Silica shell/gold core nanoparticles: correlating shell thickness with the plasmonic red shift upon aggregation

Differences in the wavelengths of the surface plasmon band of gold nanoparticles (AuNP)--before and after particle aggregation--are widely used in bioanalytical assays. However, the gold surfaces in such bioassays can suffer from exchange and desorption of noncovalently bound ligands and from nonspecific adsorption of biomolecules. Silica shells on the surfaces of the gold can extend the available surface chemistries for bioconjugation and potentially avoid these issues. Therefore, silica was grown on gold surfaces using either hydrolysis/condensation of tetraethyl orthosilicate 1 under basic conditions or diglyceroxysilane 2 at neutral pH. The former precursor permitted slow, controlled growth of shells from about 1.7 to 4.3 nm thickness. By contrast, 3-4 nm thick silica shells formed within an hour using diglyceroxysilane; thinner or thicker shells were not readily available. Within the range of shell thicknesses synthesized, the presence of a silica shell on the gold nanoparticle did not significantly affect the absorbance maximum (~5 nm) of unaggregated particles. However, the change in absorbance wavelength upon aggregation of the particles was highly dependent on the thickness of the shell. With silica shells coating the AuNP, there was a significant decrease in the absorbance maximum of the aggregated particles, from ~578 to ~536 nm, as the shell thicknesses increased from ~1.7 to ~4.3 nm, because of increased distance between adjacent gold cores. These studies provide guidance for the development of colorimetric assays using silica-coated AuNP.     

Synthesis of core-shell nanostructures of Co3O4@SiO2 with controlled shell thickness (5-20 nm) and hollow shells of silica

Synthesis of uniform silica shell over Co3O4 nanoparticles was carried out using the colloidal solutions of Tergitol and cyclohexane. The shell could be controlled to a thickness of up to 20 nm by varying different parameters such as the amount of tetraethylorthosilicate, concentration of Co3O4 nanoparticles, reaction time and the presence of water and 1-octanol. Control of the amount of water (required for hydrolysis) appears to be the key factor for controlling the shell thickness. The methodology used is suitable to form shell over nanoparticles (present in powder form; synthesized at high temperature) which have high degree of agglomeration. Hollow shells of silica were obtained by the dissolution of the oxide core of Co3O4@SiO2 core-shell nanostructures. The composition of these core-shell nanostructures was confirmed by high-resolution transmission electron microscopy and elemental mapping by energy dispersive X-ray analysis. The hollow shells were characterized by using TEM, EDX and IR. Electron paramagnetic resonance studies of the core-shell nanostructures indicate the presence of free radicals on silica shell due to the presence of dangling bonds in the silica. Increase in the magnetic susceptibility was observed for these core-shell nanostructures.     

Structural and spectral investigations of Rhodamine (Rh6G) dye-silica core-shell nanoparticles

Rhodamine (Rh6G) dye-silica core-shell nanoparticles (DSCSNPs) have been prepared by the controlled hydrolysis and condensation of single silica precursor tetraethylorthosilicate (TEOS) using the sol-gel method. Scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis reveal that dye molecules are entrapped in silica (SiO₂) shell resulting into core-shell particles of ∼30 nm diameter. These particles are also characterized by X-ray diffraction and Fourier transforms infrared spectroscopy. The results indicate that core-shell particles are all in spherical shape and have a narrow size distribution. The fluorescent and optical properties of core-shell particles have been investigated using fluorescence and UV-Visible absorption spectra. The photoluminescence in solid or liquid medium occurs at the same wavelength. The SiO₂ shell restricts the leakage and photobleaching of dye efficiently. These core-shell nanoparticles are found to be highly luminescent and stable.     

Magnetic field control of fluorescent polymer nanorods

Nanoscale objects that combine high luminescence output with a magnetic response may be useful for probing local environments or manipulating objects on small scales. Ideally, these two properties would not interfere with each other. In this paper, we show that a fluorescent polymer host material can be doped with high concentrations of 20-30 nm diameter magnetic γ-Fe2O3 particles and then formed into 200 nm diameter nanorods using porous anodic alumina oxide templates. Two different polymer hosts are used: the conjugated polymer polydioctylfluorene and also polystyrene doped with the fluorescent dye Lumogen Red. Fluorescence decay measurements show that 14% by weight loading of the γ-Fe2O3 nanoparticles quenches the fluorescence of the polydioctylfluorene by approximately 33%, but the polystyrene/Lumogen Red fluorescence is almost unaffected. The three-dimensional orientation of both types of nanorods can be precisely controlled by the application of a moderate strength (～0.1 T) external field with sub-second response times. Transmission electron microscope images reveal that the nanoparticles cluster in the polymer matrix, and these clusters may serve both to prevent fluorescence quenching and to generate the magnetic moment that rotates in response to the applied magnetic field.     

