Grafting of gold nanoparticles on polyethyleneterephthalate using dithiol interlayer

Two different procedures of grafting of polyethyleneterephthalate (PET), modified by plasma treatment, with gold nanoparticles (nanospheres) are studied. In the first procedure the PET foil was grafted with biphenyl-4,4′-dithiol and subsequently with gold nanoparticles. In the second one the PET foil was grafted with gold nanoparticles previously coated by the same dithiol. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and electrokinetic analysis were used for characterization of the polymer surface at different modification steps. Gold nanoparticles were characterized by ultraviolet–visible spectroscopy. The first procedure was found to be more effective. It was proved that the dithiol was chemically bonded to the surface of the plasma activated PET and it mediates subsequent grafting of the gold nanoparticles.     

Grafting polymers to titania nanoparticles by radical polymerization initiated by diazonium salt

The grafting of biocompatible poly(hydroxyethyl) methacrylate (PHEMA) by a very simple method onto titanium dioxide nanoparticles is reported. The selected grafting process is based on the chemical reduction of diazonium salts by reducing agents in presence of the vinylic monomer. As previously demonstrated on flat surfaces, it leads to strongly grafted and stable polymer films and has many advantages residing in a short one-step reaction occurring at atmospheric pressure, ambient air and room temperature in water. TiO₂ nanoparticles were synthesized by laser pyrolysis, giving nanoparticles with controlled size and composition. The coating, the composition, the chemical structure, and the grafted PHEMA quantities of the resulting products were investigated by Transmission electron microscopy, Infrared-attenuated total reflection, X-ray photoelectron spectroscopy, and Thermogravimetric analysis. It was demonstrated that the PHEMA shell was successfully chemically grafted onto the surface of the TiO₂ core without any significant influence on the morphology of the nanoparticles.     

Grafting of polymers from clay nanoparticles via high-dose gamma-ray irradiation

In this work, the prepared mixture of low concentration of ethyl acrylate (EA) monomers and organophilic montmorillonite (OMMT) particles in methanol solution was exposed to gamma-ray (γ-ray) irradiation. It was found that EA monomers first polymerized at relatively low radiation dose (< 10 kGy), then the polymerized PEA chains can graft onto the OMMT particles when the radiation dose increases above 185 kGy. Electron spin resonance (ESR) tests verified that a large amount of radicals could be created on PEA chains and the OMMT particles at high radiation dose. When the radicals on the PEA chains combined with the radicals on the surface of silicate layers of OMMT particles, the grafting reaction took place. Furthermore, Fourier transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) results all confirmed the presence of PEA grafting on the surface of the stacking silicate layers of OMMT particles.     

Nile red-adsorbed gold nanoparticles for selective determination of thiols based on energy transfer and aggregation

For the first time, an aqueous solution of 32-nm gold nanoparticles (GNPs), to which Nile red (NR) has been noncovalently adsorbed, has been used for sensing thiols. The as-prepared NRGNPs fluoresce weakly as a result of fluorescence resonance energy transfer between NR and the GNPs. The fluorescence of a solution containing NRGNPs at pH 4.0 increases upon the addition of thiols, but not when amines, acids, alcohols, bovine serum albumin, or hemoglobin are added. This phenomenon allows for the selective determination of thiols such as cysteamine and homocysteine, which have limits of detection of 10.2 and 10.9 nM, respectively, at a signal-to-noise ratio of 3. Interestingly, we have found that the excitation (lambda(ex) = 480 nm), emission (lambda(em) = 610 nm), and mass spectra (m/z 282) of the substance that desorbs from the GNPs in the presence of thiols are different from those of NR (lambda(ex) = 580 nm; lambda(em) = 652 nm; m/z 318), which indicates that a new product forms. When simultaneously conducting fluorescence and colorimetric assays, the selectivity of this approach further improves because at pH 4.0, the color of the NRGNPs does not change in the presence of negatively charged thiols, (e.g., N-(2-mercaptopropionyl)glycine), but changes from maroon to purple and lavender in the presence of neutral thiols (e.g., 3-mercapto-1,2-propanediol) and positively charged thiols (e.g., cysteamine), respectively, as a result of aggregation. This feature allows the types of thiols to be determined at concentrations >1.0 and 0.1 microM by the naked eye and by UV-vis absorption, respectively. Depending on the rate at which the NRGNP color changes, reduced glutathione (slow) is readily distinguishable from oxidized glutathione (no aggregation and no displacement) and from cysteine and homocysteine (fast).     

