Synthesis of hybrid nanoparticles based on magnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and luminescent CdS nanoparticles

A new approach to the synthesis of hybrid nanoparticles based on magnetic Fe₃O₄ nanoparticles and CdS quantum dots, combining magnetic and luminescence properties, has been suggested. Conditions for preparation of their stable aqueous suspensions have been found, and their optical properties have been studied. Nanocomposites produced at the molar ratio Fe₃O₄: CdS = 5: 1, which exhibited the luminescence properties) and gave stable aqueous suspensions, have turned out to be most promising. The results are evidence that the synthesized nanoparticles can be used for the development of visualizing agents for in vitro biomedical research.     

Aptamer-based fluorescent platform for ultrasensitive adenosine detection utilizing Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles and silver nanoparticles

The authors describe an aptamer-based fluorescent assay for adenosine (Ade). It is based on the interaction between silver nanoparticles (AgNPs) and CdTe quantum dots (QDs). The beacon comprises a pair of aptamers, one conjugated to Fe₃O₄ magnetic nanoparticles, the other to AgNPs. In the presence of Ade, structural folding and sandwich association of the two attachments takes place. After magnetic separation, the associated sandwich structures are exposed to the QDs. The AgNPs in sandwich structures act as the signaling label of Ade by quenching the fluorescence of QDs (at excitation/emission wavelengths of 370/565 nm) via inner filter effect, electron transfer and trapping processes. As a result, the fluorescence of QDs drops with increasing Ade concentration. The assay has a linear response in the 0.1 nM to 30 nM Ade concentration range and a 60 pM limit of detection. The assay only takes 40 min which is the shortest among the aptamer-based methods ever reported. The method was successfully applied to the detection of Ade in spiked biological samples and satisfactory recoveries were obtained.

Open image in new window

Graphical abstract Schematic of a highly efficient and convenient adenosine (Ade) fluorometric assay. It is based on the interaction between Ag nanoparticles (NPs) and CdTe quantum dots (QDs). Ade aptamers (ABA1 and ABA2) are used as recognition unit and Fe₃O₄ magnetic nanoparticles act as magnetic separator. The assay exhibits superior sensitivity and speediness.

     

Fast removal and determination of doxycycline in water samples and honey by Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

Adsorption characteristics and doxycycline (DC) removal efficiency of Fe₃O₄ magnetic nanoparticles as adsorbents have been determined by investigating the effects of pH, concentration of the DC, amount of adsorbents, contact time, ionic strength and temperature. The mechanism of adsorption was also studied. The adsorption of DC to the Fe₃O₄ magnetic nanoparticles could be described by Langmuir-type adsorption isotherms. Short contact time between the reagents, reusability of Fe₃O₄ for three times after recycling of the nanoparticles, good precision and accuracy, wide working pH range and high breakthrough volume are among the highlights of this procedure. The proposed extraction and determination procedure based on magnetic nanoparticles as adsorbent was successfully applied to the determination of DC spiked in honey and various water samples. The method presented here is fast, simple, cheap and robust, and it does not require the use of organic solvents. Also, the method needs only a magnet and can be performed in any laboratory without sophisticated equipment.     

A novel amperometric immunosensor based on Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles/chitosan composite film for determination of ferritin

A novel amperometric immunosensor was developed by immobilizing ferritin antibody (FeAb) on the surface of Fe₃O₄ magnetic nanoparticles/chitosan composite film modified glassy carbon electrode (GCE). This material combined the advantages of inorganic Fe₃O₄ nanoparticles with the organic polymer chitosan. The stepwise assembly procedure of the immunosensor was characterized by means of differential pulse voltammetry (DPV) and ac impedance. The K₃Fe(CN)₆/K₄Fe(CN)₆ was used as a marker to probe the interface and to determinate ferritin. The factors that could influence the performance of the resulting immunosensor were studied in detail. After the immunosensor was incubated with ferritin for 32 min at 35 °C, the DPV current decreased linearly with the logarithm of ferritin concentration in the range from 20 to 500 ng mL⁻¹ with a correlation coefficient of 0.995 and a detection limit of 7.0 ng mL⁻¹. This immunosensor was used to analyze ferritin in human serum samples. The analytical results showed that the developed immunoassay was comparable with the radioimmunoassay (RIA), and the studied immunosensor exhibited good accuracy, high sensitivity, and long-term stability for 3 weeks, which implies a promising alternative approach for detecting ferritin in clinical diagnosis.     