Biomimetic approach to the formation of gold nanoparticle/silica core/shell structures and subsequent bioconjugation

The encapsulation of individual nanoparticles has gained great attention as a method for both stabilizing nanoparticles and tailoring their surface properties. In particular, the encapsulation of nanoparticles with silica shells is advantageous for bioconjugation and applications to (nano)biotechnology. Herein we report a method for constructing gold nanoparticle (AuNP)/silica core/shell hybrid structures by biomimetic silicification of silicic acids. The procedure consists of surface-initiated, atom transfer radical polymerization of 2-(dimethylamino)ethyl methacrylate (DMAEMA) from AuNPs and biomimetic polycondensation of silicic acids by using poly(DMAEMA) as a synthetic counterpart for silaffins that are found in diatoms. The resulting AuNP/silica hybrids were characterized by Fourier transform infrared spectroscopy, energy dispersive x-ray spectroscopy, UV-vis spectroscopy and transmission electron microscopy. In addition, the immobilization of biological ligands onto the hybrids was investigated for potential applications to biotechnology. As a model ligand, biotin was attached onto the AuNP/silica hybrids through substitution reaction and Michael addition reaction, and the attachment was confirmed by fluorescence microscopy after complexation with fluorescein-conjugated streptavidin.     

Synthesis and characterization of a new trifunctional magnetic-photoluminescent-oxygen-sensing nanomaterial

Magnetic Fe(2)O(3) nanoparticles coated with SiO(2) chemically doped with a Ru(II) complex were prepared using a simple solution based method. Field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) showed that the Fe(2)O(3) nanoparticles with a mean diameter of ～115?nm were successfully coated with Ru(II) complex-chemically doped SiO(2) shell with a thickness of ～30?nm. The obtained nanocomposite material showed a strong magnetic response to a varying magnetic field, exhibited the bright red triplet metal-to-ligand charge transfer ((3)MLCT) emission, and its photoluminescent intensity was sensitive to oxygen concentration. Compared with the Ru(II) complex in silica gels, the Ru(II) complex in the magnetic-optical-oxygen-sensing nanocomposite demonstrated improved thermodynamic stability of emissions. These nanocomposites are also nontoxic and easily conjugated with biomolecules. Their magnetic, photoluminescent and oxygen-sensing properties make them promising candidates for cell separation, biomarkers and optical oxygen sensors, which can measure the O(2) concentration in biological bodies.     

Synthesis of monodisperse fluorinated silica nanoparticles and their superhydrophobic thin films

Monodispersive silica nanoparticles have been synthesized via the Sto?ber process and further functionalized by adding fluorinated groups using fluoroalkylsilane in an ethanolic solution. In this process, six different sizes of fluorinated silica nanoparticles of varying diameter from 40 to 300 nm are prepared and used to deposit thin films on aluminum alloy surfaces using spin coating processes. The functionalization of silica nanoparticles by fluorinated group has been confirmed by the presence C-F bonds along with Si-O-Si bonds in the thin films as analyzed by Fourier transform infrared spectroscopy (FTIR). The surface roughnesses as well as the water contact angles of the fluorinated silica nanoparticle containing thin films are found to be increased with the increase of the diameter of the synthesized fluorinated silica nanoparticles. The thin films prepared using the fluorinated silica nanoparticles having a critical size of 119 ± 12 nm provide a surface roughness of ～0.697 μm rendering the surfaces superhydrophobic with a water contact angle of 151 ± 4°. The roughness as well as the water contact angle increases on the superhydrophobic thin films with further increase in the size of the fluorinated silica nanoparticles in the films.     

