Micrometer-long gold nanowires fabricated using block copolymer templates

Micrometer-long gold nanowires were fabricated via self-assembly. Diblock copolymer films served as templates for the selective adsorption of 10 nm gold nanoparticles from solution to form well-defined nanostructures. An oxygen plasma treatment induced aggregation of the nanoparticles and the formation of continuous gold nanostructures. The electrical continuity of the nanostructures was observed using scanning electron microscopy.     

One-step controlled synthesis of anisotropic gold nanostructures with aniline as the reductant in aqueous solution

We report a general and versatile method for controlled synthesis of anisotropic gold nanostructures through the reduction of HAuCl4 by aniline in aqueous solution, without the need for an additional stabilizer or capping agent. In this approach, the reduction kinetics of AuCl-4 can be altered by simply adjusting the initial pH and temperature, inducing the formation of a wide variety of anisotropic nanostructures such as dispersed or multilayered plates, wires with networked or paramecium-like structures, and ginger-shaped particles. AFM, TEM, XRD, EDX, FTIR, and UV-vis-NIR measurements were used to characterize the resulting gold nanostructures. Investigation reveals that in situ formed polyaniline serves effectively as a capping agent to direct the shape of gold nanostructures during the slow growth process. These as-synthesized gold nanostructures exhibit strongly shape-dependent optical properties. This facile approach may be extended to the synthesis of some other anisotropic metal nanostructures such as platinum or palladium.     

Ultrafast growth of dendritic gold nanostructures and their applications in methanol electro-oxidation and surface-enhanced Raman scattering

A simple and rapid solution-phase synthesis of dendritic gold nanostructures with hyperbranched architecture is demonstrated in this report. Further investigations revealed that the morphology of the synthesized sample depended on proper parameters such as reagent concentration, reaction temperature, reagent addition sequence and stir. Moreover, the dendritic gold nanostructures exhibited a good electrocatalytic activity toward methanol electro-oxidation. When compared with sea-urchinlike and flowerlike gold nanostructures which were prepared by varying the parameters of experiment, dendritic gold nanostructures showed the highest surface-enhanced Raman scattering (SERS) sensitivity using 4-aminothiophenol (4-ATP) as probe molecules. The dendritic gold nanostructures may find potential applications in catalysis, SERS and biosensor.     

Shape-controlled electrodeposition of gold nanostructures

A one-step, nontemplated, low-cost electrochemical method for the growth of gold nanostructures with different shapes is reported here. It is the first time that nanopyramidal, nanorod-like, and spherical gold nanostructures were fabricated on polycrystalline gold substrates through electrochemical overpotential deposition (OPD) by easily manipulating the deposited potentials and concentrations of HAuCl4. X-ray diffraction and electrochemical analyses revealed that the pyramidal structures are more extensively dominated by (111) facets in comparison with the other nanostructures. The nanopyramids, which have anisotropic structures, exhibited broad extinction over the visible region, most likely due to plasmon resonance. Oxygen reduction activity of a gold electrode with the pyramidal structures was lower than those of the electrodes with the other nanostructures since the activity at the gold (111) surface is lower than that at the (100) and (110) surfaces.     

Plasmonic properties of silver nanostructures coated with an amorphous silicon-carbon alloy and their applications for sensitive sensing of DNA hybridization

The use of an amorphous silicon-carbon alloy overcoating on silver nanostructures in a localized surface plasmon resonance (LSPR) sensing platform allows for decreasing the detection limit by an order of magnitude as compared to sensors based on gold nanostructures deposited on glass. In addition, silver based multilayer structures show a distinct plasmonic behaviour as compared to gold based nanostructures, which provides the sensor with an increased short-range sensitivity and a decreased long-range sensitivity.     

Gold nanostructures: engineering their plasmonic properties for biomedical applications

The surface plasmon resonance peaks of gold nanostructures can be tuned from the visible to the near infrared region by controlling the shape and structure (solid vs. hollow). In this tutorial review we highlight this concept by comparing four typical examples: nanospheres, nanorods, nanoshells, and nanocages. A combination of this optical tunability with the inertness of gold makes gold nanostructures well suited for various biomedical applications.     

