Self-assembly of gold nanoparticles on fullerene nanospheres

A C60-pyrrolidine derivative with a hydrophobic-hydrophilic-hydrophobic structure (2-{3,4-di{2-[2-(2-decyloxyethoxy)ethoxy]ethoxy}}phenyl-3,4-fulleropyrrolidine, DTPF) has been synthesized and well-characterized. This compound could form stable nanospheres by simply injectingits tetrahydrofuran (THF) solution into water and then removing THF by purging gaseous nitrogen in sequence. Novel nanoassemblies of DTPF nanospheres and gold nanoparticles were obtained through in situ photoreduction of aqueous HAuCl4 in the presence of DTPF nanospheres, which were confirmed by UV-visible, transmission electron microscopy, X-ray powder diffraction, and X-ray photoelectron spectroscopy methods. It is proposed that the interaction between the positively charged nitrogen atom and the gold nanoparticles is the main driving force for the formation of the nanoassemblies.     

Formation of gold nanoparticles catalyzed by platinum nanoparticles: assessment of the catalytic mechanism

The understanding of how the formation of metal nanoparticles in aqueous solutions is influenced by the presence of presynthesized nanoparticles is important for precise control over size, shape, and composition of nanoparticles. New insights into the catalytic mechanism of Pt nanoparticles are gained by studying the formation of gold nanoparticles from the reduction of AuCl(4)(-) in aqueous solution in the presence of presynthesized Pt nanoparticles as a model system. The measurement of changes of the surface plasmon resonance band of gold nanoparticles, along with TEM analysis of particle size and morphology, provided an important means for assessing the reaction kinetics. The reductive mediation of Pt-H species on the Pt nanocrystal surface is believed to play an important role in the Pt-catalyzed formation of gold nanoparticles. This important physical insight is evidenced by comparison of the rates of the Pt-catalyzed formation of gold nanoparticles in the presence and in the absence of hydrogen (H(2)), which adsorb dissociatively on a Pt nanocrystal surface forming Pt-H species. Pt-H effectively mediates the reduction of AuCl(4)(-) toward the formation of gold nanoparticles. Implications of the findings to the controllability over size, composition, and morphology of metal nanoparticles in the aqueous synthesis environment are also discussed.     

Morphology-dependent voltage sensitivity of a gold nanostructure

Gold nanostructures of various morphologies, including nanospheres, nanorods, nanoprisms, and thin films, were immobilized on ITO-coated coverslips in order to investigate the response of their scattering to potential. Shifts in the plasmon band obtained by potential-modulated spectroscopic imaging indicated that the voltage sensitivity of the gold nanostructure is dependent on its morphology, with nanospheres exhibiting the lowest sensitivity and ultrathin gold films exhibiting the highest. The effects of potential on gold nanoparticles are in qualitative agreement with Mie and Gans' theories in which the shift of the gold plasma frequency is due to the charging-discharging of the nanoparticles.     

Fabrication of size-tunable gold nanoparticles array with nanosphere lithography, reactive ion etching, and thermal annealing

Two-dimensional ordered arrays of gold (Au) nanoparticles were fabricated using two different variants of the nanosphere lithography technique. First, ordered arrays of polystyrene nanospheres on Si substrate were used as deposition masks through which gold films were deposited by electron beam evaporation. After the removal of the nanospheres, an array of triangular Au nanodisks was left on the Si substrate. After thermal annealing at increasing temperature, systematic shape transition of the nanostructures from original triangular Au nanodisks to rounded nanoparticles was observed. This approach allows us to systematically vary the size and morphology of the particles. In the second and novel technique, we made use of reactive ion etching to simultaneously reduce the dimension of the masking nanospheres and create arrays of nanopores on the substrate prior to the deposition of the Au films. These samples were subsequently annealed, which resulted in size-tunable and ordered Au nanoparticle arrays with the nanoparticles nested in the nanopores of the templated substrate. With the nanoparticles anchored in the nanopores, the substrate could be useful as a template for growth of other nanomaterials.     

