Au Nanoparticle Clusters Research Articles

DNA self-assembled Au nanoparticle clusters on silver nanorod arrays for high-sensitive and multiplex detection of cancer-related biomarkers.

To sensitively detect multiple and cross-species disease-related targets from a single biological sample in a quick and reliable manner is of high importance in accurately diagnosing and monitoring diseases. Herein, a surface-enhanced Raman scattering (SERS) sensor based on a functionalized multiple-armed tetrahedral DNA nanostructure (FMTDN) immobilized silver nanorod (AgNR) array substrate and Au nanoparticle (AuNP) SERS tags is constructed to achieve both multiplex detection and enhanced sensitivity using a sandwich strategy. The sensor can achieve single, dual, and triple biomarker detections of three lung cancer-related nucleic acid and protein biomarkers, i.e., miRNA-21, miRNA-486 and carcinoembryonic antigen (CEA) in human serum. The enhanced SERS signals in multiplex detections are due to the DNA self-assembled AuNP clusters on the silver nanorod array during the assay, and the experimentally obtained relative enhancement factor ratios, 150 for AuNP dimers and 840 for AuNP trimers, qualitatively agree with the numerically calculated local electric field enhancements. The proposed FMTDN-functionalized AgNR SERS sensor is capable of multiplex and cross-species detection of nucleic acid and protein biomarkers with improved sensitivity, which has great potential for the screening and clinical diagnosis of cancer in the early stage.

Plasmon-induced spectral tunability of Perovskite nanowires

In this paper, plasmon-assisted spectral tunability in random media, composed of Perovskite (CsPbBr3) nanowires surrounded by Au nanoparticle clusters in polystyrene matrix, is achieved. The interaction between the surface plasmons and the quantum sources is observed to generate photoluminescence from the higher excited state energy levels of the excited semiconductor nanowires, which results in a blueshifted fluorescence emission of 50 nm. The localized surface plasmon properties are also determined to be tuned by plasmonic pumping of the quantum sources at different resonant frequencies. Thus, the first observation of the tunable blueshifted fluorescence emission of the semiconductor nanocrystals surrounded by plasmonic nanoparticle aggregates is achieved. The dramatic changes in the spectral profiles of the fluorescent nanowires are attributed to be due to the fast dynamics surface enhanced fluorescence mechanism.

Ion-beam-induced structure fragmentation and dewetting in Au/Ti films

We investigate the formation of Au structures by continuing fragmentation of a Au film separated from Si (100) substrate by a Ti adhesion layer. The ion-beam processing uses 2 keV Cs+ projectiles. It induces the formation of a large variety of structures with dimensions from tens of microns down to a few nanometers, and shapes that include flat Au islands and clusters of Au nanoparticles. We identify different fragmentation mechanisms. In one pathway, Au structures are formed as pinch-off droplets detached from large Au islands undergoing solid-state dewetting. In a second pathway, a continuing cracking fragmentation produces Au structures with a wide range of sizes and shows self-similarity, expressed in a power law for volume distribution of fragments Vα with α = −2.03 ± 0.05. The measured α value is consistent with theoretical results in the literature modeling strong impact fragmentation. In the last stage of fragmentation evolution, Au nanostructures are spread over a texturized Si background. They assume shapes close to hemispherical, reflecting the increasing relevance of surface tension as dimensions decrease.

Ion-Beam-Induced Structure Fragmentation and Dewetting in Au/Ti Films

We investigate the formation of Au structures by continuing fragmentation of a Au film separated from Si (100) substrate by a Ti adhesion layer. The ion-beam processing uses 2 keV Cs+ projectiles. It induces the formation of a large variety of structures with dimensions from tens of microns down to a few nanometers, and shapes that include flat Au islands and clusters of Au nanoparticles. We identify different fragmentation mechanisms. In one pathway, Au structures are formed as pinch-off droplets detached from large Au islands undergoing solid-state dewetting. In a second pathway, a continuing cracking fragmentation produces Au structures with a wide range of sizes and shows self-similarity, expressed in a power law for volume distribution of fragments Vα with α= -2.03±0.05. The measured α value is consistent with theoretical results in the literature modelling strong impact fragmentation. In the last stage of fragmentation evolution, Au nanostructures are spread over a texturized Si background. They assume shapes close to hemispherical, reflecting the increasing relevance of surface tension as dimensions decrease.

