Gold nanoparticle decoration of DNA on silicon

Electrostatic assembly of cationic nanoparticles onto the negatively charged backbone of double-stranded DNA has been shown to produce one-dimensional chains with potential use as nanoelectronic components. In this paper, micron long DNA templates stretched on aminosilane- and hexamethyldisilazane-modified silicon surfaces are used to assemble 3.5 nm gold nanoparticles passivated with cationic thiocholine. Atomic force microscopy is used to analyze the density and defects along the approximately 5 nm high structures, with comparison between positively charged and neutral surfaces. Low background adsorption of nanoparticles is facilitated by both these surface chemistries, while the neutral surface yields a more densely packed assembly.     

A calorimetric investigation of the assembly of gold nanorods to form necklaces

Interaction of gold nanorods with cysteine as well as 3-mercaptopropionic acid (MPA) has been investigated by isothermal titration calorimetry (ITC), in combination with electronic absorption spectroscopy and electron microscopy. The assembly process with MPA shows two steps, the first due to the binding of MPA to gold nanorods through the sulfur atom, and the second due to assembly of the MPA capped gold nanorods through the formation of cyclic hydrogen bonded dimers between the MPA molecules. In the case of cysteine only a single step is observed in ITC, due to the binding of the molecules to gold nanorods.     

Oriented assembly of Au nanorods using biorecognition system

The design and formation of a linear assembly of gold nanorods using a biomolecular recognition system are described. Anti-mouse IgG was immobilized on the {111} end faces of gold nanorods through a thioctic acid containing a terminal carboxyl group. The biofunctionalized nanorods can be assembled with the desired length using mouse IgG for biorecognition and binding. The gold nanorods can be assembled to extended nanorod chains, which can be as long as 3 microm. These assembled nanostructures may be used as the precursors for future nanodevices.     

Four‐Dimensional Deoxyribonucleic Acid–Gold Nanoparticle Assemblies

Organization of gold nanoobjects by oligonucleotides has resulted in many three‐dimensional colloidal assemblies with diverse size, shape, and complexity; nonetheless, autonomous and temporal control during formation remains challenging. In contrast, living systems temporally and spatially self‐regulate formation of functional structures by internally orchestrating assembly and disassembly kinetics of dissipative biomacromolecular networks. We present a novel approach for fabricating four‐dimensional gold nanostructures by adding an additional dimension: time. The dissipative character of our system is achieved using exonuclease III digestion of deoxyribonucleic acid (DNA) fuel as an energy‐dissipating pathway. Temporal control over amorphous clusters composed of spherical gold nanoparticles (AuNPs) and well‐defined core–satellite structures from gold nanorods (AuNRs) and AuNPs is demonstrated. Furthermore, the high specificity of DNA hybridization allowed us to demonstrate selective activation of the evolution of multiple architectures of higher complexity in a single mixture containing small and larger spherical AuNPs and AuNRs.     

基于AFM纳米氧化技术的金纳米粒子定点组装

二维纳米粒子矩阵列在纳米电子器件^[1,2]、表面增强喇曼活性基底^[3,4]、刻蚀掩模^[5]等领域具有广泛的应用前景。在这些纳米粒子阵列为内部,纳米粒子的排布是随机、无序的。这一缺点已经妨碍了纳米粒子阵列在上述领域中的进一步应用。基于此,人们开始关注纳米粒子的可控组装。传统的光刻技术^[6]、微接触印刷技术^[7]以及生物分子模板技术^[8]都被用来实现纳米粒子在固体表面上的可控组装,本实验室在纳米粒子的合成及可控组装方面也进行了研究^[7,9,11]。本文力图精确控制单个纳米粒子在基底表面上的组装位置。利用AFM纳米氧化技术。在硅表面构建了纳米级的化学图形化表面,通过不同的化学官能团,如甲基、氨基对金纳米粒子亲和性质的差异,实现了纳米粒子在固体表面的定点组装。     

Precise placement of gold nanorods by capillary assembly

Capillary assembly was explored for the precise placement of 25 nm × 70 nm colloidal gold nanorods on prestructured poly(dimethylsiloxane) template surfaces. The concentration of nanorods and cationic surfactant cetyltrimethylammonium bromide (CTAB), the template wettability, and most critically the convective transport of the dispersed nanorods were tuned to study their effect on the resulting assembly yield. It is shown that gold nanorods can be placed into arrayed 120-nm diameter holes, achieving assembly yields as high as 95% when the local concentration of nanorods at the receding contact line is sufficiently high. Regular arrays of gold nanorods have several benefits over randomly deposited nanorod arrangements. Each assembled nanorod resides at a precisely defined location and can easily be found for subsequent characterization or direct utilization in a device. The former is illustrated by collecting scattering spectra from single nanorods and nanorod dimers, followed by subsequent SEM characterization without the need for intricate registration schemes.     