Gram-scale synthesis of soluble, near-monodisperse gold nanorods and other anisotropic nanoparticles

An aqueous surfactant-based colloidal chemical method is reported for the synthesis of anisotropic noble-metal nanoparticles on the milligram to multigram scale. Fine control of the nucleation-growth kinetics and rodlike micelle-induced breaking of symmetry at the early stage of particle growth are responsible for high-quality anisotropic nanoparticles. Near-monodisperse gold and silver nanorods, spheroids, nanowires, platelets, or cubes of 4-50 nm dimension and controllable aspect ratio can be prepared. The method may also be extended to semiconductor systems.     

Polymer-capped gold nanoparticles and ZnO nanorods form binary photocatalyst on cotton fabrics: Catalytic breakdown of dye

This work reports the immobilization of zinc oxide (ZnO) nanostructures and gold nanoparticles (AuNPs) on cotton fabrics (CFs). The ZnO and AuNPs containing CF composite materials demonstrated excellent photocatalytic activity towards degradation of the model organic dye molecule. A two-step method was used to first create zinc oxide nanorods (ZnONRs) on the CF fibers. Subsequently, these ZnONRs were decorated with cationic polymer-capped AuNPs to yield the composite materials. A one-pot synthetic route was developed to synthesize polymer-capped AuNPs. The water-soluble cationic polymers used here are polyguanidino oxanorbornenes (PGONs) at 20 kDa and polyamino oxanorbornenes (PAONs) at 20 kDa. UV–vis was utilized to monitor the composite materials’ photocatalytic activity in degrading model organic dye molecules. All the materials were characterized by FTIR, UV–visible DRS, SEM, EDX, and XRD. The composite materials exhibited excellent photocatalytic activity and recyclability in the presence of UV light.     

Distinct plasmonic manifestation on gold nanorods induced by the spatial perturbation of small gold nanospheres

The plasmon coupling between a Au nanorod and a small Au nanosphere has been studied with scattering measurements, electrodynamic simulations, and model analysis. The spatial perturbation of the nanosphere leads to distinct spectral changes of the heterodimer. The plasmonic responses, including Fano resonance, are remarkably sensitive to the nanosphere position on the nanorod, the gap distance, and the nanocrystal dimensions. The nanosphere dipole is intriguingly found to rotate around the nanorod dipole to achieve favorable attractive interaction for the bonding dipole-dipole mode. The sensitive spectral response of the heterodimer to the spatial perturbation of the nanosphere offers an approach to designing plasmon rulers of two spatial coordinates for sensing and high-resolution measurements of distance changes.     

Three-dimensional morphology and crystallography of gold nanorods

We determine the three-dimensional shape, to within 1 nm resolution, of single-crystal gold nanorods grown in the presence of silver ions using electron tomography and thickness profile measurements. We find that, contrary to the current literature, the octagonal side-facets are sparsely packed atomic planes all belonging to the same symmetry-equivalent family, {0 5 12}. Furthermore, the rod ends terminate in a pyramid with slightly different facets, and each pyramid is connected to the sides by four small {0 5 12} "bridging" facets.     