Direct facile approach to the fabrication of chitosan-gold hybrid nanospheres

Chitosan-gold hybrid nanospheres were prepared through a direct facile approach that utilized cross-linked composite nanospheres consisting of low-molecular-weight chitosan (LWCS) and ethylenediaminetetraacetic acid (EDTA) as a precursor reaction system. EDTA was employed not only to construct the counterion interaction-based composite nanospheres with the cationic chitosan but also as the reductant for subsequent in situ gold salt reduction within the LWCS-EDTA composite nanospheres. This approach elegantly ensured that each and every nanosphere was loaded with gold nanoparticles and no nonembedded free gold nanoparticles would exist in the dispersing medium. Moreover, becauseof the noncovalent interaction between LWCS and EDTA, the EDTA reductant can be easily removed from the cross-linked nanospheres, and "pure" chitosan-gold hybrid nanospheres can be obtained. The obtained chitosan-gold hybrid nanospheres were found to have a tunable size and good dispersing stability within a wide pH range. The embedded gold nanoparticles were in the range from several to several tens of nanometers, which may be useful for sensing and imaging. Morphology studies indicated that most of the loaded gold nanoparticles were located in the interior of the hybrid nanospheres. Taking into account the good biocompatibilities of LWCS, abundant functional (amino) groups in chitosan, and the mild preparation conditions, we find that the chitosan-gold hybrid nanospheres prepared here may have tremendous potential in advanced biomedical applications.     

Effects of shape and charge of colloidal gold nanoparticles in colorimetric determination of DNA sequences

The principles of colorimetric detecting oligonucleotides with the help of gold nanospheres and nanorods are discussed. Marker sequences of fragments of HIV-1 genome and Bacillus anthracis are used as models. Experimental data are reported that demonstrate the influence of gold nanorod morphology on the reproducibility of colorimetric tests. A new method is proposed for detecting oligonucleotides based on the application of positively charged gold nanospheres in combination with absorption spectroscopy and dynamic light scattering. Charge reversal of negatively charged gold nanospheres is implemented through the bilayer adsorption of cetyltrimethylammonium bromide molecules. The sensitivity of the proposed method is comparable with the detection of DNA sequences via the colorimetric protocol using nanorods, but it is more simple and stable from the viewpoint of realization. It is shown that the colorimetric tests using gold nanorods and nanospheres do not provide reliable information on the presence of single- and three-base mismatches in target oligonucleotides.     

Green synthesis of gold nanoparticles using glycerol-incorporated nanosized liposomes

There has been enormous interest in the last decade in development methods for the inorganic synthesis of metallic nanoparticles of desired sizes and shapes because of their unique properties and extensive applications in catalysis, electronics, plasmonics, and sensing. Here we report on an environmentally friendly, one-pot synthesis of metallic nanoparticles, which avoids the use of organic solvents and requires mild experimental conditions. The developed method uses liposomes as nanoreactors, where the liposomes were prepared by encapsulating chloroauric acid and exploited the use of glycerol, incorporated within the lipid bilayer as well as in its hydrophilic core, as a reducing agent for the controlled preparation of highly homogeneous populations of gold nanoparticles. The effects of temperature, the presence of a capping agent, and the concentration of glycerol on the size and homogeneity of the nanoparticles formed were investigated and compared with solution-based glycerol-mediated nanoparticle synthesis. Well-distributed gold nanoparticle populations in the range of 2-8 nm were prepared in the designed liposomal nanoreactor with a clear dependence of the size on the concentration of glycerol, the temperature, and the presence of a capping agent whereas large, heterogeneous populations of nanoparticles with amorphous shapes were obtained in the absence of liposomes. The particle morphology and sizes were analyzed using transmission electron microscopy imaging, and the liposome size was measured using photon correlation spectroscopy.     

