Highly sensitive and selective voltammetric detection of mercury(II) using an ITO electrode modified with 5-methyl-2-thiouracil, graphene oxide and gold nanoparticles

We have developed an electrochemical sensor for highly selective and sensitive determination of Hg(II). It is based on the specific binding of 5-methyl-2-thiouracil (MTU) and Hg(II) to the surface of an indium tin oxide (ITO) electrode modified with a composite made from graphene oxide (GO) and gold nanoparticles (AuNPs). This leads to a largely enhanced differential pulse voltammetric response for Hg(II). Following optimization of the method, a good linear relationship (R?=?0.9920) is found between peak current and the concentration of Hg(II) in the 5.0–110.0 nM range. The limit of detection (LOD) is 0.78 nM at a signal-to-noise ratio of 3. A study on the interference by several metal ions revealed no interferences. The feasibility of this method was demonstrated by the analyses of real water samples. The LODs are 6.9, 1.0 and 1.9 nM for tap water, bottled water and lake water samples, respectively, and recoveries for the water samples spiked with 8.0, 50.0 and 100.0 nM were 83.9–96.8 %, with relative standard deviations ranging from 3.3 % to 5.2 %.

Solid-phase extraction of mercury(II) with magnetic core-shell nanoparticles, followed by its determination with a rhodamine-based fluorescent probe

Magnetic Fe₃O₄@SiO₂ core shell nanoparticles containing diphenylcarbazide in the shell were utilized for solid phase extraction of Hg(II) from aqueous solutions. The Hg(II) loaded nanoparticles were then separated by applying an external magnetic field. Adsorbed Hg(II) was desorbed and its concentration determined with a rhodamine-based fluorescent probe. The calibration graph for Hg(II) is linear in the 60 nM to 7.0 μM concentration range, and the detection limit is at 23 nM. The method was applied, with satisfying results, to the determination of Hg(II) in industrial waste water.

Carbon dots-based fluorescent probes for sensitive and selective detection of iodide

We report on a simple method for the determination of iodide in aqueous solution by exploiting the fluorescence enhancement that is observed if the complex formed between carbon dots and mercury ion is exposed to iodide. Fluorescent carbon dots (C-dots) were treated with Hg(II) ion which causes quenching of the emission of the C-dots. On addition of iodide, the Hg(II) ions are removed from the complex due to the strong interaction between Hg(II) and iodide. This causes the fluorescence to be restored and enables iodide to be determined in the 0.5 to 20 μM concentration range and with a detection limit of ~430 nM. The test is highly selective for iodide (over common other anions) and was used for the determination of iodide in urine.

Selective solid-phase extraction of trace mercury(II) using a silica gel modified with diethylenetriamine and thiourea

We describe a solid phase extractor for selective separation and preconcentration of Hg(II) ion. It was prepared by immobilizing the adduct of diethylenetriamine and thiourea on silica gel. The effects of solution acidity, preconcentration time, sample flow rate and volume were optimized. The results show that Hg(II) can be selectively extracted from acidic solutions and in presence of common other metal ions. The adsorbent is stable, can be reused more than 10 times, and the maximum adsorption capacity is 23 mg g^?1. Hg(II) was quantified by inductively coupled plasma optical emission spectrometry. The method has a detection limit of 23 ng L^?1, and the relative standard deviation is <2 %. The procedure was validated by analyzing two standard materials (river sediment and hair powder), and was successfully applied to the preconcentration of Hg(II) in real samples.

Aptamer based test stripe for ultrasensitive detection of mercury(II) using a phenylene-ethynylene reagent on nanoporous silver as a chemiluminescence reagent

We describe a paper-based chemiluminescence (CL) test for the determination of mercury(II) ion. A single-stranded DNA aptamer was first covalently immobilized via its amino groups to the hydroxy groups on the surface of cellulosic paper. The aptamer probes can capture Hg(II) ions due to their specific interaction with thymine. The CL reagent (a caboxylated phenylene-ethynylene referred to as P-acid) was immobilized on nanoporous silver (NPS@P-acid) and used a CL label on the aptamer. The stripe is then contacted with a sample containing Hg(II) ions and CL is induced by the addition of permanganate. CL intensity depends on the concentration of Hg(II) because Hg(II) increases the quantity of the P-acid-conjugated aptamer. The highly active surface of the NPS@P-acid composites results in an 8-fold higher CL intensity compared to the use of pure P-acid. This enables Hg(II) ion to be quantified in the 20 nM to 0.5 μM concentration range, with a limit of detection as low as 1 pM. This CL aptasensor is deemed to represent a promising tool for simple, rapid, and sensitive detection of Hg(II).