Programmable Supra‐Assembly of a DNA Surface Adapter for Tunable Chiral Directional Self‐Assembly of Gold Nanorods

An important challenge in molecular assembly and hierarchical molecular engineering is to control and program the directional self‐assembly into chiral structures. Here, we present a versatile DNA surface adapter that can programmably self‐assemble into various chiral supramolecular architectures, thereby regulating the chiral directional “bonding” of gold nanorods decorated by the surface adapter. Distinct optical chirality relevant to the ensemble conformation is demonstrated from the assembled novel stair‐like and coil‐like gold nanorod chiral metastructures, which is strongly affected by the spatial arrangement of neighboring nanorod pair. Our strategy provides new avenues for fabrication of tunable optical metamaterials by manipulating the directional self‐assembly of nanoparticles using programmable surface adapters.     

Preparation of gold nanoislands on various functionalized polymer-modified glass and ITO for electrochemical characterization of monolayer assembly of alkanethiols

Nanometer dimension of citrate-capped gold nanoparticles can be firmly bound with various functionalized polymer-modified glass plate and indium tin oxide (ITO) substrates. Herein we report 3-aminopropyltriethoxysilane, polyvinyl pyridine, polyethylene imines, etc. as binding agents to modify these substrates to stabilize the charged colloidal gold nanoparticles through electrostatic stabilization of gold nanoparticles. When gold nanoparticles pretreated substrate are exposed into the seeding growth solution, the preadsorbed gold nanoparticles grow further and then form nanoislands of gold on glass and ITO substrates. The formation of nanoislands on microscope glass slide and ITO was monitored with UV-visible spectroscopy, cyclic voltammetry, and atomic force microscopy methods. The gold nanoislands and gold nanoparticles pretreated substrates can be used as platform to study the self-assembling behavior of long chain alkanethiols such as C₁₂SH, C₁₆SH, and C₁₈SH. The binding, coverage, and electron transfer characteristics of monolayer assembly on modified gold nanoisland and nanoparticles modified substrates are studied using electrochemical studies. The gold substrates can be prepared by this method, which is simple and reproducible and can be applied to various sensor and electrocatalytic applications.     

Fabrication and self-assembly of hydrophobic gold nanorods

Hydrophobic gold nanorods were fabricated from hydrophilic gold nanorods coated with hexadecyltrimethylammonium bromide by treating with mercaptopropyltrimethoxysilane (MPS) and subsequently octadecyltrimethoxysilane (ODS). The fabrication of the hydrophobic shell went through the process of (1) binding MPS onto the nanorods, (2) hydrolysis of methoxysilanes, and (3) immobilization of ODS by dehydration condensation. The 2- or 3-D ordered structures of hydrophobic nanorods were self-assembled by the evaporation of solvent on a substrate. The aspects of 2-D assemblies were dependent on the concentration of the nanorods, as was seen in transmission electron microscopic images. At a low concentration, the nanorods assembled parallel to the substrate, whereas they stood on the substrate at a high concentration. On the other hand, in a solid of the gold nanorods, the formation of the 3-D assembly was confirmed by small-angle X-ray scattering. The assembly consisted of hexagonal arrays of the gold nanorods and their lamellar accumulation.     

Biotin-streptavidin-induced aggregation of gold nanorods: tuning rod-rod orientation

We report herein biotin-streptavidin-mediated aggregation studies of long gold nanorods. We have previously demonstrated end-to-end linkages of gold nanorods driven by the biotin-streptavidin interaction (Caswell et al. J. Am. Chem. Soc. 2003, 125, 13914). In that report, the specific binding of biotin disulfide to the gold nanorod edges was achieved due to the preferred binding of thiol molecules to the Au[111] surface (gold nanorod ends) as opposed to the gold nanorod side faces. This led to the end-end linkage of gold nanorods upon subsequent addition of streptavidin. In this report we demonstrate a simple procedure to biotinylate the entire gold nanorod surface and subsequently form a 3-D assembly by addition of streptavidin. Gold nanorods were synthesized by the three-step seeding protocol documented in our previous articles. The surface of gold nanorods was further modified by a layer of a weak polyelectrolyte, poly(acrylic acid), PAA. A biotin molecule which has an amine group at one end (biotin-PEO-amine) was anchored to the carboxylic acid group of the polyelectrolyte using the well-known carbodiimide chemistry. This process biotinylates the entire gold nanorod surface. Addition of streptavidin further leads to aggregation of gold nanorods. A closer look at the aggregates reveals a preferential side-to-side assembly of gold nanorods. The gold nanorods were characterized at each stage by UV-vis spectroscopy, light scattering, and transmission electron microscopy (TEM) measurements.     