Electrophoretic separation of gold nanoparticles according to bifunctional molecules‐induced charge and size

Gold nanospheres modified with bifunctional molecules have been separated and characterized by using agarose gel electrophoresis as well as optical spectroscopy and electron microscopy. The electrophoretic mobility of a gold nanosphere capped with 11‐mercaptoundecanoic acid (MUA) has been found to depend on the number of MUA molecules per gold nanosphere, indicating that it increases with the surface charge of the nanoparticle. The extinction spectrum of gold nanospheres capped with MUA at an MUA molecules per gold nanosphere value of 1000 and connected via 1,6‐hexanedithiol (HDT) decreases by 33% in magnitude and shifts to the red as largely as 22 nm with the increase of the molar ratio of HDT to MUA (R_HM). Gold nanospheres capped with MUA and connected via HDT have been separated successfully using gel electrophoresis and characterized by measuring reflectance spectra of discrete electrophoretic bands directly in the gel and by monitoring transmission electron microscope images of gold nanoparticles collected from the discrete bands. Electrophoretic mobility has been found to decrease substantially with the increment of HDT to MUA, indicating that the size of aggregated gold nanoparticles increases with the concentration of HDT.     

Role of halide ions and temperature on the morphology of biologically synthesized gold nanotriangles

In this paper, we demonstrate the effect of halide ions on the formation of biogenically prepared gold nanotriangles using the leaf extract of lemongrass (Cymbopogon flexuosus) plant. We have also studied the effect of halide ions on the morphology of biogenic nanotriangles. It has been shown that iodide ions have a greater propensity to transform flat gold nanotriangles into circular disk-like structures as compared to other halide ions. The study also suggests that the presence of Cl- ions during the synthesis promotes the growth of nanotriangles, whereas the presence of I- ions distorts the nanotriangle morphology and induces the formation of aggregated spherical nanoparticles. The change in the morphology of gold nanotriangles has been explained in terms of the ability of the halide ions to stabilize or inhibit the formation of (111) faces to form [111] oriented gold nanotriangles. Last, we have also shown that the temperature is an important parameter for controlling the aspect ratio and the relative amounts of gold nanotriangles and spherical particles. The results show that, by varying the temperature of reaction condition, the shape, size, and optical properties of anisotropic nanoparticles can be fine-tuned.     

Liposome induced self-assembly of gold nanoparticles into hollow spheres

Gold nanoparticles were prepared by the reduction of [(C7H15)4N]+ [AuCl4]- with 3,4-ethylenedioxythiophene (EDOT) as reductant in toluene solution. The employed stabilizers include 3,3'-thiodipropionic acid (TDPA), 1-dodecanethiol (DDT), (+/-)-10-camphorsulfonic acid (CSA), and 11-mercaptoundecanoic acid (MUA). The reaction processes were tracked by UV-vis and FT-IR spectroscopy, and the as-prepared gold nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy measurements. When TDPA and MUA, which possess both -S- and -COOH groups, were used as the stabilizer in the preparation, the as-prepared nanoparticles could self-assemble into hollow spheres. While when DDT with a -SH group or CSA with a -SO3H group was used as the protecting agents, only discrete gold nanoparticles were observed. The results show that the groups of both -S- and -COOH in the stabilizer play an important role in forming the hollow nanospheres. It is proposed that the formation mechanism of the hollow spheres is a liposome that formed between -COO- and [(C7H15)4 N]+ could act as a template to induce the self-assembly of the gold nanoparticles into the hollow spheres.     

Tailored core-shell-shell nanostructures: sandwiching gold nanoparticles between silica cores and tunable silica shells