Surfactantless synthesis of multiple shapes of gold nanostructures and their shape-dependent SERS spectroscopy

A useful method for the synthesis of various gold nanostructures is presented. The results demonstrated that flowerlike nanoparticle arrays, nanowire networks, nanosheets, and nanoflowers were obtained on the solid substrate under different experimental conditions. In addition, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) on the as-prepared gold nanostructures of various shapes were measured, and their shape-dependent properties were evaluated. The intensity of the SERS signal was the smallest for the gold nanosheets, and the flowerlike nanoparticle arrays gave the strongest SERS signals.     

基于AuCl(油胺)复合物合成形貌可控的金纳米结构

简要综述了使用一价金复合物AuCl(油胺)作为前驱物合成形貌可控的金纳米结构的相关工作. 通过改变有机溶剂、添加异质金属纳米粒子及控制反应温度等手段, 成功合成出球形的金纳米粒子(平均直径12.7 nm)、超细金纳米线(平均直径1.8 nm)及超细金纳米棒(平均直径2 nm); 并通过牺牲磁性纳米粒子模板的方法合成出枝状金纳米结构. 除了对合成方法和过程的介绍, 还简要讨论了每种纳米结构的形成机制.     

Synthesis and assembly of gold nanoparticles in organized molecular films of gemini amphiphiles

Generation and assembly of gold nanostructures were investigated in the organized molecular films of a series of gemini amphiphiles. The chloroauric acid, dissolved in the aqueous subphase, was incorporated into the monolayers of the gemini amphiphiles containing ethyleneamine spacers through an interfacial assembly. The in situ formed complex monolayers were transferred onto solid substrates, and gold nanoparticles were generated in the film by a chemical or photochemical reduction. Discrete gold nanoparticles with an absorption maximum at 550 nm were generated in the films by photoirradiation, while different gold nanostructures were obtained by chemical reduction. Depending on the chemical reductant, various shape and assembly of gold nanostructures were obtained. When reduced by hydroquinone, a tree-branched assembly of the nanoparticles was obtained and the film showed a broad band centered at around 900 nm. When NaBH 4 was applied, crooked nanowires or assembly of nanoparticles were obtained, depending on concentration, and the film showed absorption at 569 or 600 nm. Furthermore, by combining the photochemical and chemical reduction methods, i.e., the chloroaurate ion-incorporated film was initially irradiated with UV light and then subjected to chemical reduction, the optical absorption of the formed gold nanostructures can be regulated.     

Correlation analysis of TEM images of nanocrystal molecules

Quantitative characterization of images of nanocrystals and nanostructures is a challenging but important task. The development and optimization of methods for the construction of complex nanostructures rely on imaging techniques. Computer programs were developed to quantify TEM images of nanocrystal/DNA nanostructures, and results are presented for heterodimers and trimers of gold nanocrystals. The programs presented here have also been used to analyze more complex trimers and tetramers linked by branched DNA, as well as for structures made from attaching gold nanocrystals to CdSe/ZnS core-shell quantum dots. This work has the additional goal of enabling others to quickly and easily adapt the methods for their own use.     

Raman enhancement of azobenzene monolayers on substrates prepared by Langmuir-Blodgett deposition and electron-beam lithography techniques

Nanostructured metallic platforms for Raman enhancement were fabricated using Langmuir-Blodgett and electron beam (e-beam) lithography techniques. The gold platforms were inscribed on thin glass slides with the purpose of using them in a transmission geometry experimental setup under a confocal microscope. The plasmon frequency of the gold nanostructures was determined in the visible-near-infrared range for various pattern sizes prepared by Langmuir-Blodgett transfer and e-beam lithography. The surface Raman enhancement factors were determined for a monolayer of azobenzene molecules adsorbed on gold through thiol bonding and compared for both LB transfer and e-beam samples for nanostructures of comparable geometries.     