Four-Dimensional Deoxyribonucleic Acid–Gold Nanoparticle Assemblies

Organization of gold nanoobjects by oligonucleotides has resulted in many three-dimensional colloidal assemblies with diverse size, shape, and complexity; nonetheless, autonomous and temporal control during formation remains challenging. In contrast, living systems temporally and spatially self-regulate formation of functional structures by internally orchestrating assembly and disassembly kinetics of dissipative biomacromolecular networks. We present a novel approach for fabricating four-dimensional gold nanostructures by adding an additional dimension: time. The dissipative character of our system is achieved using exonuclease III digestion of deoxyribonucleic acid (DNA) fuel as an energy-dissipating pathway. Temporal control over amorphous clusters composed of spherical gold nanoparticles (AuNPs) and well-defined core–satellite structures from gold nanorods (AuNRs) and AuNPs is demonstrated. Furthermore, the high specificity of DNA hybridization allowed us to demonstrate selective activation of the evolution of multiple architectures of higher complexity in a single mixture containing small and larger spherical AuNPs and AuNRs.     

Separation of nanorods by density gradient centrifugation

The experimental conditions necessary for the synthesis of well-defined nanoparticles are often difficult to control. There is thus a compelling need for post-synthesis separation of nanoparticles polydispersed in size and shape. We demonstrate here both theoretically and experimentally that gold nanorods with diverse aspect ratios can be separated using density gradient centrifugation. By analysing the force balance of a Brownian rod falling in a Stokes flow, we derive a rigorous and predictive model that reveals the quantitative dependency of the nanorod sedimentation rates on their mass and shape. The calculations show that while mass dependency is still the dominating factor during centrifugation, the shape factor is not insignificant. Relatively heavier but long and thin rods could sediment slower than certain size of lighter spheres, and some rods and spheres with different masses and shapes may never be separated. This mass and shape dependency is exploited to separate as-prepared gold nanorod colloids by sucrose gradient centrifugation. Two layers of nanorods with narrow aspect-ratio distributions are obtained.     

Recent advances in analytical and bioanalysis applications of noble metal nanorods

In the last decade the use of anisotropic nanoparticles in analytical and bioanalytical applications has increased substantially. In particular, noble metal nanorods have unique optical properties that have attracted the interest of many research groups. The localized surface plasmon resonance (LSPR) generated by interaction of light at a specific wavelength with noble metal nanoparticles was found to depend on particle size and shape and on the constituting material and the surrounding dielectric solution. Because of their anisotropic shape, nanorods are characterized by two LSPR peaks: the transverse, fixed at approximately 530 nm, and the longitudinal, which is in the visible–near infra-red region of the spectrum and varies with nanorod aspect ratio. The intense surface plasmon band enables nanorods to absorb and scatter light in the visible and near infra-red regions, and fluorescence and two-photon induced luminescence are also observed. These optical properties, with the reactivity towards binding events that induce changes in the refractive index of the surrounding solution, make nanorods a useful tool for tracking binding events in different applications, for example assembly, biosensing, in-vivo targeting and imaging, and single-molecule detection by surface-enhanced Raman spectroscopy. This review presents the promising strategies proposed for functionalizing gold nanorods and their successful use in a variety of analytical and biomedical applications.     

Gold Nanostructures Formed in Ionic Clusters of Perfluorinated Ionomer

Summary: Gold nanoparticles and nanorods have been synthesized in the ionic cluster network of Nafion using a liquid‐phase chemical impregnation/reduction process seemingly visualizing the phase‐separated hydrated cluster network of Nafion. The spherical shape of the hydrated clusters is clearly seen by the replicated gold nanoparticles with diameters of 5–6 nm. The gold nanoparticles grow through the Nafion cluster network to form gold nanorods with diameters of 5–6 nm and a characteristic length of 12–15 nm, which compare well to the previously reported small‐angle X‐ray scattering results. Tiny channels between adjacent spherical clusters are also observed, which expand to form a rod structure by a reorganization of ion exchange sites and an elastic deformation of Nafion polymer chains. The gold nanorods become interconnected in a cascadic feature, and a tripod‐shaped nanorod structure is one of the most commonly observed structures of the replicated gold. Although further study should be performed, the synthesized gold may be used to visualize the hydrated cluster and the network structure of Nafion, which could be used as important information in identifying the morphology and ion transport phenomena of Nafion.

Gold nanoparticles and nanorods growing through a hydrated Nafion cluster network.     

