Multiple detection of proteins by SERS-based immunoassay with core shell magnetic gold nanoparticles

A highly selective and sensitive surface-enhanced Raman scattering (SERS)-based immunoassay for the multiple detection of proteins has been developed. The proposed core shell magnetic gold (Au) nanoparticles allow for successful protein separation and high SERS enhancement for protein detection. To selectively detect a specific protein in a mixed protein solution, we employed the sandwich type SERS immunoassay with core shell magnetic Au nanoparticles utilizing specific antigen–antibody interactions. Based on this proposed SERS immunoassay, we can successfully detect proteins in very low concentrations (∼800 ag/mL of mouse IgG and ∼5 fg/mL of human IgG) with high reproducibility. Magnetically assisted protein separation and detection by this proposed SERS immunoassay would provide great potential for effective and sensitive multiple protein detection. This technique allows for the straightforward SERS-based bioassays for quantitative protein detections.     

Stimuli-sensitive core/shell template particles for immobilizing inorganic nanoparticles in the core

We synthesize and characterize stimuli-sensitive core/shell particles with functional group (or material) localized in the core. We previously reported two types of hybrid particles prepared by using the template particles which were synthesized by soap-free emulsion copolymerization with N-isopropylacrylamide and glycidyl methacrylate (GMA) as monomers but by different preparation methods. GMA has advantages in immobilizing materials having several functional groups such as thiol ones. In this study, to obtain the suitable template particles for immobilizing any inorganic nanoparticles in the core, we investigated the effect of feed ratio of the two monomers. Obtained template particles were modified by thiol compounds to introduce ionic groups. They were characterized by dynamic light scattering and scanning electron microscopy. After in situ synthesis of magnetic nanoparticles in the templates, the hybrid particles were characterized directly by transmission electron microscopy. Consequently, we could obtain the hybrid core/shell particles which contained a large amount of magnetic nanoparticles (∼33 wt%) in the core.     

Ni/NiO core/shell nanoparticles for selective binding and magnetic separation of histidine-tagged proteins

Ni/NiO core/shell nanoparticles having high affinity with polyhistidine were synthesized by decomposition of a Ni surfactant complex followed by air oxidation. Ni/NiO nanoparticles showed selective and efficient binding to histidine-tagged proteins and easy separation by using a magnet. These provided a more convenient way to efficient purification of histidine-tagged proteins compared with the conventional Ni-NTA complex-bound resins and microbeads.     

Spontaneous formation of core/shell bimetallic nanoparticles: a calorimetric study

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh, Pd, or Pt) at room temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, DeltaH, was observed: DeltaH = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.     

One-pot synthesis of robust core/shell gold nanoparticles

A one-pot synthesis of thermally stable core/shell gold nanoparticles (Au-NPs) was developed via surface-initiated atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) and a dimethacrylate-based cross-linker. The higher reactivity of the cross-linker enabled the formation of a thin cross-linked polymer shell around the surface of the Au-NP before the growth of linear polymer chains from the shell. The cross-linked polymer shell served as a robust protective layer, prevented the dissociation of linear polymer brushes from the surfaces of Au-NPs, and provided the Au-NPs excellent thermal stability at elevated temperature (e.g., 110 degrees C for 24 h). This synthetic method could be easily expanded for preparation of other types of inorganic/polymer nanocomposites with significantly improved stability.     

Generation of core/shell iron oxide magnetic nanoparticles with polystyrene brushes by atom transfer radical polymerization

The functionalization of nanoparticle surfaces is required to improve the dispersion of an inorganic material inside an organic matrix. In this work, polystyrene (PS) brushes were grown on the surface of iron oxide magnetic nanoparticles with atom transfer radical polymerization and a grafting‐from approach. After polymerization, the magnetic nanoparticles had a graft density of 0.9 PS chains/nm². A sacrificial initiator was used to obtain a satisfactory result for the control of the polymerization, as its addition had to generate a sufficient concentration of persistent radicals (deactivator). A variety of techniques, such as Fourier transform infrared spectroscopy, thermogravimetric analysis, gel permeation chromatography, water contact‐angle measurements, and atomic force microscopy, were used to characterize the nanoparticles. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4744–4750, 2007     

Synthesis of orientedly bioconjugated core/shell Fe3O4@Au magnetic nanoparticles for cell separation

Orientedly bioconjugated core/shell Fe₃O₄@Au magnetic nanoparticles were synthesized for cell separation. The Fe₃O₄@Au magnetic nanoparticles were synthesized by reducing HAuCl₄ on the surfaces of Fe₃O₄ nanoparticles, which were further characterized in detail by TEM, XRD and UV-vis spectra. Anti-CD3 monoclonal antibody was orientedly bioconjugated to the surface of Fe₃O₄@Au nanoparticles through affinity binding between the Fc portion of the antibody and protein A that covalently immobilized on the nanoparticles. The oriented immobilization method was performed to compare its efficiency for cell separation with the non-oriented one, in which the antibody was directly immobilized onto the carboxylated nanoparticle surface. Results showed that the orientedly bioconjugated Fe₃O₄@Au MNPs successfully pulled down CD3⁺ T cells from the whole splenocytes with high efficiency of up to 98.4%, showing a more effective cell-capture nanostructure than that obtained by non-oriented strategy. This developed strategy for the synthesis and oriented bioconjugation of Fe₃O₄@Au MNPs provides an efficient tool for cell separation, and may be further applied to various fields of bioanalytical chemistry for diagnosis, affinity extraction and biosensor.     

