A study on gold nanoparticle synthesis using oleylamine as both reducing agent and protecting ligand

The growth kinetics and mechanism of a gold nanoparticle synthesis using water as a single phase solvent and oleylamine as both reducing agent and monolayer protection agent were studied. FT-IR and 1H NMR spectroscopic analysis revealed a conversion of oleylamine ligands to oleylamides when gold(III) was reduced to gold(I) and gold atoms. During the reaction, it was found by UV-Vis absorption spectroscopy and transmission electron microscopic study that oleylamine ligands formed large complex aggregates with gold salt instantly upon mixing these two agents together. At an elevated temperature of 80 degrees C, the complex decomposed first into very small particles and then the small particles recombined together into larger and thermally stable particles with an average core size around 9-10 nm. The oleylamide ligands formed a protecting monolayer around the nanoparticles through a hydrogen bonding network between the amide groups. The recombination of small particles into larger ones was found to follow a logistic model, as confirmed by a nonlinear regression fitting of the UV-Vis absorption data of the reaction solution with the mathematical model.     

High Surface‐Enhanced Raman Scattering Performance of Individual Gold Nanoflowers and Their Application in Live Cell Imaging

Molecular imaging techniques based on surface‐enhanced Raman scattering (SERS) face a lack of reproducibility and reliability, thus hampering its practical application. Flower‐like gold nanoparticles have strong SERS enhancement performance due to having plenty of hot‐spots on their surfaces, and this enhancement is not dependent on the aggregation of the particles. These features make this kind of particle an ideal SERS substrate to improve the reproducibility in SERS imaging. Here, the SERS properties of individual flower‐like gold nanoparticles are systematically investigated. The measurements reveal that the enhancement of a single gold nanoparticle is independent of the polarization of the excitation laser with an enhancement factor as high as 10⁸. After capping with Raman signal molecules and folic acid, the gold nanoflowers show strong Raman signal in the living cells, excellent targeting properties, and a high signal‐to‐noise ratio for SERS imaging.     

Seed-mediated synthesis of branched gold nanoparticles with the assistance of citrate and their surface-enhanced Raman scattering properties

We report an easy synthesis of highly branched gold particles through a seed-mediated growth approach in the presence of citrate. The addition of citrate in the growth solution is found to be crucial for the formation of these branched gold particles. Their size can be varied from 47 to 185?nm. The length of the thumb-like branch is estimated to be between about 5 and 20?nm, and changes slightly as the particle size increases. Owing to these obtuse and short branches, their surface plasmon resonance displays a marked red-shift with respect to the normal spherical particles. These branched gold particles exhibit stronger SERS activity than the non-branched ones, which is most likely related to these unique branching features.     

Synthesis of gold nanorods in organic media

A seed mediated approach for the synthesis of anisotropic rod shaped gold nanoparticles in organic media (toluene) is demonstrated. Pre-formed gold nanoparticles stabilized in toluene by 4-hexadecylaniline (HDA) are used as seeds. These when reacted with 1-octadecylamine (ODA) hydrophobised chloroaurate ions in toluene lead to the formation of gold nanorods. ODA or alkylamines of different chain lengths which are the chloroaurate ion phase transfer agent have been found to play a key role in the formation of the nanorods. The gold nanorods that have a five-fold symmetry evolve from multiply twinned particles and are bound at the tips by [1 11] faces and at the sides by [100] faces. The gold nanorods have been shown to grow under the shape directing effect of the alkylamines which stabilize the high energy [100] faces. The concentration of the alkylamines has been found to play a critical role in the formation of the gold nanorods. Higher concentrations of the alkylamines lead to formation of spherical particles, at times of narrow size distribution.     

