Gold Nanoparticle Dimers Research Articles

DNA‐Directed Gold Nanodimers with Tunable Sizes and Interparticle Distances and Their Surface Plasmonic Properties

A quantitative understanding of the localized surface plasmon resonances (LSPRs) of metallic nanostructures has received tremendous interest. However, most of the current studies are concentrated on theoretical calculation due to the difficulty in experimentally obtaining monodisperse discrete metallic nanostructures with high purity. In this work, endeavors to assemble symmetric and asymmetric gold nanoparticle (AuNP) dimer structures with exceptional purity are reported using a DNA self-assembly strategy through a one-step gel electrophoresis, which greatly facilitates the preparation process and improves the final purity. In the obtained Au nanodimers, the sizes of AuNPs (13, 20, and 40 nm) and the interparticle distances (5, 10, and 15 nm) are tunable. The size- and distance-dependent plasmon coupling of ensembles of single, isolated dimers in solution are subsequently investigated. The experimental measurements are correlated with the modeled plasmon optical properties of Au nanodimers, showing an expected resonance shift with changing particle sizes and interparticle distances. This new strategy of constructing monodisperse metallic nanodimers will be helpful for building more complicated nanostructures, and our theoretical and experimental understanding of the intrinsic dependence of plasmon property of metallic nanodimer on the sizes and interparticle distances will benefit the future investigation and exploitation of near-field plasmonic properties.

Surface enhanced fluorescence and Raman scattering by gold nanoparticle dimers and trimers

Dimers and trimers of gold nanoparticles were synthesized using wet chemistry method for surface enhanced fluorescence and Raman scattering. The dimers and trimers provide hot spots for enhancing the fluorescence and Raman signals, and significantly obvious enhancement is obtained from Raman signals in solution. Using finite element method, we calculate the enhancement of fluorescence and Raman signals in the experimental system. Both experimental and theoretical results show that the dimers and trimers solution can be used in micro-quantitative detection from fluorescence and Raman signals.

Reversible Switching of the Interparticle Distance in DNA-Templated Gold Nanoparticle Dimers

We produce gold nanoparticle dimers with a surface-to-surface distance that varies reversibly by a factor of 3 when hybridizing or removing a single target DNA strand. The dimers are built on one DNA template that features a stem-loop enabling the interparticle distance change. Using electrophoresis, we reach 90% sample purities and demonstrate that this chemical process is reversible in solution at room temperature for a low molar excess of the target DNA strand. The kinetics of the reaction is asymmetric due to steric hindrance in the stem-loop opening process. Furthermore, a statistical analysis of cryo-electron microscopy measurements allows us to provide the first quantitative analysis of distance changes in chemically switchable nanoparticle assemblies.

Switchable Nanodumbbell Probes for Analyte Detection

Nanodumbbell gold nanoparticle (AuNP) dimers connected by DNA show significant change in interparticle distance in the presence of a specific analyte, ATP. The nanodumbbell begins in an extended state, but after the addition of the analyte, the DNA connecting the AuNPs forms a stable hairpin, which causes a large decrease in the interparticle distance.

Photonic Engineering of Hybrid Metal–Organic Chromophores

An aureate dye: Confined electromagnetic fields in DNA-templated gold nanoparticle dimers were tuned to engineer the fluorescence properties of organic dyes in water (see picture). Purified suspensions of hybrid metal–organic chromophores featured unprecedented photophysical properties, such as a short lifetime and low quantum yield but high brightness. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Distance‐Mediated Plasmonic Dimers for Reusable Colorimetric Switches: A Measurable Peak Shift of More than 60 nm

The first reconfigurable colorimetric DNA switches based on target DNA binding are reported. This DNA binding actuates a change in the interparticle distance between gold nanoparticle dimers. A significant spectral shift of 68 nm is achievable from on-off switching. The reconfigurability is possible owing to thiol and EDC-imidazole coupling which anchors the DNA linkers to the nanoparticles. The huge spectral shift allows the unaided eye to observe single target biomolecular binding event in real time under a darkfield microscope. The limit-of-detection for target molecules in PBS and human serum are 10(-13) M and 10(-11) M respectively. An improved fabrication strategy via asymmetric functionalization is also described, assisted by solid phase synthesis which minimizes the formation of trimers and multimers.

Self-Similar Gold-Nanoparticle Antennas for a Cascaded Enhancement of the Optical Field

We experimentally demonstrate cascaded field enhancement by means of gold nanoparticle dimer and trimer antennas. The local field enhancement is probed by single-molecule fluorescence using fluorophores with high intrinsic quantum efficiency (Q(0)>80%). Using a self-similar trimer antenna consisting of 80, 40, and 20 nm gold nanoparticles, we demonstrate a fluorescence enhancement of 40 and a spatial confinement of 15 nm. Compared with a single gold nanoparticle, the self-similar trimer antenna improves the enhancement-confinement ratio by more than an order of magnitude. Self-similar antennas hold promise for high-resolution imaging and spectroscopy, ultrasensitive detection, and efficient single-photon sources.