Gap‐Plasmon Induced One‐Order Enhancement of Optical Anisotropy of 2D Black Phosphorus

Anisotropic 2D materials with unique thermoelectric, electrical, and optical characteristics offer prospects for various angle‐dependent devices. Yet, few anisotropic 2D materials are exploited. Black phosphorus (BP) is a newly rediscovered 2D material with striking in‐plane anisotropy. However, experimental illustrations of the optical anisotropy of 2D BP are very limited presumably due to the ultrathin thickness of the few‐layered BP which weakens the light–matter interaction. To solve this problem, herein a hybrid nanostructure is fabricated using a one‐step self‐assembly deposition of gold (Au) nanoparticle (NP) clusters onto the few‐layered BP residing on a silica (SiO2) substrate. Such a hybrid nanostructure can squeeze the light into AuNPs–SiO2 gap through the gap plasmon resonance, enabling the confined light to interact efficiently with the ultrathin BP film. Angle‐resolved polarized Raman spectra measurement is carried out to study the influence of the AuNPs on the in‐plane optical anisotropy of the BP. About 20 times enhancement of Raman intensity anisotropy is experimentally achieved using AuNPs. The AuNPs‐BP system is not only useful for high‐performance polarization‐dependent photonic devices but also a universal methodology for exploring the in‐plane anisotropy of low‐symmetry 2D materials. Furthermore, the high‐throughput self‐assembly fabrication shows its potential for industrial‐scale manufacturability.

One-pot synthesis of 3D Au nanoparticle clusters with tunable size and their application

In general, the preparation of Au nanoparticle clusters (NPCs) is more challenging than that of nanoparticles. The traditional multi-step method for preparing Au NPCs is time consuming and highly sensitive to the reaction conditions. Here, we report a simple and feasible method for the rapid preparation of Au NPCs (∼30 min), in which Au (III) is reduced to Au (0) by trisodium citrate, and assembled into NPCs in the presence of a trace amount of cysteine. The surface plasmon resonance peak of the Au NPCs is tunable and ranged from visible to near-IR regions by varying the content of cysteine added. The growth process of Au NPCs was monitored by dynamic light scattering, UV–vis absorption spectroscopy and transmission electron microscopy. Their elemental composition, chemical state and molecular structure of the sample surface were measured by x-ray photoelectron spectroscopy. The proposed synthesis mechanism has guiding significance for the preparation of other NPCs. Au NPCs used as surface-enhanced Raman spectroscopy substrate has a good enhancement effect because of its unique morphology.

Coupled Plasmon Modes in 2D Gold Nanoparticle Clusters and Their Effect on Local Temperature Control

Assemblies of closely separated gold nanoparticles exhibit a strong collective plasmonic response due to coupling of the plasmon modes of the individual nanostructures. In the context of self-assembly of nanoparticles, closed packed 2D clusters of spherical nanoparticles present an important composite system that promises numerous applications. The present study probes the collective plasmonic characteristics and resulting photothermal behavior of closed packed 2D Au nanoparticle clusters in order to delineate the effects of cluster size, inter-particle distance and particle size. Smaller nanoparticles (20 nm and 40 nm in diameter) that exhibit low individual scattering and high absorption were considered for their relevance to photothermal applications. In contrast to typical literature studies, the present study compares the optical response of clusters of different sizes ranging from a single nanoparticle up to large assemblies of 61 nanoparticles. Increasing the cluster size induces significant changes to the spectral position and opto-physical characteristics. Based on the model outcome, an optimal cluster size for maximum absorption per nanoparticle is also determined for enhanced photothermal effects. The effect of particle size and inter-particle distance is investigated in order to elucidate the nature of interaction in terms of near-field and far-field coupling. The photothermal effect resulting from absorption is compared for different cluster sizes and inter-particle distances considering a homogeneous water medium. A strong dependence of the steady state temperature of the nanoparticles on the cluster size, particle position in the cluster, incident light polarization and inter-particle distance provides new physical insight in local temperature control of plasmonic nanostructures.