Single-molecule detection of DNA via sequence-specific links between F1-ATPase motors and gold nanorod sensors

We report the construction of a novel biosensing nanodevice to detect single, sequence-specific target DNA molecules. Nanodevice assembly occurs through the association of an immobilized F1-ATPase molecular motor and a functionalized gold nanorod via a single 3',5'-dibiotinylated DNA molecule. Target-dependent 3',5'-dibiotinylated DNA bridges form by combining ligation and exonucleation reactions (LXR), with a specificity capable of selecting against a single nucleotide polymorphism (SNP). Using dark field microscopy to detect gold nanorods, quantitation of assembled nanodevices is sufficient to distinguish the presence of as few as 1800 DNA bridges from nonspecifically bound nanorods. The rotary mechanism of F1-ATPase can drive gold nanorod rotation when the nanorod is attached via the DNA bridge. Therefore, rotation discriminates fully assembled devices from nonspecifically bound nanorods, resulting in a sensitivity limit of one zeptomole (600 molecules).     

Controlled side-by-side assembly of gold nanorods and dye molecules into polymer-wrapped SERRS-active clusters

The controlled side-by-side assembly of gold nanorods in solution together with Raman reporter dye molecules to create small SERRS-active clusters stabilised by a surrounding polymer layer is demonstrated. This promising new class of nanotags offers several advantages over spherical nanoparticles for bioimaging and is of potential importance for a wide range of plasmon-enhanced spectroscopies and can also serve as building blocks for more complex solution-phase nanostructures.     

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications

This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed.     

Chiral DNA Origami Nanotubes with Well‐Defined and Addressable Inside and Outside Surfaces

We report the design and assembly of chiral DNA nanotubes with well‐defined and addressable inside and outside surfaces. We demonstrate that the outside surface can be functionalised with a chiral arrangement of gold nanoparticles to create a plasmonic device and that the inside surface can be functionalised with a track for a molecular motor allowing transport of a cargo within the central cavity.     

Plasmon coupling in nanorod assemblies: optical absorption, discrete dipole approximation simulation, and exciton-coupling model

The shape anisotropy of nanorods gives rise to two distinct orientational modes by which nanorods can be assembled, i.e., end-to-end and side-by-side, analogous to the well-known H and J aggregation in organic chromophores. Optical absorption spectra of gold nanorods have earlier been observed to show a red-shift of the longitudinal plasmon band for the end-to-end linkage of nanorods, resulting from the plasmon coupling between neighboring nanoparticles, similar to the assembly of gold nanospheres. We observe, however, that side-by-side linkage of nanorods in solution shows a blue-shift of the longitudinal plasmon band and a red-shift of the transverse plasmon band. Optical spectra calculated using the discrete dipole approximation method were used to simulate plasmon coupling in assembled nanorod dimers. The longitudinal plasmon band is found to shift to lower energies for end-to-end assembly, but a shift to higher energies is found for the side-by-side orientation, in agreement with the optical absorption experiments. The strength of plasmon coupling was seen to increase with decreasing internanorod distance and an increase in the number of interacting nanorods. For both side-by-side and end-to-end assemblies, the strength of the longitudinal plasmon coupling increases with increasing nanorod aspect ratio as a result of the increasing dipole moment of the longitudinal plasmon. For both the side-by-side and end-to-end orientation, the simulation of a dimer of nanorods having dissimilar aspect ratios showed a longitudinal plasmon resonance with both a blue-shifted and a red-shifted component, as a result of symmetry breaking. A similar result is observed for a pair of similar aspect ratio nanorods assembled in a nonparallel orientation. The internanorod plasmon coupling scheme concluded from the experimental results and simulations is found to be qualitatively consistent with the molecular exciton coupling theory, which has been used to describe the optical spectra of H and J aggregates of organic molecules. The coupled nanorod plasmons are also suggested to be electromagnetic analogues of molecular orbitals. Investigation of the plasmon coupling in assembled nanorods is important for the characterization of optical excitations and plasmon propagation in these nanostructures. The surface plasmon resonance shift resulting from nanorod assembly also offers a promising alternative for analyte-sensing assays.     

Ordered arrays of gold nanostructures from interfacially assembled Au@PNIPAM hybrid nanoparticles

In this Article, we report on the assembly of hybrid Au@PNIPAM core-shell particles at the air/water interface, their transfer onto solid substrates, and the controlled combustion of the organic material to produce arrays of gold nanoparticles. A detailed investigation on the assembly behavior of such soft hybrid colloids at the air/water interface was performed by correlating the surface pressure-area isotherms with SEM and AFM images from samples transferred at different surface pressures. The hybrid particles display a complex behavior at the interface, and we could distinguish three distinct phases with varying interparticle spacings at different compression. The transfer process presented enables the decoration of topologically structured substrates with gold nanoparticle arrays, and the order of the initial monolayers is retained in the arrays of inorganic gold nanoparticles. The change in monolayer morphology upon compression can therefore be used to tailor the interparticle distance between approximately 650 and 300 nm without exchanging the colloids. More sophisticated gold nanostructures can be patterned into symmetric arrays using a similar protocol, which we demonstrate for nanostars and nanorods.