Uniform arrays of gold nanoparticles with different surface roughness for surface enhanced Raman scattering

Uniform arrays of coarse and smooth gold nanoparticles with diameter about 130 nm were successfully synthesized through seed-mediated growth method, separately. Scanning and transmission electron microscopy (SEM and TEM) and X-ray diffraction (XRD) have been used to study the formation and structure of the nanocomposites. The high enhancement factor for surface-enhanced Raman scattering of coarse and smooth gold nanoparticles were estimated to be about 3.1 × 10⁶ and 2.0 × 10⁶, respectively. It is evident that the coarse gold nanostructures has higher influence factor than the smooth gold nanostructures. Therefore, these unique properties of the coarse Au nanoparticles appear to be very promising for applications as high-performance SERS substrates.     

Wires, plates, flowers, needles, and core-shells: diverse nanostructures of gold using polyaniline templates

A simple and versatile method for the synthesis of a wide range of polyaniline (PANI)-based 1D and 2D gold nanostructures of uniform size distribution with high colloidal stability is demonstrated. All the nanostructures were synthesized from oligoaniline-coated gold nanoparticle precursors. The nanostructures include nanowires of various sizes, nanoplates, and flower-like nanoparticles. These nanowires showed a pH-dependent shape transformation. Needle-like aggregates of Au/PANI were formed as the pH of the nanowire solution changed to 2.5. At higher pH (10.2), nanowires converted into spherical nanoparticles. Core-shell particles of Au/PANI composites have been achieved by the reversal of the pH of the nanowire from 10.2 to 2.9. The morphology of the nanostructures was studied by TEM and SEM. FTIR, UV-vis, XRD, and LDI MS were utilized for the characterization of the chemical composition of the nanostructures. A mechanism for the nanowire growth is proposed.     

Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium

A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments.     

The assemble,grow and lift-off (AGLO) strategy to construct complex gold nanostructures with pre-designed morphologies

The construction of metallic nanostructures with customizable morphologies and complex shapes has been an essential pursuit in nanoscience. DNA nanotechnology has enabled the fabrication of increasingly complex DNA nanostructures with unprecedented specificity, programmability and sub-nanometer precision, which makes it an ideal approach to rationally organize metallic nanostructures. Here we report an Assemble, Grow and Lift-Off (AGLO) strategy to construct robust standalone gold nanostructures with pre-designed customizable shapes in solution, using only a simple 2D DNA origami sheet as a versatile transient template. Gold nanoparticle (AuNP) seeds were firstly assembled onto the pre-designed binding sites of the DNA origami template and then additional gold was slowly deposited onto the AuNP seeds. The growing seed surfaces eventually merge with adjacent seeds to generate one continuous gold nanostructure in a pre-designed shape, which can then be lifted off the origami template. Diverse customized patterns of templated AuNP seeds were successfully transformed into corresponding gold nanostructures with the target structure transformation percentage over 80%. Moreover, the AGLO strategy can be incorporated with a magnetic bead separation platform to enable the easy recycling of the excess AuNP seeds and DNA components.

The AGLO strategy generates complex gold nanostructures with user-designed morphologies in solution, using only a simple 2D DNA origami sheet as a versatile transient template. The products are robust and stable as standalone gold nanostructures.     

Systematic Synthesis of ZnO Nanostructures

In this study, we report a simple solution‐phase method to prepare ZnO nanostructures with controllable morphologies. By using oleylamine (OAm) and dodecanol (DDL) as solvents, zinc oxide nanocrystals with tunable sizes and diverse shapes (hexagonal pyramids, bulletlike, and pencil‐like shapes) have been obtained under mild conditions. At the same time, the introduction of presynthesized gold nanocrystals can also lead to the hybrid nanostructures of gold–zinc oxide hexagonal nanopyramids. In addition, the possible formation mechanism of the as‐prepared ZnO nanostructures has been investigated. Notably, the unique optical properties of the ZnO nanostructures with different sizes and shapes have also been discussed. We hope that this strategy will be a general and effective method for fabricating other metal oxide nanocrystals.     