Fabrication of uniform magnetic nanocomposite spheres with a magnetic core/mesoporous silica shell structure

A novel kind of magnetic core/mesoporous silica shell nanospheres with a uniform particle diameter of ca. 270 nm was synthesized. The inner magnetic core endues the whole nanoparticle with magnetic properties, while the outer mesoporous silica shell shows high enough surface area and pore volume. The synthesized material is expected to be applied to targeted drug delivery and multiphase separation. The storage and release of ibuprofen into and from the pore channels of the mesoporous silica shell, as a typical example, are demonstrated.     

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.

Facile synthesis of silver core - silica shell composite nanoparticles

Combining metal nanoparticles and dielectrics (e.g. silica) to produce composite materials with high dielectric constant is motivated by application in energy storage. Control over dielectric properties and their uniformity throughout the composite material is best accomplished if the composite is comprised of metal core - dielectric shell structured nanoparticles with tunable dimensions. We have synthesized silver nanoparticles in the range of 40-100nm average size using low concentration of saccharide simultaneously as the reducing agent and electrostatic stabilizer. Coating these silver particles with silica from tetraalkoxysilanes has different outcomes depending on the alcoholic solvent and the silver particle concentration. A common issue in solution-based synthesis of core-shell particles is heterogeneous nucleation whereupon two populations are formed: the desired core-shell particles and undesired coreless particles of the shell material. We report the formation of Ag@SiO(2) core-shell particles without coreless silica particles as the byproduct in 2-propanol. In ethanol, it depends on the silver surface area available whether homogeneous nucleation of silica on silver is achieved. In methanol and 1-butanol, core-shell particles did not form. This demonstrates the significance of controlling the tetraalkoxysilane hydrolysis rate when growing silica shells on silver nanoparticles.     

One-pot synthesis of YF3@silica core/shell nanoparticles

A new one-pot synthetic method for preparing core/shell YF3@SiO2 nanoparticles with different morphologies, from spherical to elongated structures ("pearl necklace"), is described; absorbance and photoluminescence spectroscopy reveals intrinsic but no extrinsic defects in the YF3.     

Oxygen dissociation on palladium and gold core/shell nanoparticles

Oxygen dissociation reaction on gold, palladium, and gold‐palladium core/shell nanoparticles was investigated with plane wave basis set, density functional theory. Bader population analysis of charge and electron distribution was employed to understand the change of catalytic activity as a function of the nanopaticle composition. The nanoparticles’ electronic properties were investigated and the degree of core/shell charge polarization was estimated for each composition. It was found that surface polarization plays an important role in the catalysis of the initial step of electrophile reactions such as oxygen dissociation. We have investigated the O₂ adsorption energy on each nanoparticle and the activation barrier for the oxygen dissociation reaction as a function of the nanoparticle structure. Furthermore, we have investigated the influence of surface geometry, that is., surface bond lengths on the catalytic activity. We have compared the electronic and the geometry effects on the oxygen activation and dissociation. Our design rules for core/shell nanoparticles offer an effective method for control of the surface catalytic activity. Palladium and gold are often used as catalysts in synthetic chemistry. First‐principles calculations elucidate the mechanisms that control the surface reactivity of gold, palladium, and gold‐palladium core shell nanoparticles in oxygen dissociation reactions. Oxygen dissociation is promoted on the gold surface of gold/palladium core‐shell nanoparticles by favorable electron transfer from the core to the shell. Such core‐shell electronic effects can be used for fine‐tuning the nanoparticles catalytic activity.     

Decreasing the shell ratio of core-shell type nanoparticles with a ceria core and polymer shell by acid treatment

Core-shell type nanoparticles with a ceria core and polymer shell have good dispersibility. Some applications, such as fillers for increasing the refractive index and/or protecting resin films from ultraviolet (UV) light, i.e., UV cutting, require a smaller shell. Previous studies have decreased the shell weight by heat treatment in gas; however, the dispersibility of the treated nanoparticles was poor in water or alcohol. In this study, we investigated the efficacy of acid treatment for decreasing the shell weight and also evaluated the dispersibility of acid-treated nanoparticles. The thus-formed nanoparticles treated by acetic acid and formic acid show not only good dispersibility but also a well decreased shell thickness. The structure of the shell after acetic acid treatment was found to be the same as that of the untreated core-shell nanoparticles; moreover, acetic acid was present in the shell. Furthermore, by using the acetic-acid-treated nanoparticles, a transparent resin film without nanoparticle aggregation could be obtained.     

