Assembly Of Gold Nanorods Research Articles

ZIF-Mediated Gold Nanorod Assembly for Surface-Enhanced Raman Scattering Detection of 4-Nitrobenzenethiol

Nanoparticle assemblies exhibit unique properties compared to single entities due to interactions between their building blocks. Although the development of large-area assemblies has been extensively studied, finite nanoparticle assemblies with tens of building blocks have not been adequately explored. Here, we prepared a finite assembly of anisotropic gold nanorods through encapsulation by a zeolitic imidazolate framework-8 (ZIF). The three-dimensional reconstruction of the ZIF-encapsulated nanorod assembly indicated that the assembled nanorods are separate bundles aligned side-by-side, each of which serves as a nucleation center for a cube-shaped ZIF domain. Further experiments showed that the assembly pattern and the shell dimension can be controlled by the cysteamine and surfactant concentrations. Moreover, the ZIF-encapsulated nanorod assembly had twice the surface-enhanced Raman scattering signal of a single nanorod and showed higher selectivity for 4-nitrobenzenethiol versus rhodamine 6G. Our model system will significantly contribute to the development of finite anisotropic nanoparticle assemblies with microporous metal–organic framework shells and extend their applicability.

Assembly of gold nanorods with L-cysteine reduced graphene oxide for highly efficient NIR-triggered photothermal therapy

Near-infrared (NIR) photothermal therapy is an effective partner to the chemotherapy of tumors with the merits of high therapeutic ability and slight side effect on normal tissues. Herein, we synthesized gold nanorods and assembled them with L-cysteine reduced graphene oxide (AuNR@Lcyst-rGO) for efficient photothermal therapy. The high therapeutic efficacy of AuNR@Lcyst-rGO can be due to the high photothermal effect of gold nanorods and reduced graphene oxide, and the synergistic effect of them. The nontoxicity of L-cysteine also guarantees the comfortable biocompatibility of reduced graphene oxide, which is essential for the photothermal absorber used in human tissue. The results demonstrate that assembly of gold nanorods with reduced graphene oxide (AuNR@Lcyst-rGO) is a promising photothermal agent with high efficient NIR-triggered photothermal therapy efficiency, excellent stability, superior biocompatibility.

Active Plasmonics with Responsive, Binary Assemblies of Gold Nanorods and Nanospheres.

Self-assembly of metal nanoparticles has applications in the fabrication of optically active materials. Here, we introduce a facile strategy for the fabrication of films of binary nanoparticle assemblies. Dynamic control over the configuration of gold nanorods and nanospheres is achieved via the melting of bound and unbound fractions of liquid-crystal-like nanoparticle ligands. This approach provides a route for the preparation of hierarchical nanoparticle superstructures with applications in reversibly switchable, visible-range plasmonic technologies.

Tuning Hierarchical Order and Plasmonic Coupling of Large-Area, Polymer-Grafted Gold Nanorod Assemblies via Flow-Coating.

Solution-based printing of anisotropic nanostructures is foundational to many emerging technologies, such as energy storage devices, photonic elements, and sensors. Methods to rapidly (>mm/s) manufacture large area assemblies (≫cm2) with simultaneous control of thickness (<10 nm), nanoparticle spacing (<5 nm), surface roughness (<5 nm), and global and local orientational order are still lacking. Herein, we demonstrate such capability using flow-coating to fabricate robust, self-supporting mono- and bilayer films of polystyrene-grafted gold nanorods (PS-AuNRs) onto solid substrates. The relationship among solvent evaporation, deposition speed, substrate surface energy, concentration, and film thickness for solutions of such hairy hybrid nanoparticles spans the Landau-Levich and evaporative film formation regimes. In the Landau-Levich regime, solvent evaporation rapidly concentrates the PS-AuNRs, leading to the formation of thin films with distinct, randomized side-by-side domains. Alternatively, processing at slower velocities in the evaporative regime results in the global alignment of PS-AuNRs. Processing speed and substrate surface energy afford tuning of the film's optical extinction of a given PS-AuNR via fine control of inter-rod distance and subsequent plasmonic coupling between neighboring nanorods. Because the concept of the polymer-grafted nanorod can be expanded to a variety of different polymer canopies, shapes, and core materials, the processing-structure relationships established in this work will have important implications on the future development of anisotropic nanostructure-based applications.