Gold-coated iron oxide nanoparticles as a T2 contrast agent in magnetic resonance imaging

Gold-coated iron oxide (Fe3O4) nanoparticles were synthesized for use as a T2 contrast agent in magnetic resonance imaging (MRI). The coated nanoparticles were spherical in shape with an average diameter of 20 nm. The gold shell was about 2 nm thick. The bonding status of the gold on the nanoparticle surfaces was checked using a Fourier transform infrared spectrometer (FTIR). The FTIR spectra confirmed the attachment of homocysteine, in the form of thiolates, to the Au shell of the Au-Fe3O4 nanoparticles. The relaxivity ratio, R2/R1, for the coated nanoparticles was 3-fold higher than that of a commercial contrast agent, Resovist, which showed the potential for their use as a T2 contrast agent with high efficacy. In animal experiments, the presence of the nanoparticles in rat liver resulted in a 71% decrease in signal intensity in T2-weighted MR images, indicating that our gold-coated iron oxide nanoparticles are suitable for use as a T2 contrast agent in MRI.     

Characterization of silica-coated Ag nanoparticles synthesized using a water-soluble nanoparticle micelle

This article describes the synthesis of silica-coated Ag nanoparticles using a water-soluble nanoparticle micelle under basic conditions. Monodispersed Ag nanoparticles with a mean particle size of 7 nm were synthesized using AgNO₃ in the presence of ascorbic acid as a reducing agent. The Ag nanoparticles were easily re-dispersed into an aqueous solution by surface adsorption of surfactant molecules, indicating formation of water-soluble nanoparticle micelles. Silica-coated Ag nanoparticles ranging in size from 50 to 100 nm were obtained by controlling the surfactant, Ag nanoparticle and tetraethylortho silicate (TEOS) concentrations. Adsorbed surfactant monolayers on Ag nanoparticles were used as a template for the silica shell because of the hydrophobicity of TEOS. In all cases, the size of the resulting particles increased linearly as these concentrations increased. Based on transmission electron microscopy, all the Ag nanoparticles were completely covered with a silica shell. In most samples, however, Ag nanoparticle size increased from 7 to 50 nm due to evaporation of hexane by heating. Although mean particle size of silica-coated Ag nanoparticles was drastically altered, characteristic absorption peaks were observed at approximately 410 nm.     

Synthesis and characterization of model silica-gold core-shell nanohybrid systems to demonstrate plasmonic enhancement of fluorescence

In this work, gold-silica plasmonic nanohybrids have been synthesized as model systems which enable tuning of dye fluorescence enhancement/quenching interactions. For each system, a dye-doped silica core is surrounded by a 15 nm spacer region, which in turn is surrounded by gold nanoparticles (GNPs). The GNPs are either covalently conjugated via mercapto silanization to the spacer or encapsulated in a separate external silica shell. The intermediate spacer region can be either dye doped or left undoped to enable quenching and plasmonic enhancement effects respectively. The study indicates that there is a larger enhancement effect when GNPs are encapsulated in the outer shell compared to the system of external conjugation. This is due to the environmental shielding provided by shell encapsulation compared to the exposure of the GNPs to the solvent environment for the externally conjugated system. The fluorescence signal enhancement of the nanohybrid systems was evaluated using a standard HRP-anti-HRP fluorescence based assay platform.     

One-pot synthesis of thermally stable gold@mesoporous silica core-shell nanospheres with catalytic activity

A facile one-pot method has been developed to synthesize uniform gold@mesoporous silica nanospheres (Au@MSNs), which have a well-defined core-shell structure with ordered mesoporous silica as a shell. The resulting Au@MSNs have a high surface area (～521 m2/g) and uniform pore size (～2.5 nm) for the mesoporous silica shell. The diameter of the gold core can be regulated by adjusting the amount of HAuCl₄. The catalytic performance of the Au@MSNs was investigated using the reduction of 4-nitrophenol as a model reaction. The mesopores of the silica shells provide direct access for the reactant molecules to diffuse and subsequently interact with the gold cores. In addition, the Au@MSNs display the great advantage of sintering-resistance to 950 °C because the mesoporous silica shells inhibit aggregation or deformation of the gold cores. The high thermal stability enables the Au@MSNs to be employed in high-temperature catalytic reactions.      

Development of Polymeric Nanoprobes with Improved Lifetime Dynamic Range and Stability for Intracellular Oxygen Sensing