Size tunable and structure tailored core-shell-shell nanospheres containing silica cores, gold nanoparticle shells, and controlled thicknesses of smooth, corrugated, or porous silica shells over the gold nanoparticles have been synthesized. The synthesis involved the deposition of gold nanoparticles on silica cores, followed by sol-gel processing of tetraethoxysilane (TEOS) or sodium silicate to form dense or porous silica shells, respectively, over the gold nanoparticles. The structures and sizes of the resulting core-shell-shell nanospheres were found to heavily depend on the sizes of the core nanoparticles, the relative population of the gold nanoparticles on each core, and the concentration of TEOS. While a higher TEOS concentration resulted in thicker and more uniform silica shells around individual larger silica cores (approximately > or =250 nm in diameter), the same TEOS concentration resulted in aggregated and twin core-shell-shell nanostructures for smaller silica cores (approximately < or =110 nm in diameter). The thinner silica shells were synthesized by using a lower TEOS concentration. By using sodium silicate (Ung et al. J. Phys. Chem. B 1999, 103, 6770), the porous silica shells were synthesized. Controlled chemical etching of the core-shell-shell nanoparticles with an aqueous KCN solution resulted in corrugated silica shells around the gold nanoparticles or corrugated silica nanospheres with few or no gold nanoparticles. This has allowed synthesis of new types of core-shell-shell nanoparticles with tailored corrugated shells. The nanoporous silica shells provided accessible structures to the embedded metal nanoparticles as observed from the electrochemical response of the gold nanoparticles.     

Synthesis of different-sized gold nanostars for Raman bioimaging and photothermal therapy in cancer nanotheranostics

Gold nanoparticles(AuNPs) have been attractive for nanomedicine because of their pronounced optical properties.Here,we customerized the methods to synthesize two types of gold nanostars,Au nanostars-1 and Au nanostars-2,which have different spire lengths and optical properties,and also spherical AuNPs.Compared to nanospheres,gold nanostars were less toxic to a variety of cells,including macrophages.Au nanostars-1 and Au nanostars-2 also manifested a similar pattern of tissue distribution upon in vivo administration in mice to that of nanospheres,and but reveled less liver retention than nanospheres.Due to their strong absorption in the near-infrared(NIR),Au nanostars-2 induced a strong hyperthermia effect in vitro upon excitation at 808 nm,and elicited a robust photothermal therapy(PTT) efficacy in ablating tumors in a mouse model of orthotopic breast cancer using 4T1 breast cancer cells.Meanwhile,Au nanostars-1 showed a great capability to enhance the Raman signal through surface-enhanced Raman spectroscopy(SERS) in 4T1 cells.Our combined results opened a new avenue to develop Au nanostars for cancer imaging and therapy.     

Biosynthesis and characterization of gold nanoparticles produced by laccase from Paraconiothyrium variabile

During recent years investigation on the development of eco-friendly processes for production of gold nanoparticles (GNPs) have received much attention due to hazardous effects of chemical compounds used for nanoparticle preparation. In the present study, the purified laccase from Paraconiothyrium variabile was applied for synthesis of Au nanoparticles (AuNPs) and the properties of produced nanoparticles were characterized. The UV-vis spectrum of formed AuNPs showed a peak at 530 nm related to surface plasmon absorbance of GNPs represented the formation of gold nanoparticles after 20 min incubation of HAuCl(4) (0.6 mM) in the presence of 73 U laccase at 70°C. Transmission electron microscopy (TEM) image of AuNPs showed well dispersed nanoparticles in the range of 71-266 nm as determined by the laser light scattering method. The pattern of energy dispersive X-ray (EDX) of the prepared GNPs confirmed the structure of gold nanocrystals.     

Architecture of linear arrays of fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles: a new approach to the development of gold nanoparticles possessing an extremely red-shifted absorption characteristic