Weak Electrostatic Interaction Enabled Highly Oriented Assembly of Gold Nanorods onto Ultrathin Flagella Bionanofibers

Biological substrates are generally considered unfavored for electrostatic uptake of nanoparticles due to their low surface charges. Herein, the electrostatic interaction between weakly charged ultrathin flagella bionanofibers and gold nanorods (AuNRs) is investigated. It is discovered that compared with the reported AuNRs assembly onto one‐dimensional (1D) templates of strong charges, the weak electrostatic interaction here can generate more ordered 1D AuNRs array. Under strong attraction force, AuNRs can bind firmly on templates by either narrow heads or long sidewalls, resulting in less ordered 1D structure. While under weak attraction force, AuNRs can be captured only if interacting with flagella using their long sidewalls to obtain accumulative strong enough force. Another discovery is that under weak AuNRs–flagella electrostatic attraction force, the relatively stronger AuNRs–AuNRs repulsion force plays a significant role in determining the interparticle gap and the single‐ or double‐string pattern of AuNRs on ultrathin flagella. Advantage is also taken of the bio‐origin of flagella by assembling AuNRs onto flagella that are still attached to living bacterium. Such a capability makes our approach highly feasible for potential device fabrication, as individual nanoarray is hard to manipulate, but would be greatly facilitated if it is associated with a micron‐sized base, like bacteria.

Near-Infrared Chiral Plasmonic Microwires through Precision Assembly of Gold Nanorods on Soft Biotemplates

Directing the assembly of plasmonic nanoparticles into chiral superstructures has diverse applications including, chiroptical sensing, nonlinear optics, and biomedicine. Though soft template-mediated assemblies of both spherical and nonspherical gold nanoparticles have made significant progress, most approaches require sophisticated chemical synthesis or advanced methodologies. Besides, reports of structurally precise chiral plasmonic assemblies beyond nanoscale are limited. Here, we propose an efficient yet simple strategy to grow such precision assemblies up to mesoscale, which is beneficial for a broader community. Briefly, cationic gold nanorods (AuNRs) are allowed to systematically assemble along atomically precise, chiral, rodlike tobacco mosaic virus (TMV) particles via electrostatic attraction under ambient condition. This leads to spontaneous formation of helical hybrid microwires with high structural precision, as evidenced by cryogenic transmission electron microscopy and tomography. Resulting composite superstructures show a strong circular dichroism response at the plasmon wavelength of the AuNRs, which is supported by simulations using discrete dipole approximation. Further, chirality of the system is investigated at a single-microwire level using polarized dark-field scattering microscopy. An alternative chiral template, negatively charged colloidal cellulose nanocrystals, also arrange AuNRs into similar chiral microstructures. Thus, our report proposes a generic methodology to obtain chiral plasmonic response at the NIR region using inexpensive templates that will encourage the exploration of a wider range of nanoscale templates for creating hybrid mesostructures with emerging optoelectronic properties.

High spatial and energy resolution electron energy loss spectroscopy of the magnetic and electric excitations in plasmonic nanorod oligomers.

We leverage the high spatial and energy resolution of monochromated aberration-corrected scanning transmission electron microscopy to study the hybridization of cyclic assemblies of plasmonic gold nanorods. Detailed experiments and simulations elucidate the hybridization of the coupled long-axis dipole modes into collective magnetic and electric dipole plasmon resonances. We resolve the magnetic dipole mode in these closed loop oligomers with electron energy loss spectroscopy and confirm the mode assignment with its characteristic spectrum image. The energy splitting of the magnetic mode and antibonding modes increases with the number of polygon edges (n). For the n=3-6 oligomers studied, optical simulations using normal incidence and s-polarized oblique incidence show the respective electric and magnetic modes' extinction efficiencies are maximized in the n=4 arrangement.

Depletion-Mediated Uniform Deposition of Nanorods with Patterned, Multiplexed Assembly.

Device-scale, uniform, and controllable deposition of nanoparticles on various substrates is fundamentally important not only for the fabrication of thin-film devices but also for the large sample statistics of single-particle performances. However, it is challenging to obtain such predefined depositions using a simple and efficient method. Here, we present a novel strategy for obtaining the uniform and particle density/spacing-tunable deposition of nanorods on a linker-free substrate. The deposition is driven by the tailored particle-substrate depletion attraction owing to the size-matched design of the substrate roughness and the nanorod diameter. Both gold nanorods and upconversion nanorods were applied to demonstrate the generality of the method. The high particle density of more than 21 per μm2 and correspondingly the small particle spacing of fewer than 0.3 μm were achieved on a scalable substrate template. On this basis, orientational ordering and pattern-selective deposition of nanorods were realized by controlling the liquid flow rate and employing the substrate with patterned roughness areas, respectively. With the roughness-directed density-tunable depositions of nanorods integrated onto a single platform, multiplexed gold nanorod assembly and programmable surface-enhanced Raman mapping were achieved, with a promising prospect in information encoding by using the Raman signals as the translation units. The thermal stability and related transition temperature of about 160 °C of gold nanorods were also revealed as an application of single-particle statistics. This practical method could be extended to wide ranges of potential applications in plasmonic coupling devices, cryptography, or single-particle performance statistics with the feature of the high-throughput, low-cost, and scalable fabrication.

