Synthesis of multi-branched gold nanoparticles by reduction of tetrachloroauric acid with Tris base, and their application to SERS and cellular imaging

A biosensor for hydrogen peroxide was constructed by immobilizing horseradish peroxidase on chitosan-wrapped NiFe₂O₄ nanoparticles on a glassy carbon electrode (GCE). The electron mediator carboxyferrocene was also immobilized on the surface of the GCE. UV?Cvis spectra, Fourier transform IR spectra, scanning electron microscopy, and electrochemical impedance spectra were acquired to characterize the biosensor. The experimental conditions were studied and optimized. The biosensor responds linearly to H₂O₂ in the range from 1.0?×?10^?5 to 2.0?×?10^?3?M and with a detection limit of 2.0?×?10^?6?M (at S/N?=?3).

Cetyltrimethylammonium-coated magnetic nanoparticles for the extraction of bromate,followed by its spectrophotometric determination

We report on a combination of magnetic solid-phase extraction and spectrophotometric determination of bromate. Cetyltrimethylammonium ion was adsorbed on the surface of phenyl-functionalized silica-coated Fe₃O₄ nanoparticles (Ph-SiO₂@Fe₃O₄), and these materials served as the sorbent. The effects of surfactant and amount of sorbent, the composition of the desorption solution, the extraction time and temperature were optimized. Under optimized conditions, an enrichment factor of 12 was achieved, and the relative standard deviation is 2.9 % (for n?=?5). The calibration plot covers the 1–50 ng mL^?1 range with reasonable linearity (r ²?>?0.998); and the limit of detection is 0.5 ng mL^?1. The method is not interfered by ionic compounds commonly found in environmental water samples. It was successfully applied to the determination of bromate in spiked water samples.

Nickel and cobalt ferrites nanoparticles: synthesis,study of magnetic properties and their use as magnetic adsorbent for removing lead(II) ion

Nano-sized nickel ferrite (NiFe₂O₄) and cobalt ferrite particles (CoFe₂O₄) were successfully synthesized using a hydrothermal method. Techniques of X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometer, energy dispersive X-ray spectroscopy, vibrating sample magnetometer and transmission electron microscope have been used to characterize and study the as-synthesized NiFe₂O₄ and CoFe₂O₄ products. The results showed that the average size of the nickel and cobalt ferrite nanoparticles is smaller than 10 and 100 nm, respectively. The results of magnetic measurement showed that the synthesized NiFe₂O₄ and CoFe₂O₄ nanoparticles were superparamagnetic and soft ferromagnetic materials, respectively. Study of adsorption behavior showed that these nanoparticles can act as a good adsorbent for removing Pb²⁺.     

Magnetic Investigation of Various NiFe<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>4</Subscript> Ferrite Nanostructures Synthesized by Ball Milling Technique

NiFe_2?x Bi _x O₄ (x = 0, 0.1, 0.2, 0.3) nanoparticles with various grain sizes were synthesized via annealing treatment followed by ball milling of its bulk component materials. Commercially available bismuth, nickel and iron oxide powders were first mixed and then annealed at 1200 °C in an oxygen environment furnace for 4 h. The samples were then milled for 2 h by high-energy ball milling. X-ray diffraction (XRD) pattern indicated that in this stage the samples are single phase. The microstructure investigation was carried out by a scanning electron microscope with maximum magnification of 30,000. The average grain size for different samples was estimated by XRD technique and transmission electron microscopy. Magnetic behavior of the samples at room temperature was studied using an alternating gradient force magnetometry. The Néel temperature of the powders was measured by a Faraday balance. Based on magnetic studies, increase in bismuth content leads to a decrease in the saturation magnetization, coercive field and Néel temperature. This can be attributed to the substitution of Bi³⁺ ion in the ferrite system as a nonmagnetic cation.     

Magnetic titanium oxide nanoparticles for hemimicelle extraction and HPLC determination of organophosphorus pesticides in environmental water

We report on a method for the extraction of organophosphorus pesticides (OPPs) from water samples using mixed hemimicelles and magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) modified by cetyltrimethylammonium. Fe₃O₄@TiO₂ nanoparticles were synthesized by a hydrothermal process and then characterized by scanning electron microscopy and Fourier transform IR spectrometry. The effects of the quantity of surfactant, extraction time, desorption solvent, pH value, extraction volume and reuse of the sorbent were optimized with respect to the extraction of OPPs including chlorpyrifos, dimethoate, and trichlorfon. The extraction method was applied to analyze OPPs in environmental water using HPLC along with UV detection. The method has a wide linear range (100–15,000 ng L^?1), good linearity (r?>?0.999), and low detection limits (26–30 ng L^?1). The enrichment factor is ~1,000. The recoveries (at spiked levels of 100, 1,000 and 10,000 ng L^?1) are in the range of 88.5–96.7 %, and the relative standard deviations range from 2.4 % to 8.7 %.