Fluoroalkyl end-capped co-oligomeric nanoparticles, which were prepared by the reaction of fluoroalkanoyl peroxide with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 1-hydroxy-5-adamantylacrylate (Ad-HAc), were applied to the preparation of novel fluorinated co-oligomeric nanocomposite-encapsulated gold nanoparticles. These fluorinated gold nanocomposites were easily prepared by the reductions of gold ions with poly(methylhydrosiloxane) (PMHS) in the presence of the corresponding fluorinated nanoparticles and tri -n-octylamine (TOA) in 1,2-dichloroethane (DE) at room temperature. These fluorinated gold nanoparticles were isolated as wine-red powders and were found to exhibit good dispersibility in a variety of traditional organic solvents such as DE, methanol, and t-butyl alcohol to afford transparent wine-red solutions. The morphology and stability of these fluorinated co-oligomeic nanocomposite-encapsulated gold nanoparticles were characterized using transmission electron microscopy (TEM), dynamic light scattering measurements (DLS), and UV-vis spectroscopy. DLS measurements and UV-vis spectroscopy showed that these particles are nanometer-size-controlled very fine nanoparticles (185-218 nm) that exhibit a plasmon absorption band at around 530 nm. TEM images also showed that gold nanoparticles are tightly encapsulated into fluorinated co-oligomeric nanoparticle cores. Interestingly, these fluorinated co-oligomeric nanocomposites-encapsulated gold nanoparticles were found to afford linear arrays of these fluorinated nanoparticles with increases in the feed amounts of TOA. More interestingly, these fluorinated gold nanoparticles were able to afford the extremely red-shifted plasmon absorption band at around 960 nm.     

In situ formation and size control of gold nanoparticles into chitosan for nanocomposite surfaces with tailored wettability

The in situ formation of gold nanoparticles into the natural polymer chitosan is described upon pulsed laser irradiation. In particular, hydrogel-type films of chitosan get loaded with the gold precursor, chloroauric acid salt (HAuCl(4)), by immersion in its aqueous solution. After the irradiation of this system with increasing number of ultraviolet laser pulses, we observe the formation of gold nanoparticles with increasing density and decreasing size. Analytical studies using absorption measurements, atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy of the nanocomposite samples throughout the irradiation procedure reveal that under the specific irradiation conditions there are two competing mechanisms responsible for the nanoparticles production: the photoreduction of the precursor responsible for the rising growth of gold particles with increasing size and the subsequent photofragmentation of these particles into smaller ones. The described method allows the localized formation of gold nanoparticles into specific areas of the polymeric films, expanding its potential applications due to its patterning capability. The size and density control of the gold nanoparticles, obtained by the accurate increase of the laser irradiation time, is accompanied by the simultaneously controlled increase of the wettability of the obtained gold nanocomposite surfaces. The capability of tailoring the hydrophilicity of nanocomposite materials based on natural polymer and biocompatible gold nanoparticles provides new potentialities in microfluidics or lab on chip devices for blood analysis or drugs transport, as well as in scaffold development for preferential cells growth.     

In situ measurement of bovine serum albumin interaction with gold nanospheres

We present in situ observations of adsorption of bovine serum albumin (BSA) on citrate-stabilized gold nanospheres. We implemented scattering correlation spectroscopy as a tool to quantify changes in the nanoparticle brownian motion resulting from BSA adsorption onto the nanoparticle surface. Protein binding was observed as an increase in the nanoparticle hydrodynamic radius. Our results indicate the formation of a protein monolayer at similar albumin concentrations as those found in human blood. Additionally, by monitoring the frequency and intensity of individual scattering events caused by single gold nanoparticles passing the observation volume, we found that BSA did not induce colloidal aggregation, a relevant result from the toxicological viewpoint. Moreover, to elucidate the thermodynamics of the gold nanoparticle-BSA association, we measured an adsorption isotherm which was best described by an anticooperative binding model. The number of binding sites based on this model was consistent with a BSA monolayer in its native state. In contrast, experiments using poly(ethylene glycol)-capped gold nanoparticles revealed no evidence for adsorption of BSA.     

Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles: gold nanospheres, silica-gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed ( approximately 40 nm) show an absorption cross-section 5 orders higher than conventional absorbing dyes, while the magnitude of light scattering by 80-nm gold nanospheres is 5 orders higher than the light emission from strongly fluorescing dyes. The variation in the plasmon wavelength maximum of nanospheres, i.e., from approximately 520 to 550 nm, is however too limited to be useful for in vivo applications. Gold nanoshells are found to have optical cross-sections comparable to and even higher than the nanospheres. Additionally, their optical resonances lie favorably in the near-infrared region. The resonance wavelength can be rapidly increased by either increasing the total nanoshell size or increasing the ratio of the core-to-shell radius. The total extinction of nanoshells shows a linear dependence on their total size, however, it is independent of the core/shell radius ratio. The relative scattering contribution to the extinction can be rapidly increased by increasing the nanoshell size or decreasing the ratio of the core/shell radius. Gold nanorods show optical cross-sections comparable to nanospheres and nanoshells, however, at much smaller effective size. Their optical resonance can be linearly tuned across the near-infrared region by changing either the effective size or the aspect ratio of the nanorods. The total extinction as well as the relative scattering contribution increases rapidly with the effective size, however, they are independent of the aspect ratio. To compare the effectiveness of nanoparticles of different sizes for real biomedical applications, size-normalized optical cross-sections or per micron coefficients are calculated. Gold nanorods show per micron absorption and scattering coefficients that are an order of magnitude higher than those for nanoshells and nanospheres. While nanorods with a higher aspect ratio along with a smaller effective radius are the best photoabsorbing nanoparticles, the highest scattering contrast for imaging applications is obtained from nanorods of high aspect ratio with a larger effective radius.     

Spacer-mediated synthesis of size-controlled gold nanoparticles using geminis as ligands

We report a new methodology for the size-controlled aqueous synthesis of gold nanoparticles using geminis with different spacers as ligands. Geminis possess a unique structure in which two hydrophobic chains and two polar headgroups are combined via a spacer. We herein demonstrate that the spacer can be used as a tool to control particle size when geminis are used as ligands for gold nanoparticles. Varying the spacer length of geminis yields facile control over the size and size distribution of nanoparticles. For the 18-s-18-capped gold nanoparticles, FTIR and TGA experiments indicate that the geminis form bilayers on the surface of gold nanoparticles, which serve as templates that control the formation of nanoparticles. The smallest particles are obtained with a moderate spacer length (s = 8) because in that case the gemini bilayers interdigitate to the fullest degree to reach the maximum chain-chain interaction, thus yielding the most compact coating on the surface of gold nanoparticles. This work provides a new approach to the size control of nanoparticles.     

Synthesis of uniform gold nanoparticles using non-pathogenic bio-control agent: evolution of morphology from nano-spheres to triangular nanoprisms

Green synthesis of gold nanospheres with uniform diameter and triangular nanoprisms with optically flat surface was carried out using a non-pathogenic bio-control agent Trichoderma asperellum for reduction of HAuCl(4). Kinetics of the reaction was monitored by UV-Vis absorption spectroscopy. No additional capping/complexing agent was used for stabilizing the gold nanoparticles. Evolution of morphology from pseudospherical nanoparticles to triangular nanoprisms was studied by transmission electron microscopy (TEM). It revealed that three or more pseudospheres fused to form nanoprisms of different shapes and sizes. Slow rate of reduction of HAuCl(4) by constituents of cell-free fungal extract was instrumental in producing such exotic morphologies. Isolation of gold nanotriangles from the reacting masses was achieved by differential centrifugation.     

Green preparation of hollow mesoporous silica nanosphere inside-loaded gold nanoparticles and the catalytic activity

In this work, an active nano-catalyst with gold nanoparticles loaded in hollow mesoporous silica nanospheres (HMSNs/Au) was prepared by a one-pot sol-gel method, in which gold ions were loaded in hollow mesoporous silica spheres followed by sodium alginate reduction. The characterization of the HMSNs/Au were determined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption–desorption isotherms (BET). The high catalytic activity of HMSNs/Au, denoted as apparent turn-over frequency (TOF), was detected by UV-Vis spectrophotometer for the catalytic reduction of 4-nitrophenol (74.5 h^?1) and 2-nitrophenol (108.7 h^?1) in the presence of sodium borohydride solution due to the small gold nanoparticles size and overall exposure of active sites. It is expected that this ecofriendly approach to prepare inorganic composited nanoparticles as high active catalysts based on hollow mesoporous materials was a promising platform for loading noble metal nanoparticles.