Synthesis of core–shell nanoparticles with a Pt nanoparticle core and a silica shell

A method to prepare a core–shell structure consisting of a Pt metal core coated with a silica shell (Pt(in)SiO₂) is described herein. A silica shell was grown on poly(vinylpyrrolidone) (PVP)-stabilized Pt nanoparticles 2–3 nm in size through hydrolysis and condensation reactions of tetraethyl orthosilicate (TEOS) in a water/ethanol mixture with ammonia as a catalyst. This process requires precise control of the reaction conditions to avoid the formation of silica particles containing multiple Pt cores and core-free silica. The length of PVP molecules, water content, concentration of ammonia and Pt nanoparticles in solution were found to significantly influence the core–shell structure. By optimizing these parameters, it was possible to prepare core–shell particles each containing a single Pt nanoparticle with a silica layer coating approximately 10 nm thick.     

High quality and tuneable silica shell–magnetic core nanoparticles

Obtaining small (<50 nm), monodispersed, well-separated, single iron oxide core–silica (SiO₂) shell nanoparticles for biomedical applications is still a challenge. Preferably, they are synthesised by inverse microemulsion method. However, substantial amount of aggregated and multicore core–shell nanoparticles is the undesired outcome of the method. In this study, we report on the production of less than 50 nm overall size, monodispersed, free of necking, single core iron oxide–SiO₂ shell nanoparticles with tuneable shell thickness by a carefully optimized inverse microemulsion method. The high degree of control over the process is achieved by understanding the mechanism of core–shell nanoparticles formation. By varying the reaction time and precursor concentration, the thickness of silica layer on the core nanoparticles can be finely adjusted from 5 to 13 nm. Residual reactions during the workup were inhibited by a combination of pH control with shock freezing and ultracentrifuging. These high-quality tuneable core–shell nanocomposite particles exhibit superparamagnetic character and sufficiently high magnetization with great potential for biomedical applications (e.g. MRI, cell separation and magnetically driven drug delivery systems) either as-prepared or by additional surface modification for improved biocompatibility.     

Fabrication of cyclodextrin-functionalized superparamagnetic Fe3O4/amino-silane core–shell nanoparticles via layer-by-layer method

This paper presents a feasible protocol for the preparation of a novel versatile nanocomposite possessing superparamagnetism via a layer-by-layer method. We combined (3-aminopropyl)triethoxysilane-coated magnetic Fe₃O₄ nanoparticles (APTES-MNPs) with β-cyclodextrin (β-CD). The following unusual features were integrated in a single nano-system: (a) the silane coating outside the magnetic Fe₃O₄ cores derived from the hydrolysis of APTES acted as a coupling agent and provided amino group (–NH₂) for linking the CD molecule; (b) the outermost CD moieties can function as inclusion sites and specific containers for drugs and biomolecules; (c) the innermost magnetic cores were able to sense and respond to an externally applied magnetic field and their behaviors in vivo or in vitro can be artificially manipulated and navigated. The obtained nanocomposite turned out to be superparamagnetic with a relatively high saturation magnetization value of 69 emu g^?1, which implies potentially promising applications in magnetic drug delivery technology and bioseparation.     

Size-dependent thermal stresses in the core–shell nanoparticles

The thermal stress in a magnetic core–shell nanoparticle during a thermal process is an important parameter to be known and controlled in the magnetization process of the core–shell system. In this paper we analyze the stress that appears in a core–shell nanoparticle subjected to a cooling process. The external surface temperature of the system, considered in equilibrium at room temperature, is instantly reduced to a target temperature. The thermal evolution of the system in time and the induced stress are studied using an analytical model based on a time-dependent heat conduction equation and a differential displacement equation in the formalism of elastic displacements. The source of internal stress is the difference in contraction between core and shell materials due to the temperature change. The thermal stress decreases in time and is minimized when the system reaches the thermal equilibrium. The radial and azimuthal stress components depend on system geometry, material properties, and initial and final temperatures. The magnitude of the stress changes the magnetic state of the core–shell system. For some materials, the values of the thermal stresses are larger than their specific elastic limits and the materials begin to deform plastically in the cooling process. The presence of the induced anisotropy due to the plastic deformation modifies the magnetic domain structure and the magnetic behavior of the system.     