Detection of lead(II) using an glassy carbon electrode modified with Nafion, carbon nanotubes and benzo-18-crown-6

A glassy carbon electrode was modified with Nafion, carbon nanotubes and benzo-18-crown-6 to give an electrode for the selective determination of lead(II) via square wave anodic stripping voltammetry. The use of carbon nanotubes with their extraordinary electrical conductivity and strong adsorption ability warrants high sensitivity. Benzo-18-crown-6 is employed as a “molecular scavenger” because of its excellent selectivity for lead(II). The modified electrode shows enhanced sensitivity, reproducibility and selectivity for lead(II) even without applying an electrical potential during the accumulation time. It responds linearly to lead(II) in the 1 to 30 nM concentration range (with a correlation coefficient of 0.9992) after a 10-min accumulation time. The detection limit is 1 nM. The sensor exhibits excellent selectivity over other heavy metal ions such as Cd(II), Cu(II), Zn(II), and Hg(II).

Colorimetric detection of lead (II) based on silver nanoparticles capped with iminodiacetic acid

We report on a colorimetric probe for the determination of Pb(II). It is based on the use of silver nanoparticles that have been functionalizd with iminodiacetic acid (IDA-Ag NPs). The absorption spectrum and solution color of IDA-Ag NPs undergo dramatic changes on exposure to Pb(II) with a new absorption peak appearing at 650 nm and a concomitant color change from yellow to green. This is assumed to result from the aggregation of IDA-Ag NPs induced by Pb(II). Under optimum conditions, there is a linear relationship between the ratio of the absorbances at 650 and 396 nm, respectively, and the concentration of Pb(II) in the 0.4 to 8.0 μM concentration range, with a detection limit of 13 nM. The method was applied to the determination of Pb(II) in tap water and urea samples, and recoveries ranged from 93.7 % to 98.6 %.

Highly sensitive SERS probe for mercury(II) using cyclodextrin-protected silver nanoparticles functionalized with methimazole

We have developed a surface-enhanced Raman scattering (SERS) probe for the determination of mercury(II) using methimazole-functionalized and cyclodextrin-coated silver nanoparticles (AgNPs). These AgNPs in pH 10 solution containing sodium chloride exhibit strong SERS at 502 cm^?1. Its intensity strongly decreases in the presence of Hg(II). This effect serves as the basis for a new method for the rapid, fast and selective determination of trace Hg(II). The analytical range is from 0.50 μg L^?1 to 150 μg L^?1, and the limit of detection is 0.10 μg L^?1. The influence of 11 metal ions commonly encountered in environmental water samples was found to be quite small. The method was applied to the determination of Hg(II) in spiked water samples and gave recoveries ranging from 98.5 to 105.2 % and with relative standard deviations of <3.5 % (n?=?5). The total analysis time is <10 min for a single sample.

Simple optical determination of silver ion in aqueous solutions using benzo crown-ether modified gold nanoparticles

We describe a method for the modification of gold nanoparticles (Au-NPs) with benzo-15-crown-5 that led to the development of a colorimetric assay for Ag(I) ion. The brown color of a solution of the modified Au-NPs turns to purple on addition of Ag(I) ion. The ratio of the UV–vis absorption at 600 nm and 525 nm is proportional to the concentration of Ag(I) ions in the range from 20 to 950 nM, and the detection limit is 12.5 nM. Other metal ions do not interfere if present in up to millimolar concentrations. The method enables a rapid determination of Ag(I) in lake and drinking water and is amenable to bare-eye readout.

Direct electrochemistry of hemoglobin on an ionic liquid carbon electrode modified with zinc tungstate nanorods

We have constructed a new electrochemical biosensor by immobilization of hemoglobin (Hb) and ZnWO₄ nanorods in a thin film of chitosan (CTS) on the surface of carbon ionic liquid electrode. UV–vis and FT-IR spectra reveal that Hb remains in its native conformation in the film. The modified electrode was characterized by scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. A pair of well-defined redox peaks appears which indicates direct electron transfer from the electrode. The presence of CTS also warrants biocompatibility. The electron transfer coefficient and the apparent heterogeneous electron transfer rate constant were calculated to be 0.35 and 0.757 s^?1, respectively. The modified electrode displays good electrocatalytic activity for the reduction of trichloroacetic acid with the detection limit of 0.613 mmol L^?1 (3σ). The results extend the protein electrochemistry based on the use of ZnWO₄ nanorods.