Light-driven self-organization of gold clusters by linearly polarized Gaussian beam

The mechanism of optically organized and bound 2D clusters of multiple Au nanoparticles (NPs) is studied theoretically. Via the surface integration of Maxwell's stress tensor, the optical forces and torques upon every Au NPs are analyzed. The numerical results illustrate that 2D stable-equilibrium clusters (trimer, tetramer and pentamer) with wavelength-scale gaps can be produced at an off-focal plane of a linearly polarized (LP) Gaussian beam, besides 1D linear array patterns. For example, a trimer with an isosceles triangular pattern can be induced. These stably ordered cluster patterns are due to the plasmon-enhanced long-range interaction of light with these coupled Au NPs. Moreover, there is a range of the off-focal plane for inducing these ordered patterns. Our results are in agreement with the previous experiments [Yan et al. Nat. Commun. 2014; 5: 3751]. In addition, we found that these NPs are driven to transversely spin by the corresponding optical torque even though irradiated by a LP light. The study on optomechanics of the light-driven self-assembly of plasmonic colloids can be applied to 2D array patterning, which is worth further exploiting.

Large-Area Broadband Near-Perfect Absorption from a Thin Chalcogenide Film Coupled to Gold Nanoparticles.

Perfect absorbers that can efficiently absorb electromagnetic waves over a broad spectral range are crucial for energy harvesting, light detection, and optical camouflage. Recently, perfect absorbers based on a metasurface have attracted intensive attention. However, high-performance metasurface absorbers in the visible spectra require strict fabrication tolerances, and this is a formidable challenge. Moreover, fabricating subwavelength meta-atoms requires a top-down approach, thus limiting their scalability and spectral applicability. Here, we introduce a plasmonic nearly perfect absorber that exhibits a measured polarization-insensitive absorptance of ∼92% across the spectral region from 400 to 1000 nm. The absorber is realized via a one-step self-assembly deposition of 50 nm gold (Au) nanoparticle (NP) clusters onto a 35 nm-thick Ge2Sb2Te5 (GST225) chalcogenide film. An excellent agreement between the measured and theoretically simulated absorptance was found. The coalescence of the lossy GST225 dielectric layer and high density of localized surface plasmon resonance modes induced by the randomly distributed Au NPs play a vital role in obtaining the nearly perfect absorptance. The exceptionally high absorptance together with large-area high-throughput self-assembly fabrication demonstrates their potential for industrial-scale manufacturability and consequential widespread applications in thermophotovoltaics, photodetection, and sensing.

Self-assembled microrings of Au nanoparticle and Au nanorod clusters formed at the equators of Janus particles.

A method for fabricating polymer Janus particles with microring structures at their equators has been developed. This method allows gold nanoparticles and nanorods to be aligned and densely packed along the microrings.

Simultaneous Imaging and Selective Photothermal Therapy through Aptamer-Driven Au Nanosphere Clustering.

Gold (Au) nanoparticles display enhanced near-infrared (NIR) photothermal effects upon the formation of clusters. We studied the photothermal properties of Au nanosphere clusters on the single-particle level using photothermal heterodyne imaging (PTHI) microscopy to understand the enhancement mechanisms. NIR photothermal responses of Au nanoparticle clusters were found to significantly increase from monomers to trimers. The averaged PTHI signal intensity of Au nanosphere dimers and trimers is ∼10 and ∼25 times that of monomers. The NIR photothermal effect of clustered nanospheres strongly correlates with their longitudinal plasmon mode. Clustered Au nanospheres were demonstrated to exhibit dual-capability NIR photothermal imaging and therapy of human prostate cancer cells with high efficiency and selectivity. This strategy can be potentially utilized for simultaneous cancer imaging and therapy with 3D selectivity.

Template-Confined Site-Specific Electrodeposition of Nanoparticle Cluster-in-Bowl Arrays as Surface Enhanced Raman Spectroscopy Substrates.