Ammonium bicarbonate reduction route to uniform gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering

A new protocol for the synthesis of nearly monodisperse gold nanoparticles with controllable size is described. The pathway is based on the reduction of AuCl₄⁻ by ammonium bicarbonate in the presence of sodium stearate under hydrothermal conditions. The particle sizes could be easily tuned by regulating the reaction conditions including precursor concentration, reaction temperature and growth time. A tentative explanation for the reduction and growth mechanism of uniform gold nanoparticles has been proposed. The as-prepared gold particles showed good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol by excess NaBH₄, and a surface-enhanced Raman scattering (SERS) study suggested that the gold nanoparticles exhibited a high SERS effect on the probe molecule Rhodamine 6G.      

Chiral guanosine 5′-monophosphate-capped gold nanoflowers: Controllable synthesis, characterization, surface-enhanced Raman scattering activity, cellular imaging and photothermal therapy

Plasmonics and chirality in metal nanomaterials are intriguing and inspiring phenomena. Nanoscale chirality of metal nanomaterials has emerged as a hot topic in the past several years. Generally, most plasmon-induced circular dichroism (CD) responses of nanomaterials (> 10 nm) have been artificially created by modifying pre-made achiral nanomaterials with chiral agents, because the in situ generation of plasmon-induced CD responses of nanomaterials with larger size (> 10 nm) is not easy. Herein, we report a simple one-pot green synthesis of chiral gold nanoflowers (GNFs) with abundant petal-shaped tips in the chiral reduction environment arising from the presence of chiral guanosine 5??-monophosphate (5??-GMP) and the chiral reducing agent L-ascorbic acid (L-AA). Different reducing agents can impact the shape and chirality of the products. In addition, the size and chirality of the GNFs can be controlled by adjusting the reaction time. The as-synthesized GNFs have good biocompatibility and can be used for surface-enhanced Raman scattering (SERS) enhancement, cellular dark-field imaging and photothermal therapy.      

Synthesis and agglomeration of gold nanoparticles in reverse micelles

Reverse micelles prepared in the system water, sodium bis-(2-ethylhexyl) sulfoccinate (AOT), and isooctane were investigated as a templating system for the production of gold nanoparticles from Au(III) and the reducing agent sulfite. A core-shell Mie model was used to describe the optical properties of gold nanoparticles in the reverse micelles. Dynamic light scattering of gold colloids in aqueous media and in reverse micelle solution indicated agglomeration of micelles containing particles. This was verified theoretically with an analysis of the total interaction energy between pairs of particles as a function of particle size. The analysis indicated that particles larger than about 8?nm in diameter should reversibly flocculate. Transmission electron microscopy measurements of gold nanoparticles produced in our reverse micelles showed diameters of 8-10?nm. Evidence of cluster formation was also observed. Time-correlated UV-vis absorption measurements showed a red shift for the peak wavelength. This was interpreted as the result of multiple scattering and plasmon interaction between particles due to agglomeration of micelles with particles larger than 8?nm.     

Size controlled synthesis of biocompatible gold nanoparticles and their activity in the oxidation of NADH

Size and shape controlled synthesis remains a major bottleneck in the research on nanoparticles even after the development of different methods for their preparation. By tuning the size and shape of a nanoparticle, the intrinsic properties of the nanoparticle can be controlled leading tremendous potential applications in different fields of science and technology. We describe a facile route for the one pot synthesis of gold nanoparticles in water using monosodium glutamate as the reducing and stabilizing agent in the absence of seed particles. The particle diameter can be easily controlled by varying the pH of the reaction medium. Nanoparticles were characterized using scanning electron microscopy, UV-vis absorption spectroscopy, cyclic voltammetry, and dynamic light scattering. Zeta potential measurements were made to compare the stability of the different nanoparticles. The results suggest that lower pH favours a nucleation rate giving rise to smaller particles and higher pH favours a growth rate leading to the formation of larger particles. The synthesized nanoparticles are found to be stable and biocompatible. The nanoparticles synthesized at high pH exhibited a good electrocatalytic activity towards oxidation of nicotinamide adenine dinucleotide (NADH).     