A class of core‐shell nanoparticles possessing a layer of biocompatible shell and hydrophobic core with embedded oxygen‐sensitive platinum‐porphyrin (PtTFPP) dyes is developed via a radical‐initiated microemulsion co‐polymerization strategy. The influences of host matrices and the PtTFPP incorporation manner on the photophysical properties and the oxygen‐sensing performance of the nanoparticles are investigated. Self‐loading capability with cells and intracellular‐oxygen‐sensing ability of the as‐prepared nanoparticle probes in the range 0%–20% oxygen concentration are confirmed. Polymeric nanoparticles with optimized formats are characterized by their relatively small diameter (<50 nm), core‐shell structures with biocompatible shells, covalent‐attachment‐imparted leak‐free construction, improved lifetime dynamic range (up to 44 μs), excellent storage stability and photostability, and facile cell uptake. The nanoparticles’ small sensor diameter and core‐shell structure with biocompatible shell make them suitable for intracellular detection applications. For intracellular detection applications, the leak‐free feature of the as‐prepared nanoparticle sensor effectively minimizes potential chemical interferences and cytotoxicity. As a salient feature, improved lifetime dynamic range of the sensor is expected to enable precise oxygen detection and control in specific practical applications in stem‐cell biology and medical research. Such a feature‐packed nanoparticle oxygen sensor may find applications in precise oxygen‐level mapping of living cells and tissue.     

Synthesis and characterization of functionalized rhodamine B-doped silica nanoparticles

In this paper, we have prepared the fluorescent silica nanoparticles (FSNPs) covalently doped with rhodamine B (RB) dye molecules via 3-aminopropyltriethoxysilane (APTES) in reverse microemulsion method. Then by the cohydrolysis and polymerization of tetraethoxysilane (TEOS) and APTES, the surface of the FSNPs formed another thin silica shell with the functionalized amino groups. The resulting nanoparticles were characterized by infrared (IR) spectrum, transmission electron microscopy (TEM), and spectrofluorimetry. TEM showed that the particles with diameters in the range of 70–500 nm were obtained, with core and shell sizes controlled by varying component content. At the same time, the effect of RB content on the fluorescent properties of the FSNPs was studied, and the results indicated that the fluorescence intensity of the FSNPs could be precisely tuned by varying the doping amount of RB dyes. Finally, the dye leakage was also tested, displaying that RB molecules would not leak out from the silica nanoparticles after dispersing in the aqueous solution.     

Programmed Nanoparticle‐Loaded Nanoparticles for Deep‐Penetrating 3D Cancer Therapy

Tumors are 3D, composed of cellular agglomerations and blood vessels. Therapies involving nanoparticles utilize specific accumulations due to the leaky vascular structures. However, systemically injected nanoparticles are mostly uptaken by cells located on the surfaces of cancer tissues, lacking deep penetration into the core cancer regions. Herein, an unprecedented strategy, described as injecting “nanoparticle‐loaded nanoparticles” to address the long‐lasting problem is reported for effective surface‐to‐core drug delivery in entire 3D tumors. The “nanoparticle‐loaded nanoparticle” is a silica nanoparticle (≈150 nm) with well‐developed, interconnected channels (diameter of ≈30 nm), in which small gold nanoparticles (AuNPs) (≈15 nm) with programmable DNA are located. The nanoparticle (AuNPs)‐loaded nanoparticles (silica): (1) can accumulate in tumors through leaky vascular structures by protecting the inner therapeutic AuNPs during blood circulation, and then (2) allow diffusion of the AuNPs for penetration into the entire surface‐to‐core tumor tissues, and finally (3) release a drug triggered by cancer‐characteristic pH gradients. The hierarchical “nanoparticle‐loaded nanoparticle” can be a rational design for cancer therapies because the outer large nanoparticles are effective in blood circulation and in protection of the therapeutic nanoparticles inside, allowing the loaded small nanoparticles to penetrate deeply into 3D tumors with anticancer drugs.     

A new approach towards controlled synthesis of multifunctional core-shell nano-architectures: luminescent and superparamagnetic

We have developed a two-step method for synthesis of multifunctional core-shell nanoparticles with an improved structure as compared with those prepared by traditional methods used independently. The nanoparticles comprise a superparamagnetic core, an inner insulating dye-free silica shell, an outer luminescent silica shell encapsulating thousands of dye molecules and a functionalizeable surface. The innovative insertion of the isolating silica shell benefits the nanoparticles' architecture in two ways. Firstly, by keeping the dye molecules away from the magnetic core, the silica shell prevents dye luminescence quenching. Secondly, the non-magnetic shell decreases magnetic interparticle coupling, which, by reducing aggregation and preventing agglomeration, facilitates the formation of the high-quality luminescent shell in the second step of the process. The final nanoparticles being both superparamagnetic and luminescent have a great potential for theranostic applications such as ultra-sensitive detection, and in-vitro and in-vivo imaging.     

