Optimization of high-yield biological synthesis of single-crystalline gold nanoplates

In this work, single-crystalline gold nanoplates were obtained by reducing aqueous chloroauric acid solution with the extract of Sargassum sp. (brown seaweed) at room temperature. The gold nanoplates so obtained were characterized by UV-vis spectroscopy, X-ray diffraction, atomic force microscopy, and transmission electron microscopy. The formation of gold nanoplates was found to depend on a number of environmental factors, such as the time taken to age the seaweed extract, pH of the reaction medium, reaction temperature, reaction time, and initial reactant concentrations. The size of the gold nanoplates could be controlled to between 200 and 800 nm by manipulating the initial reactant concentrations. The yield of the flat gold nanocrystals relative to the total number of nanoparticles formed was as high as approximately 80-90%.     

Ultrasonic-assisted synthesis of monodisperse single-crystalline silver nanoplates and gold nanorings

A simple sonochemical route was developed for the crystal growth of uniform silver nanoplates and ringlike gold nanocrystals in a N,N-dimethylformamide solution. The platelike structures were generated from the selective growth on different crystal planes in the presence of poly(vinylpyrrolidone) and the ultrasonic-assisted Ostwald ripening processes. The silver nanoplates in solution served as the templates for the synthesis of ringlike gold crystals via a displacement reaction. Both the silver nanoplates and gold nanorings were highly oriented single crystals with (111) planes as the basal planes.     

Synthesis and characterization of high concentration block copolymer-mediated gold nanoparticles

The formation of high concentration gold nanoparticles at room temperature is reported in block copolymer-mediated synthesis where the nanoparticles have been synthesized from hydrogen tetrachloroaureate(III) hydrate (HAuCl(4)·3H(2)O) using block copolymer P85 (EO(26)PO(39)EO(26)) in aqueous solution. The formation of gold nanoparticles in these systems has been characterized using UV-visible spectroscopy and small-angle neutron scattering (SANS). We show that the presence of additional reductant (trisodium citrate) can enhance nanoparticle concentration by manyfold, which does not work in the absence of either of these (additional reductant and block copolymer). The stability of gold nanoparticles with increasing concentration has also been examined.     

High-yield synthesis of large single-crystalline gold nanoplates through a polyamine process

A polyamine process has been demonstrated for the high-yield preparation of single-crystalline gold nanoplates with several 10 microm in size, carried out by heating a concentrated aqueous solution of linear polyethylenimine and HAuCl4 at 100 degrees C. It suggests that the concentration of reactants is crucial to the formation of nanoplates.     

Facile synthesis of gold nanoplates by thermally reducing AuCl_4~- with aniline

We herein report a one-step,wet-chemical approach to synthesizing gold nanoplates in large quantities via the AuCl_4~-thermal reduction process by aniline,without introducing additional capping agent or suffactant.It is found that the reduction kinetics of AuCl_4~-is greatly altered by varying the initial molar ratio of aniline to AuCl_4~-.Moreover,further investigation reveals that the in- situ formed polyaniline could serve effectively as a capping agent to preferably adsorb the{111}facets of gold crys...     

Organic dye molecules as reducing agent for the synthesis of electroactive gold nanoplates

Highly crystalline, hexagonal and triangular nanoplates of gold are synthesized in high yield by a new wet chemical method using multifunctional molecules, Bismarck brown R (BBR) and Bismarck brown Y (BBY). This method involves a simple approach by keeping a mixture of aqueous HAuCl4 solution and BBR/BBY solution in presence of poly(vinyl pyrrolidone) for 24 h. These nanostructures show unprecedented electrochemical properties exhibiting surface confinement effect. The UV-visible (UV-vis) spectrum shows certain distinct features with absorptions at 300, 400, and 650 nm extending up to the near infrared region. Selected area electron diffraction patterns of these nanoparticles show highly oriented (111) crystal facets. X-ray diffraction analysis also confirms the predominant orientation in the (111) crystal planes with lattice constant approximately 4.07 angstroms of face-centered-cubic (fcc) gold. X-ray photoelectron (XP) and Fourier transform infrared (FTIR) spectroscopic analysis shows the presence of a fraction of reducing molecules as surface passivating agent either in the unreacted molecular state or as a mixture of reacted and unreacted product, which probably undergoes charge transfer with gold nanocrystals giving absorption at approximately 300 nm.     

Synthesis of gold nanoplates by aspartate reduction of gold chloride

Single crystal nanoplates with thickness less than 30 nm, characterized by hexagonal and truncated triangular shapes bounded mainly by [111] facets, were obtained in large quantities by aspartate reduction of gold chloride.     