Self-assembly of small gold colloids with functionalized gold nanorods

We present a general strategy to stabilize gold nanorod suspensions with mono- and bifunctional polyethylene glycol (PEG) and to attach a controlled number of nanoparticles or biomolecules. Characterization by gel electrophoresis, transmission electron microscopy (TEM), and optical dark-field microscopy show the specific binding of functionalized nanorods to their target while avoiding nonspecific binding to substrates, matrices, and other particles. Such nanorods are well suited for self-assembly of nanostructures and single-molecule labeling.     

Synthesis of monodisperse CdS nanorods catalyzed by Au nanoparticles

Semiconductor nanocrystals (dots, rods, wires, etc.) exhibit a wide range of electrical and optical properties that differ from those of the corresponding bulk materials. These properties depend on both nanocrystal size and shape. Compared with nanodots, nanorods have an additional degree of freedom, the length or aspect ratio, and reduced symmetry, which leads to anisotropic properties. In this paper, we report the Au nanoparticlecatalyzed colloidal synthesis of monodisperse CdS nanorods. Based on systematic high resolution transmission electron microscopy studies, we propose a growth mechanism for these nanorods. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Polyelectrolyte coating provides a facile route to suspend gold nanorods in polar organic solvents and hydrophobic polymers

The widely used and versatile polyelectrolyte layer-by-layer (LbL) nanoparticle coating strategy allows for gold nanorods to be transferred from aqueous media into a broad range of polar organic solvents without aggregation. The uniform dispersity and stability of the nanorods in organic solvents allows for uniform incorporation of nanorods into a variety of hydrophobic polymers.     

Surface-driven bulk reorganization of gold nanorods

Molecular dynamic simulations are used to study the structural stability of gold nanorods upon heating. We show that the global stability of the rod is governed by the free energetics of its surface. In particular, an instability of surface facets nucleates a bulk instability that leads to both surface and bulk reorganization of the rod. The surface reorganizes to form new, more stable, {111} facets, while the underlying fcc lattice completely reorients to align with this new surface structure. Rods with predominantly {111} facets remain stable until melting.     

Optical properties of the gold nanorods tuned by lead sulfide

In this paper, the optical properties of gold nanorods (GNRs) tuned by lead sulfide (PbS) were studied. GNRs used in this work were synthesized by seed-mediated methods. Using electrostatic self-assembly methods, GNRs were modified by repetition of adsorbing oppositely charged polyelectrolyte. Then GNR-PbS nanostructure was fabricated by alternatively adsorbing Pb(2+) and S(2-) ions on the surface of polyelectrolyte-modified-GNRs. The formation of PbS nanocrystals on GNRs can effectively regulate their optical properties, including longitudinal surface plasmon resonance (LSPR) and fluorescence.     

Quantum-chemical modeling of interaction between gold nanoclusters and thiols

Ab initio calculations are used to model small Au _n nanoclusters and Au _m SH clusters. The results for the Au₆, Au₈, and Au₂₀ clusters demonstrate that the substitution of a SH group for a Au atom gives a stable cluster of the same geometry if the Au atom has an acute bond angle and a negative effective charge. The example of the Au₁₀ cluster suggests that SH substitution for Au has a stabilizing effect. The modeling results are discussed with application to self-organizing thiol monolayers on gold clusters.     

Gelation effect on the synthesis of high-aspect-ratio gold nanorods

The growth process of high-aspect-ratio gold nanorods in gelled surfactant solution was studied. As for the application of gold nanorods, the surface plasmon is quite useful, whose absorption depends on their aspect ratio. Hence it is important to synthesize gold nanorods with favorable aspect ratio in high yield. For shorter nanorods (aspect ratio < -10), the synthesis and the growth mechanism have been studied well. For the longer nanorods (aspect ratio > -30), however, the growth mechanism has not yet been understood well, although it has been known that the high-aspect-ratio gold nanorods could be synthesized in high yield in gelled surfactant solution. In this paper, we studied the relationship between the growth process of high-aspect-ratio gold nanorods and the gelation of surfactant growth-solution. Small angle X-ray scattering (SAXS) revealed the microscopic feature of gelation as the structural transition of self-assembly of surfactant molecules from micellar to lamellar. These results will be helpful for better understanding on the growth mechanism of high-aspect-ratio gold nanorods.     