Sputtering deposition of Pt nanoparticles on vertically aligned multiwalled carbon nanotubes for sensing L-cysteine

A highly sensitive electrochemical sensor for determination of L-cysteine (CySH) is presented. It is based on vertically aligned multiwalled carbon nanotubes modified with Pt nanoparticles by magnetron sputtering deposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy and energy-dispersive. The electrochemistry of CySH was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The mechanism for the electrochemical reaction of CySH at the modified electrode at different pH values is discussed. The electrode exhibits a higher electrocatalytic activity towards the oxidation of CySH than comparable other electrodes. It displays a linear dependence (R ²?=?0.9980) on the concentration of CySH in the range between 1 and 500 μM and at an applied potential of +0.45 V, a remarkably low detection limit of 0.5 μM (S/N?=?3), and an outstandingly high sensitivity of 1.42?×?10³ μA?mM^?1?cm^?2, which is the highest value ever reported. The electrode also is highly inert towards other amino acids, creatinine and urea. The sensor was applied to the determination of CySH in urine with satisfactory recovery, thus demonstrating its potential for practical applications.

Preconcentration of mercury(II) using a thiol-functionalized metal-organic framework nanocomposite as a sorbent

A novel type of porous metal-organic framework (MOF) was obtained from thiol-modified silica nanoparticles and the copper(II) complex of trimesic acid. It is shown that this nanocomposite is well suitable for the preconcentration of Hg(II) ions. The nanocomposite was characterized by Fourier transfer infrared spectroscopy, X-ray powder diffraction, energy-dispersive X-ray diffraction and scanning electron microscopy. The effects of pH value, sorption time, elution time, the volume and concentration of eluent were investigated. Equilibrium isotherms were studied, and four models were applied to analyze the equilibrium adsorption data. The results revealed that the adsorption process obeyed the Langmuir model. The maximum monolayer capacity and the Langmuir constant are 210 mg g^?1 and 0.273 L mg^?1, respectively. The new MOF-based nanocomposite is shown to be an efficient and selective sorbent for Hg(II). Under the optimal conditions, the limit of detection is 20 pg mL^?1 of Hg(II), and the relative standard deviation is <7.2 % (for n?=?3). The sorbent was successfully applied to the rapid extraction of Hg(II) ions from fish, sediment, and water samples.

A glassy carbon electrode modified with antimony and poly(p-aminobenzene sulfonic acid) for sensing lead(II) by square wave anodic stripping voltammetry

We have developed a sensor for the square wave anodic stripping voltammetric determination of Pb(II). A glassy carbon electrode was modified with a thin film of an antimony/poly(p-aminobenzene sulfonic acid) composite in air-saturated aqueous solution of pH 2.0. Compared to a conventional antimony film electrode, the new one yields a larger stripping signal for Pb(II). The conditions of polymerization, the concentration of Sb(III), the pH value of the sample solution, the deposition potential and time, frequency, potential amplitude, and step increment potential were optimized. Under the optimum conditions, a linear response was observed for Pb(II) in the range of 0.5 to 150.0 μg?L^?1. The detection limit for Pb(II) is 0.1 μg?L^?1.

Water-soluble homo-oligonucleotide stabilized fluorescent silver nanoclusters as fluorescent probes for mercury ion

Water–soluble fluorescent silver nanoclusters (Ag NCs) were prepared with the assistance of commercially available polyinosinic acid (PI) or polycytidylic acid (PC). The fluorescence of the Ag NCs is effectively quenched by trace mercury(II) ions, which can be applied for their detection. The response of the Ag NCs prepared with PI to Hg(II) ion is linear in the Hg(II) concentration range from 0.05 to 1.0 μM (R²?=?0.9873), and from 0.5 to 10 μM of Hg(II) (R²?=?0.9971) for Ag NCs prepared with PC. The detection limits are 3.0 nM and 9.0 nM (at an S/N of 3), respectively. The method is simple, sensitive and fairly selective.

Fabrication of SERS active gold nanorods using benzalkonium chloride,and their application to an immunoassay for potato virus X

The authors report on a robust method for the synthesis of gold nanorods (AuNRs) with tunable dimensions and longitudinal surface plasmon resonance. The method relies on seed-mediated particle growth in the presence of benzalkonium chloride (BAC) in place of the widely used surfactant cetyltrimethyl ammonium bromide (CTAB). Uniform AuNRs were obtained by particle growth in solution, and BAC is found to stabilize the AuNRs for >1 year. The SERS activity of the resulting AuNRs is essentially identical to that of CTAB-protected nanorods. The SERS activity of the BAC protected nanorods was applied to the quantitative analysis of potato virus X (PVX). The calibration plot for PVX is linear in the 10 to 750 ng?mL^?1 concentration range, and the detection limit is 2.2 ng?mL^?1.