Nanoengineering of surface modified silica particles to form core-shell and hollow nanospheres of iron oxide

The method of synthesizing nanoshell of alpha-Fe2O3 on silica core nanoparticle and hollow alpha-Fe2O3 nanoparticles is described. The silica particles of approximately 160 nm diameter were surface modified using 3-aminopropyltrimethoxysilane (APS) for easy adsorption of iron on it. These particles were treated with FeCl3 and further heat treated up to 1000 degrees C to get alpha-Fe2O3 shell of thickness approximately 20 nm. The hollow iron oxide particles were prepared using sacrificial core removal using dilute HF solution. The particles were characterized for their structure, morphology, bonding and surface chemistry using Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD), Fourier Transform Infra Red Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS).     

Synthesis of dendrimer-stabilized gold-polypyrrole core-shell nanoparticles

Core-shell composite nanoparticles consisting of a gold core and polypyrrole shell were prepared and stabilized with the poly(amidoamine) dendrimer. An in situ redox polymerization technique was used in which pyrrole reduced Au3+ to Au and then oxidized to polypyrrole. The presence of gold nanoparticles as a core was characterized by its surface plasmon absorption peak at 534 nm. Fourier transform infrared spectroscopy confirmed the presence of polypyrrole on the nanoparticle surfaces. The average diameter of the core-shell nanoparticle is 8.7 +/- 1.8 nm with a shell thickness of approximately 1.5-2.0 nm as estimated from the transmission electron microscopy image. Dissolution of the Au core using KCN enabled the formation of hollow polymer nanospheres.     

Supported membranes embedded with fixed arrays of gold nanoparticles

We present a supported membrane platform consisting of a fluid lipid bilayer membrane embedded with a fixed array of gold nanoparticles. The system is realized by preforming a hexagonal array of gold nanoparticles (～5-7 nm) with controlled spacing (～50-150 nm) fixed to a silica or glass substrate by block copolymer lithography. Subsequently, a supported membrane is assembled over the intervening bare substrate. Proteins or other ligands can be associated with the fluid lipid component, the fixed nanoparticle component, or both, providing a hybrid interface consisting of mobile and immobile components with controlled geometry. We test different biochemical coupling strategies to bind individual proteins to the particles surrounded by a fluid lipid membrane. The coupling efficiency to nanoparticles and the influence of nanoparticle arrays on the surrounding membrane integrity are characterized by fluorescence imaging, correlation spectroscopy, and super-resolution fluorescence microscopy. Finally, the functionality of this system for live cell experiments is tested using the ephrin-A1-EphA2 juxtacrine signaling interaction in human breast epithelial cells.     

Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells

High pressure high temperature (HPHT) nanodiamonds (NDs) represent extremely promising materials for construction of fluorescent nanoprobes and nanosensors. However, some properties of bare NDs limit their direct use in these applications: they precipitate in biological solutions, only a limited set of bio‐orthogonal conjugation techniques is available and the accessible material is greatly polydisperse in shape. In this work, we encapsulate bright 30‐nm fluorescent nanodiamonds (FNDs) in 10–20‐nm thick translucent (i.e., not altering FND fluorescence) silica shells, yielding monodisperse near‐spherical particles of mean diameter 66 nm. High yield modification of the shells with PEG chains stabilizes the particles in ionic solutions, making them applicable in biological environments. We further modify the opposite ends of PEG chains with fluorescent dyes or vectoring peptide using click chemistry. High conversion of this bio‐orthogonal coupling yielded circa 2000 dye or peptide molecules on a single FND. We demonstrate the superior properties of these particles by in vitro interaction with human prostate cancer cells: while bare nanodiamonds strongly aggregate in the buffer and adsorb onto the cell membrane, the shell encapsulated NDs do not adsorb nonspecifically and they penetrate inside the cells.     

Nanoparticle-induced fluorescence lifetime modification as nanoscopic ruler: demonstration at the single molecule level

We combine interferometric detection of single gold nanoparticles, single molecule microscopy, and fluorescence lifetime measurement to study the modification of the fluorescence decay rate of an emitter close to a nanoparticle. In our experiment, gold particles with a diameter of 15 nm were attached to single dye molecules via double-stranded DNA of different lengths. Nanoparticle-induced lifetime modification (NPILM) has promise in serving as a nanoscopic ruler for the distance range well beyond 10 nm, which is the upper limit of fluorescence resonant energy transfer (FRET). Furthermore, the simultaneous detection of single nanoparticles and fluorescent molecules presented in this work provides new opportunities for single molecule biophysical studies.