Preparation of Fe3O4@C@CNC multifunctional magnetic core/shell nanoparticles and their application in a signal-type flow-injection photoluminescence immunosensor

We describe here the preparation of carbon-coated Fe₃O₄ magnetic nanoparticles that were further fabricated into multifunctional core/shell nanoparticles (Fe₃O₄@C@CNCs) through a layer-by-layer self-assembly process of carbon nanocrystals (CNCs). The nanoparticles were applied in a photoluminescence (PL) immunosensor to detect the carcinoembryonic antigen (CEA), and CEA primary antibody was immobilized onto the surface of the nanoparticles. In addition, CEA secondary antibody and glucose oxidase were covalently bonded to silica nanoparticles. After stepwise immunoreactions, the immunoreagent was injected into the PL cell using a flow-injection PL system. When glucose was injected, hydrogen peroxide was obtained because of glucose oxidase catalysis and quenched the PL of the Fe₃O₄@C@CNC nanoparticles. The here proposed PL immunosensor allowed us to determine CEA concentrations in the 0.005–50 ng?·?mL^-1 concentration range, with a detection limit of 1.8 pg?·?mL^-1.

Surfactant-enhanced liquid-liquid microextraction coupled to micro-solid phase extraction onto highly hydrophobic magnetic nanoparticles

We are presenting a simplified alternative method for dispersive liquid-liquid microextraction (DLLME) by resorting to the use of surfactants as emulsifiers and micro solid-phase extraction (μ-SPE). In this combined procedure, DLLME of hydrophobic components is initially accomplished in a mixed micellar/microemulsion extractant phase that is prepared by rapidly mixing a non-ionic surfactant and 1-octanol in aqueous medium. Then, and in contrast to classic DLLME, the extractant phase is collected by highly hydrophobic polysiloxane-coated core-shell Fe₂O₃@C magnetic nanoparticles. Hence, the sample components are the target analyte in the DLLME which, in turn, becomes the target analyte of the μ-SPE step. This 2-step approach represents a new and simple DLLME procedure that lacks tedious steps such as centrifugation, thawing, or delicate collection of the extractant phase. As a result, the analytical process is accelerated and the volume of the collected phase does not depend on the volume of the extraction solvent. The method was applied to extract cadmium in the form of its pyrrolidine dithiocarbamate chelate from spiked water samples prior to its determination by FAAS. Detection limits were brought down to the low μg L^?1 levels by preconcentrating 10 mL samples with satisfactory recoveries (96.0–108.0 %).

A lanthanide nanoparticle-based luminescent probe for folic acid

We report on a novel luminescent method for the detection of folic acid (FA), a member of the vitamin B family. Y₂O₃ nanoparticles were doped with europium(III) ions and surface-modified with captopril. Their fluorescence is quenched by FA, and intensity is a function of folic acid concentration in the 0.1 – 40 μM concentration range. The detection limit is 83 nM of FA at pH 7 and room temperature.

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.

Electrochemical sensing of hydrogen peroxide using metal nanoparticles: a review

We are reviewing the state of electrochemical sensing of H₂O₂ based on the use of metal nanoparticles. The article is divided into subsections on sensors based on nanoparticles made from Ag, Pt, Pd, Cu, bimetallic nanoparticles and other metals. Some sensors display high sensitivity, fast response, and good stability. The review is subdivided into sections on sensors based on heme proteins and on nonenzymatic sensors. We also discussed the challenges of nanoscaled sensors and their future aspects.