Magnetic nanoparticles (Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> &amp; Co<Subscript>3</Subscript>O<Subscript>4</Subscript>) and their applications in urea biosensing

Nanobiotechnology has opened a new and exciting opportunities for exploring urea biosensor based on magnetic nanoparticles (NPs) mainly Fe₃O₄ and Co₃O₄. These NPs have been extensively exploited to develop biosensors with stability, selectivity, reproducibility and fast response time. This review gives an overview of the development of urea biosensor based on Fe₃O₄ and Co₃O₄ for in vitro diagnostic applications along with significant improvements over the last few decades. Additionally, effort has been made to elaborate properties of magnetic nanoparticles (MNPs) in biosensing aspects. It also gives details of recent developments in hybrid nanobiocomposite based urea biosensor.     

The design of hybrid materials based on magnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and luminescent CdS nanoparticles for cell visualization

Hybrid nanoparticles based on Fe₃O₄ and CdS combining magnetic and luminescence properties were synthesized. The possibility of visualization of various cells by 3-mercaptopropylsilane-modified CdS nanoparticles and hybrid nanoparticles based on them using a confocal microscope was demonstrated. The synthesized materials did not show a clear-cut cytotoxicity.     

One-Pot Synthesis of Novel Amino-Functionalized Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Hybrid Microspheres for Cu(II) Removal from Aqueous Solutions

In this work, we report the development of novel amino-functionalized Fe₃O₄ hybrid microspheres adsorbent from a facial and one-step solvothermal route by using FeCl₃·6H₂O as a single iron source and 3-aminophenoxy-phthalonitrile as ource of amino groups. During solvothermal process, the nitrile groups of 3-aminophenoxy-phthalonitrile would bond with the Fe₃O₄ through the phthalocyanine cyclization reaction to form the amino-functionalized Fe₃O₄ magnetic nano-material, which was confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and thermo-gravimetric analyzer (TGA). From the scanning electron microscope (SEM) and transmission electron microscopy (TEM) observation, the resulting monodispersed amino-functionalized Fe₃O₄ hybrid microspheres with the diameters of 180–200 nm were synthesized via the self-assembly process. More importantly, as-prepared Fe₃O₄ nano-materials with abundant amino groups exhibited high separation efficiency when they were used to remove the Cu(II) from aqueous solutions. Furthermore, the adsorption isotherms of Fe₃O₄ nano-material for Cu(II) removal fitted the Langmuir isotherm model, in which the calculated maximum adsorption capacity could increase from 5.51 to 16.25 mg g^–1 at room temperature. This work demonstrated that the amino-functionalized Fe₃O₄ magnetic nano-materials were promising as efficient adsorbents for the removal of heavy metal ions from wastewater in low concentration.     

Magnetorheological characteristics of aqueous suspensions that contain Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

This investigation examines the magnetorheological (MR) characteristics of Fe₃O₄ aqueous suspensions. Magnetite particles (Fe₃O₄) were synthesized using a colloidal process and their sizes were determined to be normally distributed with an average of 10 nm by TEM. Experimental results reveal that the MR effect increases with the magnetic field and suspension concentration. The yield stress increases by up to two orders of magnitude when the sample is subjected to a magnetic field of 146 Oe/mm. In comparison with other published results, concerning a concentration of approximately 10–15% v/v, this study demonstrates that the same increase can be obtained with a concentration of nano-scale particles as low as 0.04% by volume. The viscosity was increased by an order of magnitude while the shear rate remained low; however, the increase decayed rapidly as the shear rate was raised. Finally, the MR effect caused by DC outperformed that caused by AC at the same current.     

L-phenyl alanine-attached Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> nanoparticles as an efficient catalyst for the synthesis of chromenes

In the present paper, L-phenyl alanine has been successfully linked on the surface of magnetic nanoparticles and has been characterized by FT-IR, XRD, SEM, EDS, TGA, and VSM techniques. This new catalyst was employed for one-pot synthesis of chromenes through the reaction of aldehydes, 4-hydroxycoumarin, and 2-hydroxynaphthalene-1,4-dione. Significant features of this method are short reaction time, excellent yields, use of green method, and the use of an effective and novel catalyst that could be recovered and reused several times without loss of its catalytic activity.     

