Gold Nanoparticle Dimers Research Articles

Alkyne‐Monofunctionalized Gold Nanoparticles as Massive Molecular Building Blocks

Using a tripodal, thioether‐based ligand comprising a remote protected acetylene, we efficiently stabilize small gold nanoparticles (Ø ≈ 1.2 nm) which are isolated and purified by chromatography. The 1:1 ligand‐to‐particle ratio is obtained by comparing the particles' dimensions measured by transmission electron microscopy with the weight fraction of the coating ligand determined by thermogravimetric analysis. The single ligand coating of the gold particle guarantees the presence of a single masked alkyne per particle. It can be addressed by wet chemical protocols providing the particles with the properties of “massive molecules”. The “massive molecule” nature of the particles is demonstrated by involving them in wet chemical coupling protocols like oxidative acetylene coupling providing gold nanoparticle dimers (34 % isolated yield) or alkyne‐azide “click”‐chemistry with a suitable triazide, giving trimeric particle architectures (30 % determined by transmission electron microscopy). The particle stabilization obtained by the coating ligand allows, for the first time, to treat these multi‐particle architectures by size exclusion chromatography.

Surface‐enhanced Raman spectroscopy with gold nanoparticle dimers created by sacrificial DNA origami technique

In a previously proposed method for molecular detection based on surface-enhanced Raman spectroscopy (SERS), gold nanoparticle (AuNP) dimers are formed on a substrate using DNA origami with a nanometre-scale gap between them. In this sacrificial DNA origami technique, a conjugate of two AuNPs and a DNA origami is deposited on a silicon chip, and then the DNA origami is selectively removed using vacuum ultraviolet light and ultrapure water rinsing to form surface-clean AuNP dimers. The performance of SERS-based molecular detection of AuNP dimers created using the proposed technique with a 30 nm AuNP diameter has now been evaluated. The Raman signals from the target molecules (4,4′-bipyridine) were greatly enhanced and thus successfully detected.

Competitive aptasensor with gold nanoparticle dimers and magnetite nanoparticles for SERS-based determination of thrombin.

It is known that the intensity of surface-enhanced Raman scattering (SERS) of monomeric gold nanoparticles (GNPs) is insufficient for ultrasensitive analysis. The authors describe dimeric GNPs for use in a competitive SERS and aptamer based assay for thrombin. The reagent 1,2-bis(4-pyridyl) ethylene serves as both the coupling agent and the Raman reporter on the GNP dimers. In the presence of thrombin, the hybridization of two aptamers, one attached to the GNP dimers, the other to magnetic nanoparticles, is competitively prevented. This method takes advantage of the unique "hot spots" of the GNP dimers to amplify the Raman signal. This results in an ultra-sensitive thrombin assay when compared to assays using GNP monomers. The limit of detection is as low as 1 fM of thrombin. The Raman intensity, best measured at 1612cm-1, increases linearly in the 1 fM to 10nM thrombin concentration range. The method was applied to the determinaiton of thrombin in spiked simulated body fluid and human serum. Graphical abstract This method takes advantage of the unique "hot spots" of the gold nanoparticle dimers to amplify the Raman signal. The dimers are linked to the magnetic nanoparticles via an aptamer. The use of both competitive displacementand magnetic separation greatly improves the sensitivity of the thrombin assay.

Precision Plasmonics with Monomers and Dimers of Spherical Gold Nanoparticles: Nonequilibrium Dynamics at the Time and Space Limits

Monomers and dimers of spherical gold nanoparticles (NPs) exhibit highly uniform plasmonic properties at the single-particle level due to their high structural homogeneity (precision plasmonics). R...

Simple and rapid method for homogeneous dimer formation of gold nanoparticles in a bulk suspension based on van der Waals interactions between alkyl chains

We developed a simple and rapid method for dimer and higher multimer formation of gold nanoparticles (AuNPs) in bulk suspension. A coupling of AuNPs modified with COOH-terminated alkanethiol by van-der-Waals interaction between alkyl chains was employed. We demonstrated the tunability of the interparticle gap by changing the alkyl chain length from C5 to C15. Efficient dimer formation that avoids unwanted aggregation was demonstrated for AuNPs with a diameter ranging from 20 nm to 80 nm. For all cases, we found that the interparticle gap is well-defined and uniform. For the shortest alkyl chain (C5), we achieved an interparticle gap as small as 1.0 nm.