Nanoparticle clusters have important applications in plasmonics and optical sensing fields. Various methods have been used to construct nanoparticle clusters, represented by assembling preprepared nanoparticles using DNA. However, preparation of nanoparticle clusters using a one-step method is still challenging. Herein, by using prepatterned microscale bowls as individual reaction containers, clusters of Au nanoparticles with a homogeneous structure are electrodeposited at the bottom of each bowl. The structure of the nanoparticle clusters can be simply manipulated by varying electrodeposition parameters. After coating these Au nanoparticle cluster-in-bowl arrays with a thin layer of Ag film, they can be used as surface enhanced Raman spectroscopy (SERS) substrates with an SERS enhancement factor of ∼108. Importantly, the concave bowl structures can facilitate delivery of the analytes into the crevices between the bowls and the nanoparticle clusters where SERS "hot spots" (or sensitive sites) are located. The crevices with a gradually changed gap distance between the concave bowl structure and the nanoparticle clusters are excellent traps for catching and SERS sensing of biospecies with varied sizes (e.g., viruses and proteins). We demonstrated sensitive SERS detection of viruses and proteins using the nanoparticle-cluster-in-bowl SERS substrates. This technique has the ability to control the resulting structure at specific locations with electrodeposited materials, which enables new opportunities for assembling complex surface patterns with diverse applications in optical and plasmonic fields.

In-situ liquid-cell TEM study of radial flow-guided motion of octahedral Au nanoparticles and nanoparticle clusters

The dynamic behavior of octahedral gold nanoparticles (NPs) and nanoparticle clusters (NPCs) in aqueous solution is studied by in-situ liquid-cell transmission electron microscopy (TEM). The octahedral Au NPs/NPCs show preferential orientations in the liquid cell, due to the interaction with the SiNx window. The Au NPs show long-range reversible hopping and three-dimensional (3D) rotational motions in the liquid environment. At the same time, the Au NPCs and NPs perform slow stick-slip and stick-roll motions, respectively, with a centripetal trend. The centripetal motions were explained by a liquid evaporation-induced radial flow model, in which the NPCs/NPs trajectories are controlled by Stokes forces and surface friction by the silicon nitride window. The calculated radius-dependent force (Fc) on the NPCs/NPs shows a semi-linear correlation with the distance r between the NPCs/NPs and the center of mass, accompanied with stochastic fluctuations, in agreement with the model predictions. This work thus demonstrates the effectiveness of in situ liquid-cell TEM for the in-depth understanding of complicated liquid flow and force interactions in nanomaterials.

Core-Shell Nanoparticle Clusters Enable Synergistic Integration of Plasmonic and Catalytic Functions in a Single Platform.

Designing controlled hybrid nanoarchitectures between plasmonic and catalytic materials is of paramount importance to fully exploit each function of constituent materials. This study reports a new synthetic strategy for the realization of colloidal clusters of core-shell nanoparticles with plasmonic cores and catalytically active shells. The Au@M (M = Pd or Pt) nanoparticle clusters (NPCs) with a high density of sub-1 nm interparticle gaps are successfully prepared by the deposition of M shells onto thermally activated Au NPCs. NPCs with other metal, metal sulfide, and metal oxide shells can also be synthesized by using the present approach. The prepared Au@M NPCs show remarkably enhanced plasmonic performance compared to their Au@M nanoparticle counterparts due to the localization of a strong electromagnetic field at the interparticle gaps, while the inherent catalytic function of shells is intact. In situ real-time Raman spectroscopy and plasmon-enhanced electrocatalysis experiments demonstrate that the controlled assembly of core-shell nanoparticles is a very effective route for the synergistic integration of plasmonic and catalytic functions in a single platform.

Colloidal Clusters of Plasmonic Nanoparticles with Controlled Topological Parameters

AbstractDevising colloidal nanoparticle assemblies with finely tuned topological parameters is critical to the development of efficient and reliable plasmonic platforms that can enable promising applications, such as surface‐enhanced Raman scattering (SERS). Here, we report a facile synthesis strategy for the preparation of stable colloidal clusters of Au nanoparticles (Au NPCs) with well‐controlled structural parameters, including the average number and size of constituent nanoparticles and the size of interparticle gaps, in which the galvanic replacement of Ag nanoprisms with controlled amount of Au precursors yielded Au NPCs with maneuvered particle sizes, while the other structural factors were intact. The present approach could allow the precise exploration of the influence of particle size on the SERS activity of nanoparticle assemblies. Notably, the prepared Au NPCs showed different particle‐size dependency of their SERS activity along with the change in analyte concentration. Finite difference time domain simulation studies revealed that the experimental results can be correlated with the relative contributions of the magnitude of near‐field enhancement and areal density of hot spots in the Au NPCs, which are determined by the size of constituent nanoparticles. This study therefore provides key design guidelines to optimize the plasmonic function of nanostructure assemblies.