In Situ Tracking of Colloidally Stable and Ordered Assemblies of Gold Nanorods

Solution-phase self-assembly of anisotropic nanoparticles into complex 2D and 3D assemblies is one of the most promising strategies toward obtaining nanoparticle-based materials and devices with unique optical properties at the macroscale. However, controlling this process with single-particle precision is highly demanding, mostly due to insufficient understanding of the self-assembly process at the nanoscale. We report the use of in situ environmental scanning transmission electron microscopy (WetSTEM), combined with UV/vis spectroscopy, small-angle X-ray diffraction (SAXRD) and multiscale modeling, to draw a detailed picture of the dynamics of vertically aligned assemblies of gold nanorods. Detailed understanding of the self-assembly/disassembly mechanisms is obtained from real-time observations, which provide direct evidence of the colloidal stability of side-to-side nanorod clusters. Structural details and the forces governing the disassembly process are revealed with single particle resolution as well as in bulk samples, by combined experimental and theoretical modeling. In particular, this study provides unique information on the evolution of the orientational order of nanorods within side-to-side 2D assemblies and shows that both electrostatic (at the nanoscale) and thermal (in bulk) stimuli can be used to drive the process. These results not only give insight into the interactions between nanorods and the stability of their assemblies, thereby assisting the design of ordered, anisotropic nanomaterials but also broaden the available toolbox for in situ tracking of nanoparticle behavior at the single-particle level.

Synthesis of Solution-Stable End-to-End Linked Gold Nanorod Dimers via pH-Dependent Surface Reconfiguration.

End-to-end dimers of gold nanorods are predicted to be excellent substrates for surface-enhanced spectroscopy. However, the synthesis of solution-stable end-to-end dimers remains challenging. We exploit the pH-dependent configurational change of polyelectrolytes to initiate and terminate the gold nanorod assembly formation to produce end-to-end linked dimers in high yield. The gold nanorods are first overcoated with a polyelectrolyte, and the end-to-end attachment is initiated by adding a thiol linker in acidic medium. The assembly formation is then terminated at the dimer stage by changing the pH of the medium by the addition of an appropriate amount of 1,4-diazabicyclo[2.2.2]octane (DABCO).The nanorod dimers synthesized here are stable in solution for a week without any additional surface encapsulation.

Effects of Aspect Ratio Heterogeneity of an Assembly of Gold Nanorod on Localized Surface Plasmon Resonance

We examine the effects of aspect ratio (AR) heterogeneity of an assembly of gold nanorods (GNRs) in a colloid on the total cross-section for its light scattering via localized surface plasmons at visible wavelengths. We observe the extraordinary broadening of the extinction spectrum of light through an assembly of GNRs, a colloidal mixture of those having two different ARs. The interparticle distance estimated as ∼1.2-1.3 μm, being greater than the incident wavelength, allows the radiative dipolar coupling to govern the long-range interaction between GNRs. We find that the coupling enhanced local fields can activate the nonresonant polarization of GNRs to turn into a quasi-resonant one. These higher-order effects for GNR polarization can produce the deviation of total cross-section of GNRs assembly beyond the simple sum of an individual cross-section of GNRs that are assumed to have no such long-range coupling. The extraordinary properties of the extinction spectrum need to be taken into account for modulating the spectral distribution of electromagnetic field in photonic devices where an assembly of GNRs is utilized for field enhancement such as those for surface-enhanced spectroscopy, highly efficient photovoltaics, photothermal nanotherapy, and ultrathin absorption filters.

Gold Nanorod Assemblies: The Roles of Hot-Spot Positioning and Anisotropy in Plasmon Coupling and SERS.

Plasmon-coupled colloidal nanoassemblies with carefully sculpted “hot-spots” and intense surface-enhanced Raman scattering (SERS) are in high demand as photostable and sensitive plasmonic nano-, bio-, and chemosensors. When maximizing SERS signals, it is particularly challenging to control the hot-spot density, precisely position the hot-spots to intensify the plasmon coupling, and introduce the SERS molecule in those intense hot-spots. Here, we investigated the importance of these factors in nanoassemblies made of a gold nanorod (AuNR) core and spherical nanoparticle (AuNP) satellites with ssDNA oligomer linkers. Hot-spot positioning at the NR tips was made possible by selectively burying the ssDNA in the lateral facets via controlled Ag overgrowth while retaining their hybridization and assembly potential at the tips. This strategy, with slight alterations, allowed us to form nanoassemblies that only contained satellites at the NR tips, i.e., directional anisotropic nanoassemblies; or satellites randomly positioned around the NR, i.e., nondirectional nanoassemblies. Directional nanoassemblies featured strong plasmon coupling as compared to nondirectional ones, as a result of strategically placing the hot-spots at the most intense electric field position of the AuNR, i.e., retaining the inherent plasmon anisotropy. Furthermore, as the dsDNA was located in these anisotropic hot-spots, this allowed for the tag-free detection down to ~10 dsDNA and a dramatic SERS enhancement of ~1.6 × 108 for the SERS tag SYBR gold, which specifically intercalates into the dsDNA. This dramatic SERS performance was made possible by manipulating the anisotropy of the nanoassemblies, which allowed us to emphasize the critical role of hot-spot positioning and SERS molecule positioning in nanoassemblies.