Shape-controlled synthesis of gold icosahedra and nanoplates using Pluronic P123 block copolymer and sodium chloride

Gold icosahedra with an average diameter of about 600 nm were easily prepared by heating an aqueous solution of the amphiphilic block copolymer, poly(ethylene oxide)₂₀-poly(propylene oxide)₇₀-poly(ethylene oxide)₂₀ (Pluronic P123), and hydrogen tetrachloroaurate(III) trihydrate (HAuCl₄·3H₂O) at 60 °C for 25 min. When sodium chloride (NaCl:HAuCl₄ molar ratio=10:1) was added to this aqueous solution, gold nanoplates were produced. The chloride ion was found to be a key component in the formation of the gold nanoplates by facilitating the growth of {111} oriented hexagonal/triangular gold nanoplates, because similar gold nanoplates were produced when LiCl or KCl was added to the aqueous solution instead of NaCl, while gold nanocrystals having irregular shapes were produced when NaBr or NaI was added.     

Surface plasmon modes of gold nanospheres, nanorods, and nanoplates in an organic solvent: phase-transfer from aqueous to organic media

We present a process for the phase-transfer of gold nanoparticles from an aqueous to an organic medium with normal alkanethiols. This method can be applied not only to large nanospheres (d~100 nm) but also to anisotropic nanoparticles like nanorods and nanoplates. It allows the comparison of the nanoparticle optical properties when they are dispersed in both aqueous and organic media.     

Silver-assisted colloidal synthesis of stable, plasmon resonant gold patches on silica nanospheres

Patchy particles possessing heterogeneous surface composition show great promise as self-organizing building blocks for new classes of hierarchical functional structures. A major hurdle is the scalable synthesis of stable patches on nanosized core particles with arbitrarily defined patch number and coverage. So far, few methods have been reported which could be expected to meet these challenges. Recently, we described the heterogeneous nucleation and growth of silver patches on silica nanospheres via a template free colloidal route. The patches produced, although tunable in size and number and showing interesting plasmon resonant properties, were rather unstable and degraded rapidly during attempts to process them further. In the present work, therefore, we set out to explore if related approaches can be employed to produce patchy particles involving gold, which is known to be more stable. The differences between typical patch precursors Ag(+) and [AuCl(x)(OH)(4-x)](-) and their respective interactions with amorphous silica make this a significant challenge. We show that preformed small silver patches in addition to the presence of a reducing agent are necessary for the formation of gold patches conformal to the silica nanosphere surface. Systematic study of the process parameters and their influence on the patchy particle morphology as well as in-depth analytical transmission electron microscopy investigation of the patch composition reveal that patches spread over the silica surface via a cycle of galvanic dissolution and redeposition of silver. The resulting gold patchy particles remain stable during subsequent storage or washing and display tunable plasmon resonances within the visible and near-IR spectrum.     

Dissolution-recrystallization mechanism for the conversion of silver nanospheres to triangular nanoplates

A solution chemistry method for transforming polycrystalline Ag spherical particles into single crystalline triangular Ag nanoplates has been developed. The synthesis consists of three consecutive steps: (1) the synthesis of Ag nanospheres by NaBH(4) reduction of AgNO(3) in the presence of sodium citrate; (2) the conversion of citrate-stabilized Ag nanospheres into SDS (sodium dodecyl sulfate)-stabilized Ag nanospheres, and (3) the aging of the SDS-stabilized Ag nanospheres in 0.01 M NaCl solution. Our study indicates that the shape evolved through a Ag nanoparticle dissolution- and re-deposition process; and demonstrated the critical role of SDS in the process: SDS regulates the dynamics in the dissolved O(2)/Cl(-) etching of the Ag nanospheres and the reduction of the released Ag(+) by citrate ions in the same solution. SDS also functions as a shape-directing agent to assimilate the Ag(0) atoms into single crystalline triangular Ag nanoplates. A model for the shape conversion is also proposed which provides the clue for the synthesis of anisotropic Ag nanoparticles with other shapes (rods, wires, cubes, etc.).     

Transformation of silver nanospheres into triangular nanoplates through a photoinduced process

Triangular silver nanoplates exhibit excellent optical and catalytic properties in many fields, such as catalysts, sensors and bio-medicine. In this paper, triangular nanoplates were generated just in the presence of sodium citrate through a light-induced ripening process, which were converted from spherical silver nanoparticles by reducing silver nitrate with sodium borohydride. By using UV–Vis spectroscopy, particle size analyzer, transmission electron microscopy (TEM) and Ag⁺ concentration analysis, the effects of precursors during the preparation of triangular nanoplates were systematically investigated and the optimal experimental conditions were determined. Based on density functional theory (DFT), the adsorption energies of citrate ion, malate ion and tartronate ion on Ag (1 1 1), (1 1 0) and (1 0 0) were calculated. In addition, theoretical calculations coupled with experimental observations showed that citrate ion as capping agent could more preferentially bind to Ag (1 1 1) and thus blocked Ag (1 1 1) while only allowing extensive growth along the lateral direction. This well explains sodium citrate is an efficient agent in preparing triangular silver nanoplates.     