Self-Assembled Plasmonic Metamolecules Exhibiting Tunable Magnetic Response at Optical Frequencies

A bottom-up self-assembly approach is used to synthesize pseudospherical clusters of Au nanoparticles with low size and shape polydispersity. Such plasmonic metamolecules (PMMs) with various diameters are prepared from two different AuNP building block sizes, enabling the investigation of the size-dependent optical properties of these structures. Trends in the UV–vis spectra are reproduced theoretically using generalized multiparticle Mie theory as either the AuNP or PMM diameter are changed. The calculated results indicate that features in the spectra of large PMMs can be associated with magnetic dipole resonances, which strengthen and red-shift with increasing PMM size. Finally, effective medium theory is used to demonstrate that materials composed of these PMMs could exhibit a bulk isotropic magnetic response at optical frequencies.

Sensitive Detection of Biomolecules by Surface Enhanced Raman Scattering using Plant Leaves as Natural Substrates

Detection of biomolecules is highly important for biomedical and other biological applications. Although several methods exist for the detection of biomolecules, surface enhanced Raman scattering (SERS) has a unique role in greatly enhancing the sensitivity. In this work, we have demonstrated the use of natural plant leaves as facile, low cost and eco-friendly SERS substrates for the sensitive detection of biomolecules. Specifically, we have investigated the influence of surface topography of five different plant leaf based substrates, deposited with Au, on the SERS performance by using L-cysteine as a model biomolecule. In addition, we have also compared the effect of sputter deposition of Au thin film with dropcast deposition of Au nanoparticles on the leaf substrates. Our results indicate that L-cysteine could be detected with high sensitivity using these plant leaf based substrates and the leaf possessing hierarchical micro/nanostructures on its surface shows higher SERS enhancement compared to a leaf having a nearplanar surface. Furthermore, leaves with drop-casted Au nanoparticle clusters performed better than the leaves sputter deposited with a thin Au film.

Probed adhesion force of living lung cells with a tip-modified atomic force microscope.

The mechanical properties of the extracellular matrix play an important role in bio-microenvironment activities. Herein, atomic force microscope (AFM) was used to measure the interaction between Au and Ag nanoparticle (NP) clusters on the surface of human fetal lung cells. Using (3-mercapto-propyl) triethoxysilane (MPTMS), NP clusters were grafted onto the apex of AFM tip, and then, the adhesion force between the tip and the cell was analyzed. The measured adhesion force increased from 92 pN for AFM tip to 332 pN for that modified with MPTMS. The increase is most probably contributed by the nonspecific interactions between the apex of the modified AFM tip and the surface of the cells. The adhesion forces between the surface of NPs clusters grafted AFM tip and that of lung cells were dramatically reduced as NPs clusters were replaced by MPTMS. For the former, as the Au NPs cluster was applied, the adhesion force reached to 122 pN, whereas it significantly augmented with the addition of the cluster's size and dimension on the AFM tip. For the case of Ag cluster grafted on AFM tip, its adhesion force with the surface of the cells significantly lowered and reduced to 56 pN. Presumably, the electrostatic or van der Waals force between the two surfaces results in the variation of measurements. It is also very likely that the cell-surface interactions are probably varied by the nature of the contact surfaces, like the force-distance of attraction. The result is significant for understanding the the nature of the interactions between the surface of NPs and the membrane of lung cells.

Two-Dimensional Nanoparticle Cluster Formation in Supercritical Fluid CO2.

Supercritical fluid carbon dioxide (sc-CO2) is capable of depositing nanoparticles in small structures of silicon substrates because of its gas-like penetration, liquid-like solvation abilities, and near-zero surface tension. In nanometer-sized shallow wells on silicon surface, formation of two-dimensional (2D) monolayer metal nanoparticle (NP) clusters can be achieved using the sc-CO2 deposition method. Nanoparticles tend to fill nanostructured holes first, and then, if sufficient nanoparticles are available, they will continue to cover the flat areas nearby, unless defects or other surface imperfections are available. In addition, SEM images of two-dimensional gold (Au) nanoparticle clusters formed on a flat silicon surface with two to a dozen or more of the nanoparticles are provided to illustrate the patterns of nanoparticle cluster formation in sc-CO2.

The Role of Adhesion in Gold Nanoparticles for Cancer Detection and Treatment

This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.