Stepwise Ligand-induced Self-assembly for Facile Fabrication of Nanodiamond-Gold Nanoparticle Dimers via Noncovalent Biotin-Streptavidin Interactions.

Nanodiamond-gold nanoparticle (ND-AuNP) dimers constitute a potent tool for controlled thermal heating of biological systems on the nanoscale, by combining a local light-induced heat source with a sensitive local thermometer. Unfortunately, previous solution-based strategies to build ND-AuNP conjugates resulted in large nanoclusters or a broad population of multimers with limited separation efficiency. Here, we describe a new strategy to synthesize discrete ND-AuNP dimers via the synthesis of biotin-labeled DNA-AuNPs through thiol chemistry and its immobilization onto the magnetic bead (MB) surface, followed by reacting with streptavidin-labeled NDs. The dimers can be easily released from MB via a strand displacement reaction and separated magnetically. Our method is facile, convenient, and scalable, ensuring high-throughput formation of very stable dimer structures. This ligand-induced self-assembly approach enables the preparation of a wide variety of dimers of designated sizes and compositions, thus opening up the possibility that they can be deployed in many biological actuation and sensing applications.

Surface Plasmon Coupling in Dimers of Gold Nanoparticles: Experiment and Theory for Ideal (Spherical) and Nonideal (Faceted) Building Blocks

The surface plasmon (SP) coupling in dimers of spherical and faceted gold nanoparticles was investigated experimentally and computationally at the single-particle level. Individual ideal dimers of two spherical gold nanoparticles with a constant gap, filled by a self-assembled monolayer of 1,8-octanedithiol linker molecules, exhibit highly uniform dark-field (DF) scattering spectra. In contrast, single nonideal dimers of two faceted gold nanoparticles with the same constant gap exhibit a high degree of spectral nonuniformity. We attribute this significant spectral heterogeneity to the many possible gap morphologies, that is, the many possible configurations of the crystal facet orientations at the junction of the two faceted particles in nonideal dimers. This configurational complexity is reduced in so-called hybrid dimers, which comprise an ideal spherical particle and a nonideal faceted particle. Hybrid dimers were therefore investigated theoretically and experimentally for revealing the influence of cr...

Manipulating the confinement of electromagnetic field in size-specific gold nanoparticles dimers and trimers.

The intriguing light–matter interactions can be governed by controlling the particle size and shape, electromagnetic interactions and dielectric properties and local environment of the metal nanostructures. Amongst the different approaches that have been engendered to manipulate light at the nanoscale, the self-assembly of metallic nanostructures with controllable interparticle distances and angular orientations, which strongly impact their optical attributes, is one of the viable avenues to exploit their utility in a diverse range of niche applications. The simplest geometrical architectures that enable such modulations are dimers with changeable interparticle distances and trimers with an additional degree of angular orientation to correlate the plasmonic observables with the observed spectral characteristics. Wet chemical approaches have been adopted in this study for the synthesis of size-selective gold nanoparticles, and appropriate organic linkers have judiciously been employed to induce plasmonic interactions amongst the gold nanoparticles in close proximity to each other. The combination of experimental observations and electromagnetic simulations adopted to probe the plasmonic interactions revealed that the electrodynamic coupling effect was very sensitive to particle size, interparticle distances and angular orientations in these simple nanoassemblies. The capability to precisely manipulate the electric field at the junctions between these plasmon-coupled nanoparticles could pave the way for the application of these nanoassemblies in surface-enhanced spectroscopies and sensing applications.

Direct SERS tracking of a chemical reaction at a single 13nm gold nanoparticle.

Metal nanoparticles (NPs) with decreased sizes are promising catalysts in energy and medicine. Measuring the local reactions and simultaneously acquiring molecular insights at single small NPs, however, remain an experimental challenge. Here we report on surface-enhanced Raman spectroscopic (SERS) tracking of catalytic reactions of single 13 nm gold NPs (GNPs) in situ. We designed spatially isolated (>1.5 μm of inter-dimer space) GNP dimers, each of which consisted of two GNPs with sizes of ∼200 and ∼13 nm, respectively. This design integrates the SERS and catalytic activities into a single entity, while eliminating the crosstalk between adjacent particles, which allows us to trace the redox-derived spectral evolution at single 13 nm GNPs for the first time. We also quantified the reaction kinetics of each individual GNP and analyzed the average behavior of multiple GNPs. There is a large variability among different particles, which underscores the significance of single particle analysis.