Transmetalation reaction between hydrophobic silver nanoparticles and aqueous chloroaurate ions at the air-water interface

The transmetalation reaction between a sacrificial nanoparticle and more noble metal ions in solution has emerged as a novel method for creating unique hollow and bimetallic nanostructures. In this report, we investigate the possibility of carrying out the transmetalation reaction between hydrophobic silver nanoparticles assembled and constrained at the air-water interface and subphase gold ions. We observe that facile reduction of the subphase gold ions by the sacrificial silver nanoparticles occurs resulting in the formation of elongated gold nanostructures that appear to cross-link the sacrificial silver particles. This transmetalation reaction may be modulated by the insertion of an electrostatic barrier in the form of an ionizable lipid monolayer between the silver nanoparticles and the aqueous gold ions that impacts the gold nanoparticle assembly. Transmetalation reactions between nanoparticles constrained into a close-packed structure and appropriate metal ions could lead to a new strategy for metallic cross-linking of nanoparticles and generation of coatings with promising optoelectonic behavior.     

Amine‐Functionalized Polyglycidyl Methacrylate Microsphere as a Unified Template for the Synthesis of Gold Nanoparticles and Single‐Crystal Gold Plates

Polyglycidyl methacrylate (PGMA) microspheres, crosslinked and surface‐functionalized by amine, can be used as a solid‐state template for the synthesis of gold (Au) crystals in the forms of either nanoparticles (NPs) or plates. It is discovered that the polymer microsphere acts as an internal template to cultivate Au NPs inside the microsphere or an external template to generate the single‐crystal plates depending on the critical concentration (C_cr) of gold ions. The ion–dipole interaction and the structure‐dependent solubility of gold induce two distinct gold nanostructures in the presence of the functionalized polymer microspheres. The catalytic activity and long‐term storage of the developed gold nanostructures that can be easily scaled‐up for mass production through the developed novel methodology is demonstrated.     

Towards Electrochemiluminescence Microscopy Exploration of Plasmonic-Mediated Phenomena at the Single-Nanoparticle Level

The rational design of functional plasmonic metasurfaces and metamaterials requires the development of high-throughput characterization techniques compatible with operando conditions and capable of addressing single-nanostructures. In their work, Wei et al. demonstrate the use of electrochemiluminescence microscopy to investigate the mechanism behind plasmon-enhanced luminescence induced by gold nanostructures. The use of gold plasmonic arrays was exploited to achieve the rapid spectroscopic evaluation of all the individual nanostructures, and the correlation of the results with high- resolution electron microscopy analysis, guaranteeing a strict one-to-one correspondence. The authors were able to identify two different mechanisms for the enhancement of [Ru(bpy)₃]²⁺-tri-n-propylamine electrochemiluminescence mediated by single gold nanoparticles and by small plasmonic clusters. In the future, the proposed characterization could be used for the rapid and in situ spectroscopic analysis of more complex plasmonic nanostructures and metasurfaces.     

Silica-void-gold nanoparticles: temporally stable surface-enhanced Raman scattering substrates

Reproducible detection of a target molecule is demonstrated using temporally stable solution-phase silica-void-gold nanoparticles and surface-enhanced Raman scattering (SERS). These composite nanostructures are homogeneous (diameter = 45 +/- 4 nm) and entrap single 13 nm gold nanoparticle cores inside porous silica membranes which prevent electromagnetic coupling and aggregation between adjacent nanoparticles. The optical properties of the gold nanoparticle cores and structural changes of the composite nanostructures are characterized using extinction spectroscopy and transmission electron microscopy, respectively, and both techniques are used to monitor the formation of the silica membrane. The resulting nanostructures exhibit temporally stable optical properties in the presence of salt and 2-naphthalenethiol. Similar SERS spectral features are observed when 2-naphthalenethiol is incubated with both bare and membrane-encapsulated gold nanoparticles. Disappearance of the S-H Raman vibrational band centered at 2566 cm(-1) with the composite nanoparticles indicates that the target molecule is binding directly to the metal surface. Furthermore, these nanostructures exhibit reproducible SERS signals for at least a 2 h period. This first demonstration of utilizing solution-phase silica-void-gold nanoparticles as reproducible SERS substrates will allow for future fundamental studies in understanding the mechanisms of SERS using solution-phase nanostructures as well as for applications that involve the direct and reproducible detection of biological and environmental molecules.