Simple and Rapid High‐Yield Synthesis and Size Sorting of Multibranched Hollow Gold Nanoparticles with Highly Tunable NIR Plasmon Resonances

Branched gold nanoparticles with sharp tips are considered excellent candidates for sensing and field enhancement applications. Here, a rapid and simple synthesis strategy is presented that generates highly branched gold nanoparticles with hollow cores and a ca.100% yield through a simple one‐pot seedless reaction at room temperature in the presence of Triton X‐100. It is shown that multibranched hollow gold nanoparticles of tunable dimensions, branch density and branch length can be obtained by adjusting the concentrations of the reactants. Insights into the formation mechanism point toward an aggregative type of growth involving hollow core formation first, and branching thereafter. The pronounced near‐infrared (NIR) plasmon band of the nanoparticles is due to the combined contribution from hollowness and branching, and can be tuned over a wide range (≈700–2000 nm). It is also demonstrated that the high environmental sensitivity of colloidal dispersions based on multibranched hollow gold nanoparticles can be boosted even further by separating the nanoparticles into fractions of given sizes and improved monodispersity by means of a glycerol density gradient. The possibility to obtain highly monodisperse multibranched hollow gold nanoparticles with predictable dimensions (50–300 nm) and branching and, therefore, tailored NIR plasmonic properties, highlights their potential for theranostic applications.     

Synthesis of gold nanowire networks and nanoparticles by tyrosine reduction of chloroaurate

A simple and facile synthesis of gold nanowire networks and sol particles at room temperature is presented using L-tyrosine (Tyr) as both the reducing and capping agent. The synthesis conditions with varying the gold precursor concentration ([HAuCl4], 0.1-2.5 mM) and concentration ratio of tyrosine to gold precursor R ([Tyr]/[HAuCl4], 0.05-10) were identified for the preparation of network-like nanowires and sol nanoparticles. Gold sol particles with sizes between 10 and 18 nm were mostly obtained at R > or = 0.2. Network-like gold nanowires with average diameters as thin as 8 nm can be reproducibly synthesized at R < or = 0.1. The experimental data revealed that the phenolic and carboxyl group of Tyr were oxidized to form quinone and alcohol, respectively. The growth process was examined to elucidate the influence of the synthesis conditions on different morphologies, showing marked difference in isotropic and anisotropic growth of gold nanostructures at different synthesis conditions. The study showed that tyrosine possesses excellent reducing capability with short nucleation period and long growth period as compared with other amino acids.     

Preparation of gold nanoparticles in an aqueous medium using 2-mercaptosuccinic acid as both reduction and capping agent

Monolayer protected gold nanoparticles with diameters above 10 nm were prepared by a simple, one step reaction in water. 2-mercaptosuccinic acid (MSA) was used both as reduction agent for hydrogen tetrachloroaurate (HAuCl4) and as stabilizing agent for the gold nanoparticles. Size distribution and surface chemistry were investigated by UV-Vis spectroscopy, scanning electron microscopy and Fourier Transform Infrared Spectroscopy. Particle size can be controlled by adjusting the molar portions of the reactants. The resulting particles are efficiently stabilized against aggregation when MSA is used in a concentration of 40% and above. Below a minimum MSA concentration a long-term particle growth is observed.     

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.     

Flower-shaped gold nanoparticles: synthesis, characterization and their application as SERS-active tags inside living cells

The detection of Raman signals inside living cells is a topic of great interest in the study of cell biology mechanisms and for diagnostic and therapeutic applications. This work presents the synthesis and characterization of flower-shaped gold nanoparticles and demonstrates their applicability as SERS-active tags for cellular spectral detection. The particles were synthesized by a facile, rapid new route that uses ascorbic acid as a reducing agent of gold salt. Two triarylmethane dyes which are widely used as biological stains, namely malachite green oxalate and basic fuchsin, were used as Raman-active molecules and the polymer mPEG-SH as capping material. The as-prepared SERS-active nanoparticles were tested on a human retinal pigment epithelial cell line and found to present a low level of cytotoxicity and high chemical stability together with SERS sensitivity down to picomolar particle concentrations.     