Dark Plasmon Modes in Symmetric Gold Nanoparticle Dimers Illuminated by Focused Cylindrical Vector Beams

The plasmon hybridization model of electromagnetic coupling between plasmonic nanoparticles predicts the formation of lower energy “bonding” and higher energy “antibonding” modes in analogy with the quantum mechanical description of chemical bonding. For a symmetric metallic nanoparticle dimer excited by linearly polarized light, the hybridization picture predicts that in-phase coupling of the dipole moments is optically allowed, creating bright “modes”, whereas the out-of-phase coupling is dark due to the cancellation of the oppositely oriented dipole moments (in the quasistatic approximation). These bright modes are electric dipolar in nature and readily couple to scalar (i.e., linearly or circularly polarized) beams of light. We show that focused cylindrical vector beams, specifically azimuthally and radially polarized beams, directly excite dark plasmon modes in symmetric gold nanoparticle (AuNP) dimers at normal incidence. We use single-particle spectroscopy and electrodynamics simulations to study the resonance scattering of AuNP dimers illuminated by azimuthally and radially polarized light. The electric field distributions of the focused azimuthal or radial beams are locally polarized perpendicular or parallel to the AuNP dimer axis, but with opposite directions at each particle. Therefore, the associated combinations of single-particle dipole moments are out-of-phase, and the excitation (resonance) is of so-called “dark modes”. In addition, multipole expansion of the fields associated with each scattering spectrum shows that the vector beam excitation involves driving multipolar, e.g., magnetic dipolar and electric quadrupolar, modes, and that they even dominate the scattering spectra (vs electric dipole). This work opens new opportunities for investigating dark plasmon modes in nanostructures, which are difficult to selectively excite by conventional polarized light.

Dumbbell gold nanoparticle dimer antennas with advanced optical properties.

Plasmonic nanoantennas have found broad applications in the fields of photovoltaics, electroluminescence, non-linear optics and for plasmon enhanced spectroscopy and microscopy. Of particular interest are fundamental limitations beyond the dipolar approximation limit. We introduce asymmetric gold nanoparticle antennas (AuNPs) with improved optical near-field properties based on the formation of sub-nanometer size gaps, which are suitable for studying matter with high-resolution and single molecule sensitivity. These dumbbell antennas are characterized in regard to their far-field and near-field properties and are compared to similar dimer and trimer antennas with larger gap sizes. The tailoring of the gap size down to sub-nanometer length scales is based on the integration of rigid macrocyclic cucurbituril molecules. Stable dimer antennas are formed with an improved ratio of the electromagnetic field enhancement and confinement. This ratio, taken as a measure of the performance of an antenna, can even exceed that exhibited by trimer AuNP antennas composed of comparable building blocks with larger gap sizes. Fluctuations in the far-field and near-field properties are observed, which are likely caused by distinct deviations of the gap geometry arising from the faceted structure of the applied colloidal AuNPs.

Ultrasensitive detection of microRNA-21 based on plasmon-coupling-induced electrochemiluminescence enhancement

Noble metal nanoparticles possess excellent optical and electrical properties, and have been widely used in the construction of biosensors and in surface-enhanced spectroscopy. Herein, we describe an enzyme-assisted ultra-sensitive biosensor with gold nanoparticle (GNP) dimers, based on a localized surface plasmon resonance (LSPR)-enhanced electrochemiluminescence (ECL) mechanism. CdS nanocrystals (NCs) acted as ECL emitters, and the GNP dimers were constructed by hybridization of DNA strands on the surface of an electrode modified with CdS NCs after an enzyme-assisted cyclic amplification process. The plasmon-coupling-induced electromagnetic field enhancement effects of the GNP dimers resulted in an increase in ECL intensity of as much as 6.3-fold under optimized conditions. Based on this LSPR-ECL sensor platform, the detection limit for microRNA-21 is as low as 3.6 fM with a wide linear range from 10 fM to 20 pM with good sensitivity and selectivity.

Temperature-Dependent Plasmonic Responses from Gold Nanoparticle Dimers Linked by Double-Stranded DNA.