Toward Plasmonic Polymers

We establish the concept of a plasmonic polymer, whose collective optical properties depend on the repeat unit. Experimental and theoretical analyses of the super- and sub- radiant plasmon response of plasmonic polymers comprising repeat units of single nanoparticles or dimers of gold nanoparticles show that (1) the redshift of the lowest energy coupled mode becomes minimal as the chain approaches the infinite chain limit at a length of ∼10 particles, (2) the presence and energy of the modes are sensitive to the geometries of the constituents, that is, repeat unit, but (3) spatial disorder and nanoparticle heterogeneity have only small effects on the super-radiant mode.

Solid Phase Supported “Click”-Chemistry Approach for the Preparation of Water Soluble Gold Nanoparticle Dimers

We investigated the potential of the Cu(I) catalyzed azide-alkyne cycloaddition between water soluble azide and alkyne functionalized gold nanoparticles in terms of dimer formation via a solid phase support. Alkyne and azide lipoic acid derivatives are prepared and utilized as stabilizing ligands for 15 nm gold colloids. For the solid phase supported click reaction first citrate stabilized gold nanoparticles are immobilized on amine terminated silicon wafers. In the following step the citrate ligands of the upper free accessible nanoparticle surface are exchanged against a mixture of the alkyne derivative of lipoic acid and lipoic acid. Upon addition of lipoic acid/lipoic acid azide derivative stabilized 15 nm gold nanoparticles and the Cu(I) catalyst solution covalent interparticle coupling between immobilized and gold nanoparticles added is achieved. The formed structures are analyzed by scanning electron microscopy directly on the solid support. It is demonstrated that the yield of dimeric structures on the solid phase support increases with increased molar ratio of the catalyst, thus indicating that dimers are indeed formed by covalent bond formation. Upon treatment with ultrasound the formed structures could be released and detected with transmission electron microscopy measurements.

Polarization Properties of a CdSe/ZnS and Au Nanoparticle Dimer

A hybrid CdSe/ZnS quantum dot and gold nanoparticle dimer is assembled using AFM nanomanipulation. The quantum dot acquires a pronounced polarization dependence on the incident excitation light due to the excitation of localized surface plasmons in the gold nanoparticle (see picture). A large polarization contrast ratio beyond the maximum field enhancement is observed and explained quantitatively.

Water-Based Assembly and Purification of Plasmon-Coupled Gold Nanoparticle Dimers and Trimers

We describe a simple one-pot water-based scheme to produce gold nanoparticle groupings with short interparticle spacings. This approach combines a cross-linking molecule and a hydrophilic passivation layer to control the level of induced aggregation. Suspensions of dimers and trimers are readily obtained using a single electrophoretic purification step. The final interparticle spacings allow efficient coupling of the particle plasmon modes as verified in extinction spectroscopy.

Controlled Formation of Gold Nanoparticle Dimers Using Multivalent Thiol Ligands

Approaches for the controlled formation of gold nanoparticle dimers are investigated. These are based on a locally confined surface modification of gold nanoparticles followed by bridging two particles with an organic linker. A key factor in these approaches is the use of multivalent ligands. Citrate-stabilized gold nanoparticles are immobilized on a glass surface and mono- and multivalent thiol ligands are investigated regarding their ability to inactivate the nanoparticles sites facing away from the glass. A successful locally confined functionalization is only possible if multivalent ligands are used in this step. The application of monovalent ligands results in less stable particles without a permanent regioselective functionalization. This result can be explained by the dynamic equilibrium between bound and free ligands. Subsequently, the sites of the nanoparticles previously bound to the glass surface are functionalized with thiol ligands additionally bearing a reactive group. Approaches using dithiol linkers, diamine linkers, and coupling complementary functionalized particles are investigated. The highest yield of stable dimers is obtained from conditions where nanoparticles which are regioselectively functionalized with an N-hydroxysuccinimide ester are reacted with complementary amino-functionalized particles. The application of nanoparticles with activated carboxyl groups is essential since standard carboxyl activation agents induce an aggregation of the nanoparticles due to a reaction with remaining citrate molecules on the nanoparticle surface which reduces significantly electrostatic stabilization. This versatile approach using complementary regioselective with multivalent ligands functionalized nanoparticles may be also used for the coupling of particles with different size, shape, or composition, as well as a control of the interparticle distance.

Optical and Topological Characterization of Gold Nanoparticle Dimers Linked by a Single DNA Double Strand

We demonstrate that symmetric or asymmetric gold nanoparticle dimers with substantial scattering cross sections and plasmon coupling can be produced with a perfectly controlled chemical environment and a high purity using a single DNA linker as short as 7 nm. A statistical analysis of the optical properties and morphology of single dimers is performed using darkfield and cryo-electron microscopies. These results, correlated to Mie theory calculations, indicate that the particle dimers are stretched in water by electrostatic interactions.