Optical determination of glucose and hydrogen peroxide using a nanocomposite prepared from glucose oxidase and magnetite nanoparticles immobilized on graphene oxide

Fe₃O₄ nanoparticles were deposited on sheets of graphene oxide (GO) by a precipitation method, and glucose oxidase (GOx) was then immobilized on this material to produce a GOx/Fe₃O₄/GO magnetic nanocomposite containing crosslinked enzyme clusters. The 3-component composite functions as a binary enzyme that was employed in a photometric method for the determination of glucose and hydrogen peroxide where the GOx/Fe₃O₄/GO nanoparticles cause the generation of H₂O₂ which, in turn, oxidize the substrate N,N-diethyl-p-phenylenediamine to form a purple product with an absorption maximum at 550 nm. The absorbance at 550 nm can be correlated to the concentration of glucose and/or hydrogen peroxide. Under optimized conditions, the calibration plot is linear in the 0.5 to 600 μM glucose concentration range, and the detection limit is 0.2 μM. The respective plot for H₂O₂ ranges from 0.1 to 10 μM, and the detection limit is 0.04 μM. The method was successfully applied to the determination of glucose in human serum samples. The GOx/Fe₃O₄/GO nanoparticles are reusable.

Sensitive electrochemical sensor for hydrogen peroxide using Fe3O4 magnetic nanoparticles as a mimic for peroxidase

A sensor for hydrogen peroxide is described that is based on an indium tin oxide electrode modified with Fe₃O₄ magnetic nanoparticles which act as a mimic for the enzyme peroxidase and greatly improve the analytical performance of the sensor. The amperometric current is linearly related to the concentration of H₂O₂ in the range from 0.2 mM to 2 mM, the regression equation is y?=?-0.5–1.82x, the correlation coefficient is 0.998 (n?=?3), and the detection limit is 0.01 mM (S/N?=?3). The sensor exhibits favorable selectivity and excellent stability.

Peroxidase-like activity of magnetoferritin

Magnetoferritin is a spherical biomacromolecule with a diameter of about 12 nm. It consists of a protein shell composed of apoferritin that is surrounding magnetic nanoparticles of magnetite (Fe₃O₄) or maghemite (γ-Fe₂O₃). Magnetoferritins with various iron content (loading factor) were synthetically prepared and their peroxidase-like activities studied via the oxidation of the chromogenic substrate N,N-diethyl-p-phenylenediamine sulfate by hydrogen peroxide to give a purple product with an absorption maximum at 551 nm. Magnetoferritin with higher loading factor exhibits a higher peroxidase-like activity. The catalytic activity was successfully applied to the determination of hydrogen peroxide in the 5.8 to 88.2 mM concentration range.

Y2O3: Eu,Zn nanocrystals as a fluorescent probe for the detection of biotin

We report on the application of nanocrystals (NCs) of the type Y₂O₃: Eu,Zn as a probe for the fluorescent detection of biotin in aqueous solution. The NCs were dispersed in water in the presence of various surface modifiers including mercaptoethanol (ME), monoethanolamine and ethylene glycol. Both the absorbance of surfactant and the stability of the suspensions were investigated in order to optimize the experimental conditions. ME is found to be the most suitable surfactant for stabilization of the suspended NCs. Their photoluminescence intensity is found to be quenched by biotin. The Stern-Volmer constant for the quenching process is 7.6?×?10³ M^?1. This NC probe can be applied to the detection of biotin in the 1–60 μM concentration range with detection limit of 1.89 μM. The possible mechanisms of quenching also are discussed.

Structural and Magnetic Properties of Chemically Synthesized Pd-Modified NiFe2O4 Nanoparticles

Magnetic nanoparticles of NiFe₂O₄-Pd composites have been synthesized using a simple, low cost, sol-gel auto-combustion method. As-prepared samples were sintered at 800 ℃ for 6 h in order to develop the crystalline phase. X-ray diffraction confirmed the spinel structure of the ferrite samples. Structural morphology and size of the nanoparticles were evaluated using a field emission scanning electron microscope. Magnetic hysteresis loops were obtained at 300 and 100 K using a physical properties measurement system. The value of saturation magnetization was observed to decrease at the temperatures with the increase of Pd contents up to 5% but then a sudden rise in saturation magnetization was observed for the addition of 10% Pd in NiFe₂O₄.     