Pd(II) anchored to modified Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles as a new magnetically recoverable catalyst for epoxidation of styrene

A new support for Pd(II) was synthesized via the functionalization of Fe₃O₄ nanoparticles with N-(2-aminoethyl)acetamide. PdCl₂ was anchored to the support for obtaining a heterogeneous magnetically recoverable catalyst for Pd(II). High yield and excellent selectivity were obtained for the green epoxidation of styrene derivatives using H₂O₂ as a green oxidant in H₂O as the solvent at 100 °C. Also, the recovered catalyst is applicable for four times without significant decrease in yield.     

Carbon-coated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles with surface amido groups for magnetic solid phase extraction of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) prior to their quantitation by ICP-MS

A magnetic nanosorbent was prepared from Fe₃O₄ nanoparticles and polyacrylamide using a solvothermal process. Two functions are achieved simultaneously in this process: The first consists in the formation of a carbon layer around the Fe₃O₄ nanoparticles, and the second one in the functionalization with an amido group. This combination allows the protection of Fe₃O₄ nanoparticles from dissolution in acid medium during heavy metal adsorption. The adsorbent was characterized by SEM, TEM, EDS, FTIR, TGA, and in terms of surface area. Results showed the Fe₃O₄ nanoparticles to be embedded in a sheet of carbon with folded surfaces which is functionalized with amido groups. The nanosorbent was applied to the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) via magnetic solid phase extraction (mag-SPE). The effects of pH value, eluent type and sample volume were optimized. The validation of the procedure was verified by the analysis of a wheat gluten certified reference material (8418). The limits of detection for the above ions range from 1 to 110 ng L^?1. The relative standard deviations are <10%. The procedure was successfully applied to the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) from various water and food samples.

Open image in new window

Graphical abstract Schematic of a new magnetic nanosorbent synthesized from Fe₃O₄ nanoparticles and polyacrylamide using a solvothermal method. The sorbent was used for the enrichment of Cr(III), Co(II), Cd(II), Zn(II) and Pb(II) in water and food samples for their ICP-MS detection.

     

Synthesis of spiro[pyrazoloquinoline-oxindoles] and spiro[chromenopyrazolo-oxindoles] promoted by guanidine-functionalized magnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Magnetic nanoparticles (MNPs) Fe₃O₄-immobilized guanidine (Fe₃O₄ MNPs-guanidine) have been used as an efficient catalyst for the preparation of spiro[pyrazoloquinoline-oxindoles] and spiro[chromenopyrazolo-oxindoles] by four-component reactions of phenylhydrazine or hydrazine hydrate, isatins, ketoesters and naphthylamine or 2-naphthol under reflux condition in ethanol. This method provides several advantages including mild reaction conditions, the applicability to a wide range of substrates, the reusability of the catalyst and low catalyst loading.     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Preconcentration of Pb(II) by using Mg(II)-doped NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles as a magnetic solid phase extraction agent

Magnesium(II)-doped nickel ferrite (Mg–NiFe₂O₄) nanoparticles are introduced as a new adsorbent for magnetic solid phase extraction of lead(II) ions from aqueous solutions. The structure and morphology of the adsorbent was characterized by FTIR, X-ray diffraction and scanning electron microscopy. The effects of pH value, amount of adsorbent, type, concentration and volume of the eluent and adsorption/desorption time on the extraction efficiency were studied. Following elution with hydrochloric acid, Pb(II) ions were quantified by flame atomic absorption spectrometry. Under optimized conditions, the calibration graph is linear in the 0.5–125 ng mL^?1 Pb(II) ion concentration range. Other figures of merit include (a) a 0.2 ng mL^?1 limit of detection, (b) an enrichment factor of 200, (c) an intra-day relative standard deviation (for n =?6 at 50 ng mL^?1) of 1.6%, and (d) an inter-day precision of 3.8%. The method was validated by the analysis of the certified reference material, NIST SRM 1566b. It was successfully applied to the determination of Pb(II) ion in spiked water samples, industrial wastewater and acidic lead battery waters.