DNA is a powerful tool to assemble gold nanoparticles into discrete structures with tunable plasmonic properties for photonic or biomedical applications. Because of their photothermal properties or their use in biological media, these nanostructures can experience drastic modifications of the local temperature that can affect their morphology and, therefore, their optical responses. Using single-nanostructure spectroscopy, we demonstrate that, even with a fully stable DNA linker, gold particle dimers can undergo substantial conformational changes at temperatures larger than 50 °C and aggregate irreversibly. Such temperature-dependent resonant optical properties could find applications in imaging and in the design of nonlinear photothermal sources. Inversely, to provide fully stable DNA-templated plasmonic nanostructures at biologically relevant temperatures, we show how passivating the gold nanoparticles using amphiphilic surface chemistries renders the longitudinal plasmon resonance of gold particle dimers nearly independent of the local temperature.

Acoustic Mode Hybridization in a Single Dimer of Gold Nanoparticles.

The acoustic vibrations of single monomers and dimers of gold nanoparticles were investigated by measuring for the first time their ultralow-frequency micro-Raman scattering. This experiment provides access not only to the frequency of the detected vibrational modes but also to their damping rate, which is obscured by inhomogeneous effects in measurements on ensembles of nano-objects. This allows a detailed analysis of the mechanical coupling occurring between two close nanoparticles (mediated by the polymer surrounding them) in the dimer case. Such coupling induces the hybridization of the vibrational modes of each nanoparticle, leading to the appearance in the Raman spectra of two ultralow-frequency modes corresponding to the out-of-phase longitudinal and transverse (with respect to the dimer axis) quasi-translations of the nanoparticles. Additionally, it is also shown to shift the frequency of the quadrupolar modes of the nanoparticles. Experimental results are interpreted using finite-element simulations, which enable the unambiguous identification of the detected modes and despite the simplifications made lead to a reasonable reproduction of their measured frequencies and quality factors. The demonstrated feasibility of low-frequency Raman scattering experiments on single nano-objects opens up new possibilities to improve the understanding of nanoscale vibrations with this technique being complementary with single nano-object time-resolved spectroscopy as it gives access to different vibrational modes.

Enhanced Fluorescence of a Dye on DNA-Assembled Gold Nanodimers Discriminated by Lifetime Correlation Spectroscopy

The surface plasmon modes of metal nanoparticles provide a way to efficiently enhance the excitation and emission from a fluorescent dye. We have employed DNA-directed assembly to prepare dimers of gold nanoparticles and used their longitudinally coupled plasmon mode to enhance the fluorescence emission of an organic red-emitting dye, Atto-655. The plasmon-enhanced fluorescence of this dye using dimers of 80 nm particles was measured at the single-molecule detection level. The top enhancement factors were above 1000-fold in 71% of the dimers within a total of 32 dimers measured, and in some cases, they reached almost 4000-fold, in good agreement with model simulations. Additionally, fluorescence lifetime correlation analysis enabled the separation of enhanced from nonenhanced emission simultaneously collected in our confocal detection volume. This approach allowed us to recover a short relaxation component exclusive to enhanced emission that is attributed to the interaction of the dye with DNA in the inte...

Multiplexed mRNA Sensing and Combinatorial-Targeted Drug Delivery Using DNA-Gold Nanoparticle Dimers.

The design of nanoparticulate systems which can perform multiple synergistic functions in cells with high specificity and selectivity is of great importance in applications. Here we combine recent advances in DNA-gold nanoparticle self-assembly and sensing to develop gold nanoparticle dimers that are able to perform multiplexed synergistic functions within a cellular environment. These dimers can sense two mRNA targets and simultaneously or independently deliver one or two DNA-intercalating anticancer drugs (doxorubicin and mitoxantrone) in live cells. Our study focuses on the design of sophisticated nanoparticle assemblies with multiple and synergistic functions that have the potential to advance sensing and drug delivery in cells.

Spectroscopic and Hydrodynamic Characterisation of DNA-Linked Gold Nanoparticle Dimers in Solution using Two-Photon Photoluminescence.