The effect of gold nanorods on cell-mediated collagen remodeling

Cardiac fibroblasts, the noncontractile cells of the heart, contribute to myocardial maintenance through the deposition, degradation, and organization of collagen. Adding polyelectrolyte-coated gold nanorods to three-dimensional constructs composed of collagen and cardiac fibroblasts reduced contraction and altered the expression of mRNAs encoding beta-actin, alpha-smooth muscle actin, and collagen type I. These data show that nanomaterials can modulate cell-mediated matrix remodeling and suggest that the targeted delivery of nanomaterials can be applied for antifibrotic therapies.     

Nanosphere molecularly imprinted polymers doped with gold nanoparticles for high selectivity molecular sensors

We report the first attempt of using molecularly imprinted polymers (MIPs) in the shape of nanoparticles that were doped with gold nanoparticles (AuNPs) for surface enhanced Raman scattering (SERS)-based sensing of molecular species.Specifically,AuNPs doped molecularly imprinted nano-spheres (AuNPs@nanoMIPs) were synthesized by one-pot precipitation polymerization using Sudan Ⅳ as the template for the SERS sensing.The AuNPs@nanoMIPs were characterized by various modes of scanning transmission electron microscopy (STEM) that showed the exact location of the AuNPs inside the MIP particles.The effects of Au concentration and solution stirring on the shape and the polydispersity of the particles were studied.Significant enhancement of the Raman signals was observed only when the MIP particles were doped with the AuNPs.The SERS signal improved significantly with increase in the Au concentration inside the AuNPs@nanoMIPs.Selectivity measurements of the Sudan Ⅳ imprinted AuNPs@nanoMIPs carried out with different Sudan derivatives showed high selectivity of the AuNPs-doped MIP particles.     

Multiple surface plasmon modes for a colloidal solution of nanoporous gold nanorods and their comparison to smooth gold nanorods

The paper represents a novel approach to investigating localized surface plasmon (LSP) resonance modes of nanoporous Au nanorods (NRs) in a solution phase with control over surface morphology. Au NRs, which have distinctive features such as nanopores and ligaments, showed interesting LSP resonance modes depending on the surface morphology and the total length of the structure. Compared with the analogous smooth surface NRs, the LSP modes of nanoporous NRs are red-shifted, which can be interpreted as a longer effective rod length and larger amplitude of plasmon oscillation.     

Analysis of rat plasma proteins desorbed from gold and methyl- and hydroxyl-terminated alkane thiols on gold surfaces

It is believed that adsorbed blood or plasma components, such as water, peptides, carbohydrates and proteins, determine key events in the concomitant inflammatory tissue response close to implants. The aim of the present study was to develop a procedure for the collection and analysis of minor amounts of proteins bound to solid metal implant surfaces. The combination of a sodium dodecyl sulfate washing method coupled with a polyacylamide gel electrophoretic protein separation technique (SDS–PAGE), Western blot and image analysis enabled the desorption, identification and semiquantification of specific proteins. The analyzed proteins were albumin, immunoglobulin G, fibrinogen and fibronectin. Concentration procedures of proteins were not required with this method despite the small area of the test surfaces. The plasma proteins were adsorbed to pure gold and hydroxylated and methylated gold surfaces, which elicit different tissue responses in vivo and plasma protein adsorption patterns in vitro. The image analysis revealed that the pure gold surfaces adsorbed the largest amount of total and specific proteins. This is in accordance with previous ellipsometry/antibody experiments in vitro. Further, the principles described for the protein analysis can be applied on implant surfaces ex vivo. ©©2000 Kluwer Academic Publishers