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Graphical abstract SERS-active gold nanorods (AuNRs) have been prepared by using benzalkonium chloride as stabilization agent. Effects of chemical parameters on AuNRs have been explored and AuNRs were used in quantitative analysis of potato virus X (PVX).

     

Bulk polymer nanoparticles containing a tetrakis(3-hydroxyphenyl)porphyrin for fast and highly selective separation of mercury ions

We report on the synthesis of polymeric nanoparticles (PNPs) containing a tetrakis(3-hydroxyphenyl)porphyrin, and their use for the separation of mercury(II) ion. The PNPs were prepared by bulk polymerization from methacrylic acid (the monomer), ethyleneglycol dimethacrylate (the cross-linker), 2,2′-azobisisobutyronitrile (the radical initiator) and the mercury(II) complex of 5,10,15,20-tetrakis(3-hydroxyphenyl)-porphyrin. The Hg(II) ion was then removed by treatment with dilute hydrochloric acid. The PNPs were characterized by colorimetry, FT-IR spectroscopy, and scanning electron microscopy. The material is capable of binding Hg(II) from analyte samples. Bound Hg(II) ions can be eluted with dilute nitric acid and then quantified by cold vapor AAS. The extraction efficiency, the effects of pH, preconcentration and leaching times, sample volume, and of the nature, concentration and volume of eluent were investigated. The maximum adsorption capacity of the PNPs is 249 mg g^?1, the relative standard deviation of the AAS assay is 2.2 %, and the limit of detection (3σ) is 8 ng.L^?1. The nanoparticles exhibit excellent selectivity for Hg(II) ion over other metal ions and were successfully applied to the selective extraction and determination of Hg(II) ion in spiked water samples.

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 %

Amperometric nonenzymatic glucose sensor based on a glassy carbon electrode modified with a nanocomposite made from nickel(II) hydroxide nanoplates and carbon nanofibers

We report on a highly sensitive and selective nonenzymatic glucose sensor based on a glassy carbon electrode modified with a composite prepared from nickel(II) hydroxide nanoplates and carbon nanofibers. The nanocomposite was characterized by scanning electron microscopy and powder X-ray diffraction. Electrodes modified with pure Ni(OH)₂ and with the nanocomposite were characterized by electrochemical impedance spectroscopy. Cyclic voltammetric and amperometric methods were used to investigate the catalytic properties of the modified electrodes for glucose electrooxidation in strongly alkaline solution. The sensor exhibits a wide linear range (from 0.001 to 1.2 mM), a low detection limit (0.76 μM), fast response time (< 5 s), high sensitivity (1038.6 μA?·?mM^?1?·?cm^?2), good reproducibility, and long operational stability. Application of the nonenzymatic sensor for monitoring glucose in real samples was also demonstrated.

Templated in-situ synthesis of gold nanoclusters conjugated to drug target bacterial enoyl-ACP reductase,and their application to the detection of mercury ions using a test stripe

Fluorescent gold nanoclusters (AuNCs) were synthesized using a drug target bacterial enoyl-ACP reductase (FabI) as a template. The physical and chemical properties of the AuNCs were studied by UV-vis absorption, fluorescence, X-ray photoelectron spectroscopy and TEM. The AuNCs-FabI conjugate was prepared by in situ reduction of tetrachloroaurate in the presence of FabI. The conjugated particles were loaded onto nylon membranes by taking advantage of the electrostatic interaction between the negatively charged AuNCs@FabI and the nylon film which is positively charged at pH 7.4. This results in the formation of a test stripe with sensor spots that can be used to detect Hg(II) ion in the 1 nM to 10 μM concentration range. The test stripes are simple, convenient, selective, sensitive, and can be quickly read out with bare eyes after illumination with a UV lamp.

Thermally treated bare gold nanoparticles for colorimetric sensing of copper ions

We demonstrate a sensitive and rapid colorimetric assay for selective detection of copper ions based on the strong coordination between Cu(II) ions and the tetrahydroxyaurate anions [Au(OH)₄]^? on the surface of thermally treated bare gold nanoparticles (GNPs). The method for making the unmodified GNPs is simple and results in a nanomaterial with a highly specific response to Cu(II). The thermal treatment of the bare GNPs and the recognition of Cu(II) ions is accomplished in a single step within 5 min. The presence of Cu(II) causes the color to change from red to purple-blue. The limit of detection (LOD) is 0.04 μM of Cu(II) when using UV–vis spectrometry and ratioing the absorbances at 650 and 515 nm, respectively. The method also is amenable to bare eye (visual) inspection and in this case has an LOD of 2.0 μM of Cu(II).