Two-photon photoluminescence (TPPL) emission spectra of DNA-gold nanoparticle (AuNP) monoconjugates and the corresponding DNA-linked AuNP dimers are obtained by photon time-of-flight spectroscopy. This technique is combined with two-photon photoluminescence fluctuation correlation spectroscopy (TPPL-FCS) to simultaneously monitor the optical and hydrodynamic behaviour of these nano-assemblies in solution, with single-particle sensitivity and microsecond temporal resolution. In this study, the AuNPs have an average core diameter of 12 nm, which renders their dark-field plasmonic light scattering too weak for single-particle imaging. Moreover, as a result of the lack of plasmonic coupling in the dimers, the optical extinction, scattering and photoluminescence spectra of the DNA-AuNP complexes are not sufficiently different to distinguish between monomers and dimers. The use of TPPL-FCS successfully addresses these bottlenecks and enables the distinction between AuNP monomers and AuNP dimers in solution by measurement of their hydrodynamic rotational and translational diffusion.

Nanotemplate-Guided Self-Assembly of Gold Nanoparticles and its Application to Plasmonic Bio/Chemical Sensing

This paper presents a high-precision and high-yield nanotemplate-guided self-assembly process for spherical gold nanoparticles. This process enables us to arrange particles in designated patterns on a substrate with nanotemplates. These particles are trapped on the nanotemplate by liquid-air interfacial force during drying of the colloidal solution. In this method, particle concentration and electrostatic interaction between particles have a considerable effect on the assembly yield. The particle concentration should be optimized based on the template pattern. A nanogap-controlled particle arrangement with a high yield is achieved by controlling the electrostatic interaction, which is accomplished by adding an electrolyte. This technique enables control of the plasmonic resonance properties of metal nanoparticles on substrates for many emerging applications. Among them, this paper discusses the application of nanotemplate-guided self-assembly to an ultrasensitive nanostructure for surface-enhanced Raman spectroscopy. The gold nanoparticle dimer, which has been reported as the highest Raman enhancing structure, is directionally arrayed on a substrate. The highest enhancement can be achieved when the direction of a particle connection for a dimer is matched to the polarization direction of incident light. A considerable enhancement can be achieved at all dimers. The fabricated structures are evaluated by focusing on the polarization angle. The 10-11-M limit of detection and a 0.05-s rapid detection are achieved by using 4,4-bipyridine molecules with single-molecule sensitivity.

Plasmonic Nanoparticle Dimers with Reversibly Photoswitchable Interparticle Distances Linked by DNA

We report the assembly and optical characterization of stimulus-responsive gold nanoparticle dimers using azobenzene-modified hairpin DNA. We demonstrate a reversible, light-triggered actuation of the interparticle distance using reversible trans-to-cis photoisomerization of azobenzene. UV exposure leads to an extension of the dimers and concomitant blue shift of their scattering spectra, whereas blue light reverses the process. We use single-particle dark-field scattering spectroscopy to quantify the interparticle distances of the DNA-hairpin-linked nanoparticle heterodimers in the open and closed hairpin states. Analyzing the plasmon peak shifts for nearly 100 dimers with the plasmon ruler equation yields an average interparticle distance of 14.3 ± 1.7 nm in the closed (trans-azobenzene) and 17.7 ± 1.5 nm in the open (cis-azobenzene) state, which are in good agreement with finite-difference time-domain (FDTD) electrodynamic simulations of the dimers. We conclude that larger photoreversible plasmon shift...

Y-Shaped DNA Duplex Structure-Triggered Gold Nanoparticle Dimers for Ultrasensitive Colorimetric Detection of Nucleic Acid with the Dark-Field Microscope.

Herein, we present a novel gold nanoparticle (AuNP) enumeration-based colorimetric aptamer biosensor for ultrasensitive detection of nucleic acid. This AuNP enumeration-based colorimetric method takes advantages of the distinctive and strong localized surface plasmon resonance light scattering with the dark-field microscope. In our model system, first, cost-effective DNA1 instead of expensive 2-thioethyl ether acetic acid was capped on the surface of AuNPs to form a dense DNA1 layer. Then, two DNA strands (DNA2 and DNA3) in two different solutions were separately asymmetrically functionalized on the AuNPs capped dense DNA1 layer. The subsequent binding of the target DNA could trigger the formation of perfect complementary DNA with a Y shape and adjust the distance between nanoparticles to form AuNP dimers, accompanied by a color change from green to yellow as observed, and thereby modulated the performance of the sensor, which resulted in the ultrahigh sensitivity. With this design, a 43 aM limit of detection was obtained, which exhibited an increase of at least 5-9 orders of magnitude in sensitivity over other colorimetric sensors fabricated using conventional strategies.