Open image in new window

Graphical abstract Schematic of the synthesis of Mg(II)-doped NiFeO₄ nanoparticles and their application as a magnetic sorbent for solid-phase extraction of a Pb(II) ions prior to determination by flame atomic absorption spectrometry (FAAS).

     

Surface chemistry of nanoscale Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> dispersed in magnetic fluids

The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe₃O₄ core with single domain and the average grain size around 8–12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers adsorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case. Supported by the National Natural Science Foundation of China (Grant No. 50476039), and Guangdong Provincial Department of Science and Technology (Grant No. 2004A10-703001)     

A Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript>@graphene quantum dot core-shell structured nanomaterial as a fluorescent probe and for magnetic removal of mercury(II) ion

The authors describe the synthesis of a multifunctional nanocomposite with an architecture of type Fe₃O₄@SiO₂@graphene quantum dots with an average diameter of about 22 nm. The graphene quantum dots (GQDs) were covalently immobilized on the surface of silica-coated magnetite nanospheres via covalent linkage to surface amino groups. The nanocomposite displays a strong fluorescence (with excitation/emission peaks at 330/420 nm) that is fairly selectively quenched by Hg²⁺ ions, presumably due to nonradiative electron/hole recombination annihilation. Under the optimized experimental conditions, the linear response to Hg²⁺ covers the 0.1 to 70 μM concentration range, with a 30 nM lower detection limit. The high specific surface area and abundant binding sites of the GQDs result in a good adsorption capacity for Hg²⁺ (68 mg?g^?1). The material, due to its superparamagnetism, can be separated by using a magnet and also is recyclable with EDTA so that it can be repeatedly used for simultaneous detection and removal of Hg²⁺ from contaminated water.

Open image in new window

Graphical abstract A schematic view of preparation process for the Fe₃O₄@SiO₂@graphene quantum dots nanocomposite (denoted as Fe₃O₄@SiO₂@GQDs). The graphene quantum dots were covalently immobilized on the surface of silica-coated magnetite nanospheres (Fe₃O₄@SiO₂) via covalent linkage to surface amino groups.

     

Study of electrochemical behavior of the Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles in aprotic media

Peculiarities of electrochemical behavior of the Fe₃O₄ magnetic nanoparticles immobilized on the surface of a platinum electrode in aprotic organic media were investigated. Possible scheme of electrochemical behavior of nanoparticles depending on pre-electrolysis potential (–1.3,–2.5 V) was suggested. The effect of pre-electrolysis time, potential scan rate and nature of supporting electrolyte on the processes investigated was determined. A linear dependence of electrochemical oxidation signal versus the concentration of nanoparticles in modifying suspension in the concentration range of 0.05—0.5 g L^–1 was observed. The results of the performed research allow using magnetite nanoparticles as a direct signal-generating label in electrochemical immunoassay.     

Comparison of the Solubility of ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> in High Temperature Water

As the solubility is a direct measure of stability, this study compares the solubilities of ZnFe₂O₄, Fe₃O₄ and Fe₂O₃ in high temperature water. Through literature analysis and formula derivation, it is shown that it is reasonable to assume ZnFe₂O₄ and Fe(OH)₃ coexist when ZnFe₂O₄ is dissolved in water. Results indicated that the solubility of ZnFe₂O₄ is much lower than that of Fe₂O₃ or Fe₃O₄. The low solubility of ZnFe₂O₄ indicates that it is more protectively stable as an anticorrosion phase. Moreover, the gap between the solubility of ZnFe₂O₄ and that of Fe₃O₄ or Fe₂O₃ was enlarged with an increase of temperature. This means that ZnFe₂O₄ is more protective at higher temperatures. Further analysis indicated that with the increase of temperature, the solubility of ZnFe₂O₄ changed little while those of Fe₂O₃ or Fe₃O₄ changed a lot. Little change of the solubility of ZnFe₂O₄ with increase of temperature showed that ZnFe₂O₄ is stable. The very low and constant solubility of ZnFe₂O₄ suggests that it is more protective than Fe₂O₃ and Fe₃O₄, especially in water at higher temperature.