Synthesis of NiAu alloy and core–shell nanoparticles in water-in-oil microemulsions

NiAu alloy nanoparticles with various Ni/Au molar ratios were synthesized by the hydrazine reduction of nickel chloride and hydrogen tetrachloroaurate in the microemulsion system. They had a face-centered cubic structure and a mean diameter of 6–13 nm, decreasing with increasing Au content. As Au nanoparticles did, they showed a characteristic absorption peak at about 520 nm but the intensity decreased with increasing Ni content. Also, they were nearly superparamagnetic, although the magnetization decreased significantly with increasing Au content. Under an external magnetic field, they could be self-organized into the parallel lines. In addition, the core–shell nanoparticles, Ni₃Au₁@Au, were prepared by the Au coating on the surface of Ni₃Au₁ alloy nanoparticles. By increasing the hydrogen tetrachloroaurate concentration for Au coating, the thickness of Au shells could be raised and led to an enhanced and red-shifted surface plasmon absorption.     

One-pot synthesis and characterization of rhodamine derivative-loaded magnetic core–shell nanoparticles

A new method to produce elaborate nanostructure with magnetic and fluorescent properties in one entity is reported in this article. Magnetite (Fe₃O₄) coated with fluorescent silica (SiO₂) shell was produced through the one-pot reaction, in which one reactor was utilized to realize the synthesis of superparamagnetic core of Fe₃O₄, the formation of SiO₂ coating through the condensation and polymerization of tetraethylorthosilicate (TEOS), and the encapsulation of tetramethyl rhodamine isothiocyanate-dextran (TRITC-dextran) within silica shell. Transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, and X-ray diffraction (XRD) were carried out to investigate the core–shell structure. The magnetic core of the core–shell nanoparticles is 60 ± 10 nm in diameter. The thickness of the fluorescent SiO₂ shell is estimated at 15 ± 5 nm. In addition, the fluorescent signal of the SiO₂ shell has been detected by the laser confocal scanning microscopy (LCSM) with emission wavelength (λ_em) at 566 nm. In addition, the magnetic properties of TRITC-dextran loaded silica-coating iron oxide nanoparticles (Fe₃O₄@SiO₂ NPs) were studied. The hysteresis loop of the core–shell NPs measured at room temperature shows that the saturation magnetization (M _s) is not reached even at the field of 70 kOe (7T). Meanwhile, the very low coercivity (H _c) and remanent magnetization (M _r) are 0.375 kOe and 6.6 emu/g, respectively, at room temperature. It indicates that the core–shell particles have the superparamagnetic properties. The measured blocking temperature (T _B) of the TRITC-dextran loaded Fe₃O₄@SiO₂ NPs is about 122.5 K. It is expected that the multifunctional core–shell nanoparticles can be used in bio-imaging.     

Co x Ag1−x core–shell nanoparticles: magnetic and magneto-optical studies

The magneto-optical properties of 14-nm Co _x Ag_1?x core–shell nanoparticles (x=0.7, 0.8, and 0.35) deposited on different substrates are investigated at room temperature in the photon-energy range from 0.8 to 4.8 eV. Particles with low Ag content show spectra very similar to pure Co nanoparticles while particles with high Ag content have totally different features, where the Ag plasma edge dominates the spectra. The spectral features of the polar Kerr rotation depend on particle composition. The ageing process and development of an oxide layer influence the particles’ core–shell structures and magnetization curves. Co-rich particles exhibit lower resistance to the oxidation process as compared to Ag-rich ones. The quality of the nanoparticles was checked by transmission electron microscopy in respect of time scale.     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Encapsulation and controlled release from core–shell nanoparticles fabricated by plasma polymerization

Core–shell nanostructures have been synthesized by plasma deposition in radio-frequency plasma reactor. Silica and KCl nanoparticles were encapsulated by deposition of isopropanol-based films of amorphous hydrogenated carbon. Through control of the deposition time, under constant deposition rate of 1 nm/min, particles are encapsulated in a layer of plasma polymer with thickness between 15 and 100 nm. Films are robust, chemically inert, thermally stable up to 250°C. The permeability of the shells is determined by depositing films of various thickness onto KCl nanoparticles and monitoring the dissolution of the core in aqueous solution. The dissolution profile is characterized by an initial rapid release, followed by a slow release that lasts up to 30 days for the thickest films. The profile is analyzed by Fickian diffusion through a spherical matrix. We find that this model captures very accurately the entire release profile except for the first 12 hours during which, the dissolution rate is higher than that predicted by the model. The overall diffusion coefficient for the dissolution of KCl is 3 × 10⁻²¹ m²/s.     