Fluorescence-based immunoassay for human chorionic gonadotropin based on polyfluorene-coated silica nanoparticles and polyaniline-coated Fe3O4 nanoparticles

We report on an ultrasensitive fluorescence immunoassay for human chorionic gonadotrophin antigen (hCG). It is based on the use of silica nanoparticles coated with a copolymer (prepared from a fluorene, a phenylenediamine, and divinylbenzene; PF@SiO₂) that acts as a fluorescent label for the secondary monoclonal antibody to β-hCG antigen. In parallel, Fe₃O₄ nanoparticles were coated with polyaniline, and these magnetic particles (Fe₃O₄@PANI) served as a solid support for the primary monoclonal antibody to β-hCG antigen. The PF@SiO₂ exhibited strong fluorescence and good dispersibility in water. A fluorescence sandwich immunoassay was developed that enables hCG concentrations to be determined in the 0.01–100 ng·mL^?1 concentration range, with a detection limit of 3 pg·mL^?1.

Template-Free Hydrothermal Synthesis of Hollow α-FeOOH Urchin-Like Spheres and Their Conversion to α-Fe2O3 Under Low-Temperature Thermal Treatment in Air

Hollow α-FeOOH urchin-like spheres were synthesized by a simple hydrothermal method at 160 °C for 12 h and their thermal conversion to hollow α-Fe₂O₃ urchin-like spheres was performed at 300 °C for 2 h in air. The results from X-ray diffraction and electron microscopy analyses reveal that hollow α-FeOOH urchin-like spheres were completely transformed to hollow α-Fe₂O₃ urchin-like spheres without a significant morphological change. Also, the effect of hydrothermal treatment temperature (170–200 °C for 12 h) on the phase structure and morphology of the final product was investigated. Pure α-FeOOH, the mixture of α-FeOOH and α-Fe₂O₃, and pure α-Fe₂O₃ with different morphologies were obtained at <180, 180–190 and 200 °C, respectively. The obtained materials can be used in the photodegradation of organic pollutants under visible light irradiation.     

Direct electrochemistry and electrocatalysis of myoglobin using an ionic liquid-modified carbon paste electrode coated with Co3O4 nanorods and gold nanoparticles

A nanohybrid biomaterial was fabricated by mixing Co₃O₄ nanorods, gold nanoparticles (Au-NPs) and myoglobin (Mb), and depositing it on the surface of a carbon paste electrode containing the ionic liquid N-hexylpyridinium hexafluorophosphate as the binder. UV–vis and FT-IR revealed the Mb in the composite film to have remained in its native structure. A pair of well-defined redox peaks appears in cyclic voltammograms and indicates direct electron transfer from the Mb to the underlying electrode. The results are attributed to the favorable orientation of Mb in the composite film, to the synergistic effects of Co₃O₄ nanorods and Au-NPs. The modified electrode shows excellent electrocatalytic ability towards the reduction of substrates such as trichloroacetic acid and nitrite, and displays good stability and reproducibility.

A glassy carbon electrode modified with a film composed of cobalt oxide nanoparticles and graphene for electrochemical sensing of H2O2

We have prepared a graphene-based hybrid nanomaterial by electrochemical deposition of cobalt oxide nanoparticles (CoO_xNPs) on the surface of electrochemically reduced graphene oxide deposited on a glassy carbon electrode (GCE). Scanning electron microscopy and cyclic voltammetry were used to characterize the immobilized nanoparticles. Electrochemical determination of H₂O₂ is demonstrated with the modified GCE at pH 7. Compared to GCEs modified with CoO_xNPs or graphene sheets only, the new electrode displays larger oxidative current response to H₂O₂, probably due to the synergistic effects between the graphene sheets and the CoO_xNPs. The sensor responds to H₂O₂ with a sensitivity of 148.6 μA mM^?1 cm^?2 and a linear response range from 5 μM to 1 mM. The detection limit is 0.2 μM at a signal to noise ratio (SNR) of three. The method was successfully applied to the determination of H₂O₂ in hydrogen peroxide samples.

Protein-directed in situ synthesis of platinum nanoparticles with superior peroxidase-like activity, and their use for photometric determination of hydrogen peroxide

Platinum nanoparticles (Pt-NPs) with sizes in the range from 10 to 30 nm were synthesized using protein-directed one-pot reduction. The model globular protein bovine serum albumin (BSA) was exploited as the template, and the resulting BSA/Pt-NPs were studied by transmission electron microscopy, energy dispersive X-ray spectroscopy, and resonance Rayleigh scattering spectroscopy. The modified nanoparticles display a peroxidase-like activity that was exploited in a rapid method for the colorimetric determination of hydrogen peroxide which can be detected in the 50 μM to 3 mM concentration range. The limit of detection is 7.9 μM, and the lowest concentration that can be visually detected is 200 μM.