Solution route synthesis of dendrite Cu6Sn5 powders, anode material for lithium-ion batteries

Intermetallic dendrite particles, such as Cu₆Sn₅ compound, possible anode materials for high power lithium-ion batteries, can be synthesized by using solution technique. Solution route method can induce the formation of the compound by performing a redox reaction between metal chloride salts and metallic reducing powder in a suitable solvent. The morphological features and single-phase formation corresponding to different processing conditions including solvent type, reducing agent particle size, and reaction temperature, were determined. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) results illustrate the dendritic morphology of Cu₆Sn₅ particles with small amount of impurities, which can be synthesized by using ethylene glycol as solvent and zinc powder as reducing agent. Reducing agent particle size and reaction temperature have a very small effect on the formation of the Cu₆Sn₅ dendrite powder.     

Photochemical synthesis of biopolymer coated Aucore-Agshell type bimetallic nanoparticles

Spherical Au nanoparticles have been prepared in the presence of a biopolymer, sodium alginate using UV-photoactivation technique. The particles are sodium alginate coated and are extremely stable. These Au nanoparticles have been used as seed for the synthesis of Aucore-Agshell type bimetallic nanoparticles. Sodium alginate is a carbohydrate-based biopolymer. In this synthesis it acts both as a reducing agent and a stabilizer for the evolved particles. Therefore, no extra capping agent is required from outside to make the generated particle stable. By varying the seed to silver ion ratios and using photoactivation technique Aucore-Agshell type bimetallic nanoparticles with various sizes and compositions have been synthesized. The method is very simple and reproducible and does not need any manipulative skill. Characterizations of these bimetallic nanoparticles have been done from their UV-visible spectroscopy, TEM/EDX, and AFM results. UV-visible extinction spectra reveal that the seed particles have an absorption maxima approximately 527 nm, attributed to the surface plasmon of the pure gold nanoparticles. From the TEM images the particle size of the gold seed particles was calculated to be 8.6 nm. The growth of bimetallic nanoparticles with time has been monitored. The finally evolved bimetallic Aucore-Agshell nanoparticles have a size in the range between approximately 10-14 nm. The particles are very stable and may have the potential for biological and catalytic applications.     

Shape-controlled synthesis of cobalt oxide nanocrystals using cobalt acetylacetonate

Cobalt oxide nanocrystals (NCs) with different morphologies have been successfully synthesized through the decomposition of cobalt (II) acetylacetonate (Co(acac)₂) in nonpolar solvent. The growth temperature of NCs was set at 30 °C lower than the nucleation temperature to prepare monodisperse NCs. By tuning the injection speed of paraffin oil, CoO nanoparticles and nanoflowers have been obtained, respectively. The variation in ligand concentration changing speed due to different injection speed of extra paraffin oil is supposed to be the reason for the formation of CoO NCs with different nanostructures. The structure and shape properties of as-synthesized cobalt oxide NCs have been studied and characterized using XRD and TEM.     

Biosynthesis of gold and silver nanoparticles using Emblica Officinalis fruit extract, their phase transfer and transmetallation in an organic solution

The design, synthesis and characterization of biologically synthesized nanomaterials have become an area of significant interest. In this paper, we report the extracellular synthesis of gold and silver nanoparticles using Emblica Officinalis (amla, Indian Gooseberry) fruit extract as the reducing agent to synthesize Ag and Au nanoparticles, their subsequent phase transfer to an organic solution and the transmetallation reaction of hydrophobized silver nanoparticles with hydrophobized chloroaurate ions. On treating aqueous silver sulfate and chloroauric acid solutions with Emblica Officinalis fruit extract, rapid reduction of the silver and chloroaurate ions is observed leading to the formation of highly stable silver and gold nanoparticles in solution. Transmission Electron Microscopy analysis of the silver and gold nanoparticles indicated that they ranged in size from 10 to 20 nm and 15 to 25 nm respectively. Ag and Au nanoparticles thus synthesized were then phase transferred into an organic solution using a cationic surfactant octadecylamine. Transmetallation reaction between hydrophobized silver nanoparticles and hydrophobized chloroaurate ions in chloroform resulted in the formation of gold nanoparticles.     