CuGaS2 hollow spheres from Ga–CuS core–shell nanoparticles

A liquid gallium emulsion was prepared as a starting material using ultrasound treatment in ethylene glycol. Core–shell particles of Ga@CuS were successfully synthesized by deposition of a CuS layer on gallium droplets through sonochemical deposition of copper ions and thiourea in an alcohol media. The core and shell of Ga@CuS products were composed of amorphous gallium metal and covellite phase CuS, which transformed into chalcopyrite CuGaS₂ hollow spheres after sulfurization at 450 °C, which was the lowest crystallization temperature. The formation of hollow nanostructures was ascribed to the Kirkendall mechanism, in which liquid gallium particles play an important role as reactive templates. In conclusion, we obtained CuGaS₂ hollow spheres with a 430 nm outer diameter and 120 nm shell thickness that had the same crystal structure and electrical properties as bulk CuGaS₂.     

Synthesis and characterisation of highly fluorescent core–shell nanoparticles based on Alexa dyes

Current and future developments in the emerging field of nanobiotechnology are closely linked to the rational design of novel fluorescent nanomaterials, e.g. for biosensing and imaging applications. Here, the synthesis of bright near infrared (NIR)-emissive nanoparticles based on the grafting of silica nanoparticles (SNPs) with 3-aminopropyl triethoxysilane (APTES) followed by covalent attachment of Alexa dyes and their subsequent shielding by an additional silica shell are presented. These nanoparticles were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM) and fluorescence spectroscopy. TEM studies revealed the monodispersity of the initially prepared and fluorophore-labelled silica particles and the subsequent formation of raspberry-like structures after addition of a silica precursor. Measurements of absolute fluorescence quantum yields of these scattering particle suspensions with an integrating sphere setup demonstrated the influence of dye labelling density-dependent fluorophore aggregation on the signaling behaviour of such nanoparticles.     

Green synthesis and characterization of Au@Pt core–shell bimetallic nanoparticles using gallic acid

In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core–shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl₄⁻ and PtCl₆²⁻, where the AuCl₄⁻ ions are preferentially reduced to Au cores and the PtCl₆²⁻ ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl₄/H₂PtCl₆, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core–shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH₄ reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core–shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.     

Stable and pH-responsive core–shell nanoparticles based on HEC and PMAA networks via template copolymerization

Taking advantage of the specific hydrogen bonding interactions, stable and pH-responsive core–shell nanoparticles based on hydroxyethyl cellulose (HEC) and polymethacrylic acid (PMAA) networks, with a 〈D _h 〉 size ranging from 190 to 250 nm, can be efficiently prepared via facile one-step co-polymerization of methacrylic acid (MAA) and N,N′-methylenebisacrylamide (MBA) on HEC template in water. Using dynamic light scattering, electrophoretic light scattering, fluorescence spectrometry, thermo-gravimetric analysis, TEM, and AFM observations, the influence of crosslinker MBA as well as the reaction parameters were studied. The results show that after the introduction of crosslinker MBA, the nanoparticles became less compact; their size exhibited a smaller pH sensitivity, and their stability against pH value was improved greatly. Furthermore, the size, structure, and pH response of the nanoparticles can be adjusted via varying the reaction parameters: nanoparticles of smaller size, more compact structure, and higher swelling capacity were produced as pH value of the reaction medium increased or the HEC/MAA ratio decreased; while nanoparticles of smaller size, less compact structure and smaller swelling capacity were produced as the total feeding concentration increased.     

Synthesis of high quality and monodisperse CdS:Mn/ZnS and CdS:Mn/CdS core–shell nanoparticles

CdS:Mn²⁺/ZnS and CdS:Mn²⁺/CdS core–shell nanoparticles were synthesized in aqueous medium via chemical precipitation method in an ambient atmosphere. Polyvinylpyrrolidone (PVP) was used as a capping agent. The effect of the shell (ZnS and CdS) thickness on CdS:Mn²⁺ nanoparticles was investigated. Inorganically passivated core/shell nanocrystals having a core (CdS:Mn²⁺) diameter of 4 nm and a ZnS-shell thickness of ∼0.5 nm exhibited improved PL intensity. Optimum concentration of doping ions (Mn²⁺) was selected through optical study. For all the core–shell samples two emission peaks were observed, the first one is band edge emission in the lower wavelength side due to energy transfer to the Mn²⁺ ions in the crystal lattice; the second emission is characteristic peak of Mn²⁺ ions (⁴T₁ → ⁶A₁). The XRD, TEM and PL results showed that the synthesized core–shell particles were of high quality and monodisperse.     