Femtomolar DNA detection by parallel colorimetric darkfield microscopy of functionalized gold nanoparticles

We introduce a sensing platform for specific detection of DNA based on the formation of gold nanoparticles dimers on a surface. The specific coupling of a second gold nanoparticle to a surface bound nanoparticle by DNA hybridization results in a red shift of the nanoparticle plasmon peak. This shift can be detected as a color change in the darkfield image of the gold nanoparticles. Parallel detection of hundreds of gold nanoparticles with a calibrated true color camera enabled us to detect specific binding of target DNA. This enables a limit of detection below 1.0 × 10 −14 M without the need for a spectrometer or a scanning stage.

Copper(ii) coordination compounds as building blocks for the formation of gold nanoparticle dimers

A new way for gold nanoparticle dimer formation based on the coordination interaction of a benzimidazole copper(ii) complex with gold nanoparticles has been proposed.

Plasmonic Nanoparticle Dimers for Optical Sensing of DNA in Complex Media

We introduce a new sensing modality based on the actuation of discrete gold nanoparticle dimers. Binding of the target DNA leads to a geometrical extension of the dimer, thereby yielding a spectral blue shift in the hybridized plasmon mode as detected by single nanostructure scattering spectroscopy. The magnitude and opposite direction of this shift enabled us to spectroscopically distinguish the target from nonspecific binding and to detect the target in complex media like serum.

Immobilization of Gold Nanoparticles on Aluminum Oxide Nanoporous Structure for Highly Sensitive Plasmonic Sensing

In this work, we investigate the optical properties of a nanostructure design with plasmonic gold nanoparticles (AuNPs) and photonic thin-film multilayers of aluminum oxide on an aluminum film. An aluminum oxide nanoporous surface fabricated by the two-step anodizing method is treated with cationic poly(allyl amine) to fix AuNPs on the surface. The porous nanostructure partially trapped two nanoparticles, producing a small number of nanoparticle dimers on the substrate surface. The experimental and simulation results show that the plasmonic spectra of these gold nanoparticle dimers (AuNDs) are enhanced by the interference spectra of the Al2O3/Al multilayer. On the basis of the longitudinal localized surface plasmon resonance (LSPR) band of AuNDs, our nanostructure substrate showed a high sensitivity to various solutions with different refractive indices, thus showing promising potential for the to development of a new nanosensor for the label-free monitoring of biomolecular interactions.

Alignment, Rotation, and Spinning of Single Plasmonic Nanoparticles and Nanowires Using Polarization Dependent Optical Forces

We demonstrate optical alignment and rotation of individual plasmonic nanostructures with lengths from tens of nanometers to several micrometers using a single beam of linearly polarized near-infrared laser light. Silver nanorods and dimers of gold nanoparticles align parallel to the laser polarization because of the high long-axis dipole polarizability. Silver nanowires, in contrast, spontaneously turn perpendicular to the incident polarization and predominantly attach at the wire ends, in agreement with electrodynamics simulations. Wires, rods, and dimers all rotate if the incident polarization is turned. In the case of nanowires, we demonstrate spinning at an angular frequency of approximately 1 Hz due to transfer of spin angular momentum from circularly polarized light.

High-throughput fabrication of nanoantennae over large areas for biosensing and nanospectroscopy

We report on a simple and high-throughput method for the fabrication of gold and silver nanoparticle dimers with extremely small gaps and extending over large areas, using colloidal lithography and shadow thermal-evaporation techniques. The plasmon resonances of the individual dimers with various structural parameters were studied, as well as their coupling phenomena in the nearly touching regime. The method presented enables fabrication of efficient and low-cost plasmonics structures for applications such as surface-enhanced Raman scattering, plasmon-enhanced fluorescence, and biosensing.

Probing the Conformational Distributions of Subpersistence Length DNA

We have measured the bending elasticity of short double-stranded DNA (dsDNA) chains through small-angle x-ray scattering from solutions of dsDNA-linked dimers of gold nanoparticles. This method, which does not require exertion of external forces or binding to a substrate, reports on the equilibrium distribution of bending fluctuations, not just an average value (as in ensemble fluorescence resonance energy transfer) or an extreme value (as in cyclization), and in principle provides a more robust data set for assessing the suitability of theoretical models. Our experimental results for dsDNA comprising 42–94 basepairs are consistent with a simple wormlike chain model of dsDNA elasticity, whose behavior we have determined from Monte Carlo simulations that explicitly represent nanoparticles and their alkane tethers. A persistence length of 50 nm (150 basepairs) gave a favorable comparison, consistent with the results of single-molecule force-extension experiments on much longer dsDNA chains, but in contrast to recent suggestions of enhanced flexibility at these length scales.