (1.08 μg L⁻¹), benzene (0.86 μg L⁻¹), ethylbenzene (0.74 μg L⁻¹), carbon tetrachloride (0.55 μg L⁻¹), m/p-xylene (0.48 μg L⁻¹) and tetrachloroethene (0.46 μg L⁻¹), compounds which are very commonly detected in urban runoff from most cities. The results of the VOC distribution showed that port activity was not the main source of VOCs along the Fortaleza Coast, but that the contribution from urban runoff seemed more significant.     

Voltammetric determination of tert-butylhydroquinone in biodiesel using a carbon paste electrode in the presence of surfactant

This paper reports an electroanalytical method developed for determining the antioxidant tert-butylhydroquinone (TBHQ) in biodiesel, based on the enhancement effect of cetyltrimethylammonium bromide (CTAB). In pH 6.5 Britton–Robinson buffer, a poorly defined oxidation peak was observed for TBHQ at a carbon paste electrode (CPE). In the presence of low concentrations of CTAB, however, the oxidation peak current was markedly increased. Several parameters were studied and optimized for the development of this methodology, and under optimal conditions the oxidation peak current was proportional to TBHQ concentration in the range of (1.05–10.15) × 10⁻⁶ mol L⁻¹, with limits of detection and quantification of 7.11 × 10⁻⁸ mol L⁻¹ and 2.37 × 10⁻⁷ mol L⁻¹, respectively, by linear sweep voltammetry (LSV). The method was applied to TBHQ determination in soybean biodiesel samples. The results were satisfactory in comparison with those obtained using high-performance liquid chromatography (HPLC).     

Microwave-radiated synthesis of gold nanoparticles/carbon nanotubes composites and its application to voltammetric detection of trace mercury(II)

Gold nanoparticles/carbon nanotubes (Au-NPs/CNTs) composites were rapidly synthesized by microwave radiation, and firstly applied for the determination of trace mercury(II) by anodic stripping voltammetry (ASV). The structure and composition of the synthesized Au-NPs/CNTs nanocomposites were characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), UV–vis absorption spectroscopy and cyclic voltammetry. Au-NPs/CNTs nanocomposites modified glassy carbon electrode (Au-NPs/CNTs/GCE) exhibited excellent performance for Hg(II) analysis. A wide linear range (5 × 10⁻¹⁰–1.25 × 10⁻⁶ mol/L) and good repeatability (relative standard deviation of 1.84%) were obtained for Hg(II) detection. The limit of detection was found to be 3 × 10⁻¹⁰ mol/L (0.06 μg/L) at 2 min accumulation, while the World Health Organization’s guideline value of mercury for drinking water is 1 μg/L, suggesting the proposed method may have practical utility.     

Synthesis and reactions of heterodinuclear organopalladium–cobalt complexes acting as copolymerization catalyst for aziridine and carbon monoxide

A series of heterodinuclear acylpalladium–cobalt complexes having a bidentate nitrogen ligand, L₂(RCO)Pd–Co(CO)₄ (L₂ = bpy, R = Me (5), Ph (6); L₂ = tmeda, R = Me (7), Ph (8); L₂ = phen, R = Me (9), Ph (10)) are prepared by metathetical reactions of PdRIL₂ with Na⁺[Co(CO)₄]⁻ followed by treatment with CO. These complexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 6, 8, and 9 are determined by X-ray structure analysis. Geometry at Pd is essentially square planar and the Co atom is considered to have d¹⁰ tetrahedral structure, where cobalt(-I) anion coordinates to palladium(II) cation. Heterodinuclear organopalladium–cobalt complexes are shown to catalyze copolymerization of aziridines and CO under mild conditions. Reaction of (dppe)MePd–Co(CO)₄ (1) with aziridine gives a cationic (aziridine)palladium(II) complex with [Co(CO)₄]⁻ anion, [PdMe(aziridine)(dppe)]⁺[Co(CO)₄]⁻ (13).     

Micro-electrodeposition in the presence of ionic liquid for the preconcentration of trace amounts of Fe,Co, Ni and Zn from aqueous samples

The paper presents the preconcentration of trace elements via electrodeposition onto a (micro)aluminum cathode in the presence of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆] as a supporting electrolyte. The advantages of the proposed method include very simple instrumentation for the preconcentration of trace elements and low-cost reagents. The experiment showed that the use of ionic liquid in the electrodeposition process significantly improves sensitivity, recovery and detection limits for the determination of trace amounts of iron, cobalt, nickel and zinc. The preconcentrated metals were determined using X-ray fluorescence spectrometry. The optimum parameters for electrodeposition such as pH, the volume of the analyzed solution, the voltage and the deposition time were studied. Under the optimized conditions, the detection limits were 5, 2, 3 and 6 μg L^− 1 for iron, cobalt, nickel and zinc, respectively. The precision and recovery of the method were in the range of 3–5.5%, and 92–103%, respectively. The calibration was performed using aqueous standards of Fe(III), Co(II), Ni(II) and Zn(II) in the range 0.01–0.25 mg L^− 1. The method was applied successfully in water analysis.     

Layer-by-layer assembled DNA functionalized single-walled carbon nanotube hybrids for arsenic(III) detection

Based on layer-by-layer assembled DNA functionalized single-walled carbon nanotube hybrids, a DNA biosensor for the detection of arsenic(III) in a nearly physiological pH environment was developed. The redox process between arsenic(III) and arsenic(0) on the biosensor was proved. The growth of those hybrids on glassy carbon electrode was monitored by detecting arsenic(III). The arsenic(III) current on the biosensor was similar over a broad pH range (3.0–8.0) and the limit of detection (S/N = 3) was 0.05 μg L⁻¹ at pH 7.0. The biosensor can be reused up to 16 times.