Surface-enhanced vibrational spectroscopy of adsorbates on microemulsion synthesized gold nanoparticles

Very small (<10 nm) monodisperse gold nanoparticles (AuNPs) coated with a monolayer of decanethiol were prepared and their surface-enhanced infrared absorption (SEIRA) spectra were measured in the transmission mode. The AuNPs were prepared by the borohydride reduction of HAuCl(4) inside reverse micelles that were made by adding water to a hexane solution of sodium bis(2-ethylhexyl)sulfosuccinate (AOT). The gold nanoparticles were then stabilized by the addition of decanethiol. Subsequent addition of p-nitrothiophenol both facilitated the removal of excess AOT and showed that the gold surface was completely covered by the decanethiol. SEIRA spectra of decanethiol on gold particles prepared in AOT microemulsions were about twelve times more intense than corresponding layers on gold produced by electroless deposition and gave a significantly less noisy spectrum compared to the corresponding surface-enhanced Raman spectrum. The surface-enhanced Raman scattering (SERS) spectra of the same samples showed that the most intense spectrum was obtained from gold nanoparticles with a mean diameter of 2.5 nm. This result is in contrast to previous statements that SERS spectra could only be obtained from particles larger than 10 nm.     

Precision Synthesis: Designing Hot Spots over Hot Spots via Selective Gold Deposition on Silver Octahedra Edges

A major challenge in plasmonic hot spot fabrication is to efficiently increase the hot spot volumes on single metal nanoparticles to generate stronger signals in plasmon‐enhanced applications. Here, the synthesis of designer nanoparticles, where plasmonic‐active Au nanodots are selectively deposited onto the edge/tip hot spot regions of Ag nanoparticles, is demonstrated using a two‐step seed‐mediated precision synthesis approach. Such a “hot spots over hot spots” strategy leads to an efficient enhancement of the plasmonic hot spot volumes on single Ag nanoparticles. Through cathodoluminescence hyperspectral imaging of these selective edge gold‐deposited Ag octahedron (SEGSO), the increase in the areas and emission intensities of hot spots on Ag octahedra are directly visualized after Au deposition. Single‐particle surface‐enhanced Raman scattering (SERS) measurements demonstrate 10‐fold and 3‐fold larger SERS enhancement factors of the SEGSO as compared to pure Ag octahedra and non‐selective gold‐deposited Ag octahedra (NSEGSO), respectively. The experimental results corroborate well with theoretical simulations, where the local electromagnetic field enhancement of our SEGSO particles is 15‐fold and 1.3‐fold stronger than pure Ag octahedra and facet‐deposited particles, respectively. The growth mechanisms of such designer nanoparticles are also discussed together with a demonstration of the versatility of this synthetic protocol.     

Gold/palladium and silver/palladium colloids as novel metallic substrates for surface-enhanced Raman scattering

New surface-enhanced Raman scattering (SERS) substrates, composed of gold or silver colloidal nanoparticles doped with palladium, were prepared. These novel colloids are stable and maintain a satisfactory SERS efficiency, even after long aging. The interest in doping the coinage metal nanoparticles with palladium is due to the well-known catalytic activity of this metal. Transmission electron microscopy (TEM) and ultraviolet-visible absorption spectroscopy were used to characterize the shape and size of the metal particles. It was found that these bimetallic colloidal nanoparticles have a core-shell structure, with gold or silver coated with palladium clusters.