One-step sonochemical syntheses of Ni@Pt core–shell nanoparticles with controlled shape and shell thickness for fuel cell electrocatalyst

We demonstrate a facile one-step method to synthesize Ni@Pt core–shell nanoparticles (NPs) with a control over the shape and the Pt-shell thickness of the NPs. By adjusting the relative reactivity of the Pt and Ni reagents in ultrasound-assisted polyol reactions, two Ni@Pt NP samples of the same composition (Ni/Pt = 1) and size (3–4 nm) but with different particle shape (octahedral vs. truncated octahedral) and different Pt-shell thicknesses (1–2 vs. 2–3 monolayer) are obtained. The control is achieved by using different Ni reagents, Ni(acac)₂ (acac = acetylacetonate) and Ni(hfac)₂ (hfac = hexafluoroacetylacetonate). A reaction mechanism that can explain all of the observations is proposed. The Ni@Pt NPs show up to threefold higher mass activity than pure Pt NPs in oxygen reduction reaction. Between the two Ni@Pt NP samples, the one composed of octahedral NPs with the thicker Pt-shell has higher activity than the other.     

Structure and magnetism of Co:CoO core–shell nanoclusters

Transmission electron microscopy (TEM) and electron diffraction (ED) are used to investigate the nanostructures of two ensembles of Co:CoO core–shell particles. TEM images show that particles of size about 12 nm are almost fully oxidized, while particles with size about 18 nm have a core–shell structure where a Co core is surrounded by a shell of CoO. ED simulation confirms that the larger particles have an fcc-structured Co core and a rock-salt CoO shell structure, while the smaller particles mostly have the rock-salt CoO structure. The core–shell structure is responsible for the unusual magnetic properties of the Co:CoO nanoclusters, especially the occurrence of inverted hysteresis loops (proteresis), but previous research has been indirect, largely based on magnetic measurements and on a cross-comparison with granular materials. Our measurements show that the structures have ferromagnetic fcc Co cores of varying sizes down to 1 nm which are surrounded by antiferromagnetic rock-salt CoO shells. The core radii obtained from the TEM pictures are used to estimate the exchange interactions responsible for proteresis and to pinpoint the core-size window in which proteresis occurs.     

Anomalous infrared and visible light absorption and local structure of Ag–Au core/shell nanoparticles

We measured infrared and visible light absorption spectra and EXAFS for Ag–Au core/shell particles. The shell thickness and core diameter can be evaluated from the EXAFS results, which are almost consistent with those obtained using TEM. The influence of a thinner shell only slightly appeared in the visible absorption spectra, whereas the influence appeared strongly in the infrared absorption spectra. The spectra of the material in the vicinity of the particle surface appear in the infrared spectra. On the other hand, the spectra of the rather more internal material are observed in the visible spectra. It is thought that the influence of the core metal is different in the visible spectra from the infrared spectra. By considering the penetration depth, this phenomenon can be explained.     

Effective gene delivery based on facilely synthesized “core–shell” Ag@PDA@PEI nanoparticles

Journal of Nanoparticle Research - The management of diabetes, in contrast to the treatment of the disease, is basically aimed at controlling the blood glucose level. Besides the primary changes...     

ZnO–CuO core–shell nanorods and CuO-nanoparticle–ZnO-nanorod integrated structures

ZnO–CuO core–shell nanorods and CuO-nanoparticle–ZnO-nanorod integrated structures were synthesized for the first time by a two-stage solution process. Scanning electron microscopy and high-resolution transmission electron microscopy show that the diameter and the length of the nanorods are around 60 and 800 nm, respectively. The morphologies of outer CuO could be varied from nanoparticles to nanoshells by adjusting the solvent and dipping processes of copper (II) nitrate solution. The CuO nanoparticles are single-crystalline or highly textured structures with size of around 30 nm. The CuO shell with thickness of around 10 nm is constructed of nanocrystals with sizes in the range of 3–10 nm embedded in an amorphous matrix. Room-temperature cathodoluminescence measurements of the CuO–ZnO nanocomposites exhibit relatively sharp ultraviolet emissions at 380 nm as well as broad green and yellow emissions at 500 and 585 nm. The p-CuO/n-ZnO one-dimensional nanocomposites are promising for optoelectronic nanodevice applications.