Structural effects of amphiphilic block copolymers on the gold nanoplates synthesis. Experimental and theoretical study

Geometric and multi-arms gold nanoplates were synthesized by direct reaction between two different amphiphilic block copolymers and KAuCl₄ in aqueous solution. Amphiphilic copolymers containing blocks of ε-caprolactone and N-vinyl-2-pyrrolidone were used. The block copolymer structures and concentration play a key role on the morphology and size of gold nanoparticles. Copolymers have a dual function as reductant and stabilizer agent. The gold nanoparticles obtained were characterized by transmission electron microscopy (TEM), UV–visible spectroscopy (UV–vis) and dynamic light scattering (DLS). On the other hand, electronic structure calculations, based on density functional theory were performed to support the experimental results. The simple models built with small clusters of gold and co-monomer units provide planar structures complexes with higher stabilization energies. These results agree with the nanoplates obtained experimentally. Moreover, the reactivity analysis based on monoelectronic properties suggests that the formation of aggregates between complexes is favored.     

Polygonal gold nanoplates in a polymer matrix

Polygonal gold nanoplates are generated in situ in poly(vinyl alcohol) film through thermal treatment, the polymer serving as the reducing agent and stabilizer for the nanoparticle formation and enforcing preferential orientation of the plates. The rare pentagonal as well as the more commonly observed hexagonal, triangular and square/rectangle shapes are obtained by fine-tuning the Au/PVA ratio and the time and temperature of fabrication.     

Pear fruit extract-assisted room-temperature biosynthesis of gold nanoplates

In this paper, a single-step room-temperature biosynthetic route for producing gold nanostructures using pear fruit is reported. The alkaline conditions of the pear fruit extract induced gold nanoparticles with plate-like morphologies. Successfully biosynthesized triangular and hexagonal nanoplates were observed, elegantly assembled with hexagonal gold nanoparticles. Nanostructure size, crystal nature, purity and morphologies were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoemission spectroscopy (XPS) and energy dispersive X-ray analysis (EDAX). The edge lengths of the nanostructures ranged from 200 to 500 nm. Using AFM analysis, the nanohexagons were observed to have a thickness ranging from 12 to 20 nm. The XRD patterns showed a (1 1 1) preferential orientation of the nanostructures. The XPS and EDAX analysis also confirmed the presence of pure-phase Au without any substantial impurities. The preparation of nanostructured gold particles using pear fruit provides an environmentally friendly option, as compared to currently available chemical and/or physical methods.     

Facile synthesis of concave gold nanoplates in hexagonal liquid crystal made of SDS/water system

Concave gold nanoplates are obtained in hexagonal liquid crystal (LLC) made of SDS (sodium dodecyl sulfate)/glycine/HAuCl(4) aqueous solution system where glycine plays the key role. All plates are single-crystals, characterized by {111} facets, with concave centers of regular hexagonal or triangular shapes, and with better electrocatalytic activity than gold nanoplates.     

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.     

Thermal aqueous solution approach for the synthesis of triangular and hexagonal gold nanoplates with three different size ranges

The synthesis of gold nanoplates was carried out in an aqueous solution by thermal reduction of HAuCl(4) with trisodium citrate in the presence of cetyltrimethylammonium bromide (CTAB) surfactant in just 5-40 min. The sizes of the gold nanoplates can be varied from as small as tens of nanometers in width, to several hundreds of nanometers, and even a few microns in width by changing the reagent concentrations, solution temperature, and the reaction time. A [CTAB]/[HAuCl(4)] ratio of 6 in the reaction solution was found to be favorable for the formation of gold nanoplates. The nanoplates possess well-defined shapes with sharp edges. The small nanoplates exhibit mainly a triangular shape, while larger nanoplates show a mixture of triangular, hexagonal, truncated triangular, and other symmetrical structures. The nanoplates are composed of essentially (111) lattice planes, as revealed by both XRD and TEM results. Nanoplates with widths from several hundreds of nanometers to a few microns absorb light strongly in the near-infrared region. The growth mechanism of these nanoplates was investigated. The ability to synthesize gold nanoplates with these different size ranges in large scale in aqueous solution using simple CTAB capping surfactant should allow more diverse applications of gold nanoplates.     

Optimization of plasmonic heating by gold nanospheres and nanoshells

Gold nanoparticles have strong and tunable absorption peaks in their optical extinction spectra, a phenomenon that has recently been exploited to generate localized heating in the vicinity of these particles. However the optimum particle geometry and illumination regime to maximize these effects appears not to have been previously examined in any detail. Here we show that the interplay between the particles' absorption cross-sections, volume, and surface area lead to there being specific conditions that can maximize particle temperature and surface heat flux. Optical absorption efficiencies were calculated from the formulation of Mie, and radiative, convective, and conductive heat transfer models were used to model the thermal performance of particles in different situations. Two technologically relevant scenarios for illumination, namely, irradiation by sunlight at 800 W/m2 and by a monochromatic laser source of 50 kW/m2 tuned to the peak absorption wavelength, were considered. For irradiation by sunlight, the resultant heat flux is optimized for an 80 nm diameter nanoshell with an aspect ratio of 0.8, while for irradiation by laser the maximum heat flux is found for 50 nm nanoshells, with an aspect ratio of 0.9.