Ultrafast hydrothermal synthesis of high quality magnetic core phenol-formaldehyde shell composite microspheres using the microwave method

An ultrafast, facile, and efficient microwave hydrothermal approach was designed to fabricate magnetic Fe(3)O(4)/phenol-formaldehyde (PF) core-shell microspheres for the first time. The structure of the Fe(3)O(4)/PF core-shell microspheres could be well controlled by the in situ polycondensation of phenol and formaldehyde with magnetic Fe(3)O(4) clusters as the seeds in an aqueous solution without any surfactants. The effect of synthetic parameters, such as the feeding amounts of phenol, the dosages of formaldehyde, the reaction temperatures, and the microwave heating time, on the morphologies and sizes of the Fe(3)O(4)/PF microspheres were investigated in details. The phenol-formaldehyde shell is found to be evenly coated on Fe(3)O(4) clusters within 10 min of the irradiation. The as-prepared microspheres were highly uniform in morphology, and the method was found to allow the shell thickness to be finely controlled in the range of 10-200 nm. The properties of the composite microspheres were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetic analysis (TGA), Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). The as-prepared Fe(3)O(4)/PF microspheres were monodisperse and highly dispersible in water, ethanol, N,N-dimethyformamide, and acetone, a beneficial quality for the further functionalization and applications of the Fe(3)O(4)/PF microspheres.     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

Hot-injection synthesis of iron/iron oxide core/shell nanoparticles for T2 contrast enhancement in magnetic resonance imaging

Here we report a new, bench-top synthesis for iron/iron oxide core/shell nanoparticles via the thermal decomposition of Fe(η(5)-C(6)H(3)Me(4))(2). The iron/iron oxide core/shell nanoparticles are superparamagnetic at room temperature and show improved negative contrast in T(2)-weighted MR imaging compared to pure iron oxides nanoparticles, and have a transverse relaxivity (r(2)) of 332 mM(-1) s(-1).     

Synthesis of highly monodisperse particles composed of a magnetic core and fluorescent shell

Highly monodisperse particles composed of a magnetic silica core and fluorescent polymer shell were synthesized with a combined technique of heterocoagulation and soap-free emulsion polymerization. Prior to heterocoagulation, monodisperse, submicrometer-sized silica particles were prepared with the Stober method, and magnetic nanoparticles were prepared with a modified Massart method in which a cationic silane coupling agent of N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride was added just after coprecipitation of Fe (2+) and Fe (3+). The silica particles with negative surface potential were heterocoagulated with the magnetic nanoparticles with positive surface potential. The magnetic silica particles obtained with the heterocoagulation were treated with sodium silicate to modify their surfaces with silica. In the formation of a fluorescent polymer shell onto the silica-coated magnetic silica cores, an amphoteric initiator of 2,2'-azobis[ N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was used to control the colloidal stability of the magnetic cores during the polymer coating. The polymerization of St in the presence of a hydrophobic fluorophore of pyrene could coat the cores with fluorescent polymer shells, resulting in monodisperse particles with a magnetic silica core and fluorescent polymer shell. Measurements of zeta potential for the composite particles in different pH values indicated that the composite particles had an amphoteric property originating from VA-057 initiator.     

Optically active composite nanoparticles with chemical bonds between core and shell

A facile methodology was developed to prepare a novel type of core/shell nanoparticles (NPs) with optical activity and with chemical bonds between the cores and shells. The cores were prepared via catalytic emulsion copolymerization of substituted acetylene comonomers in which one monomer contains azo groups in side chains. For preparing the core/shell NPs, the azo groups in the seed particles (i.e., cores) subsequently act as initiators for vinyl monomer to undergo free radical polymerizations, yielding the shells. This situation resulted in chemical bonds between cores and shells. Both the seed emulsion and core/shell nanoparticle emulsion exhibited optical activity, derived from the polyacetylenes adopting helical conformation of predominant handedness. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Atom transfer radical polymerization synthesis and magnetic characterization of MnFe2O4/polystyrene core/shell nanoparticles

An atom transfer radical polymerization route is developed for the coating of MnFe2O4 nanoparticles with polystyrene yielding the core-shell nanoparticles with size <15 nm. Magnetic studies show a decrease in coercivity after the formation of polystyrene shell, which is considered due to the reduction of magnetic surface anisotropy upon polymer coating. The MnFe2O4 nanoparticles as the magnetic core were separately prepared by a reverse micelle microemulsion method. Polymerization initiators are chemically attached onto the surface of nanoparticles. The modified nanoparticles are then used as macro-initiators in the subsequent polymerization reaction. This approach provides great flexibility in the selection of magnetic core. Consequently, magnetic tunability is able to be introduced into these core/shell nanoparticulate systems to achieve the desired superparamagnetic response.