In situ monitoring of silver adsorption on assembled gold nanorods by surface-enhanced Raman scattering

Self-assembly of metal nanocrystals is able to create a gap of sub-nanometer distance for concentrating incoming light by the strong coupling of surface plasmon resonance, known as a ‘hot spot’. Although the plasmonic property of silver is better than other metals in the visible range, the superior Raman enhancement of silver compared to gold is still under debate. To provide direct evidence, in this work, we studied the silver adsorption on assembled gold nanorods (AuNRs) using in situ surface-enhanced Raman scattering (SERS) measurements. The self-assembled AuNR multimers were used as the SERS substrate, where the 4-mercaptophenol (MPh) molecules in our experiment played dual roles as both probe molecules for the Raman scattering and linking molecules for the AuNR assembly in a basic environment. Silver atoms were adsorbed on the surface of gold nanorod assemblies by reduction of Ag+ anions. The stability of the adsorbed silver was guaranteed by the basic environment. We monitored the SERS signal during the silver adsorption with a home-built in situ Raman spectroscope, which was synchronized by recording the UV–vis absorption spectra of the reaction solution to instantly quantify the plasmonic effect of the silver adsorption. Although a minor change was found in the plasmonic resonance wavelength or intensity, the measured SERS signal at specific modes faced a sudden increase by 2.1 folds during the silver adsorption. The finite element method (FEM) simulation confirmed that the silver adsorption corresponding to the plasmonic resonance variation gave little change to the electric field enhancement. We attributed the mode-specific enhancement mechanism of the adsorption of silver to the chemical enhancement from charge transfer (CT) for targeting molecules with a specific orientation. Our findings provided new insights to construct SERS substrates with higher enhancement factor (EF), which hopefully would encourage new applications in the field of surface-enhanced optical spectroscopies.

Temperature-Induced Tunable Assembly of Columnar Phases of Nanorods.

We report on the assembly of gold nanorods functionalized with poly(ethylene glycol) in aqueous suspensions by electrostatic control and hydrogen bonds provided by polyelectrolyte linkers (i.e., interpolymer complexation processes). Small-angle X-ray scattering reveals that the quality and stability of the assemblies into the hexagonal columnar phases increase with temperature. Our study shows that the lattice constant of the ordered structures is tunable over a wide range of values by the interplay between electrostatic and hydrophobic effects.

In situ modulation of gold nanorod's surface charge drives the growth of end-to-end assemblies from dimers to large networks that enhance single-molecule fluorescence by 10 000-fold.

End-to-end assemblies of anisotropic plasmonic nanostructures with small nanogaps are of great interest as they create strong hot spots for enhancing weak fluorescence and/or scattering of molecules. Here we report the growth of dithiol-linked end-to-end assemblies of gold nanorods from dimers to large networks containing thousands of individual nanorods, directed by in situ tuning of nanorod's surface charge. Surface charge was lowered to initiate the aggregation process but was subsequently increased to achieve slow tip-specific growth over seven days to form end-to-end networks of nanorods, which were stable in solution for over one month. Furthermore, we showed that these assemblies contained strong plasmonic hot spots which enhanced the fluorescence signal of a weak emitter by 104-fold. This enhancement is approximately 10-fold larger than that obtained using a single gold nanorod and is comparable to the largest enhancement obtained using more expensive lithographically made in-plane antenna arrays.

Morphologies of self-assembled gold nanorod-surfactant-lipid complexes at molecular level

Gold nanorods (GNRs) have aroused the extensive interest of many researchers in recent years due to their unique physicochemical properties. However, the toxic cetyltrimethylammonium bromide (CTAB) is often introduced into the process of synthesizing GNRs, which hinders the wide-range applications of GNRs in clinical practice. To reduce the toxicity, the CTAB molecules coated on the surface of GNRs should be replaced by nontoxic and biocompatible agents such as phospholipid. Thus the component and morphology of the mixed coating agents on the surface of GNRs affect the physicochemical properties of GNRs. To study the morphology and properties of the coated GNRs at a molecular level, we investigate the self-assembly of GNRs, CTAB, and dimyristoyl phosphatidylcholine (DMPC) by using solvent-free dissipative particle dynamics simulations. Our results show that the morphology of the assembled complex mainly depends on the CTAB/DMPC molar ratio, while neither of the interaction strength between GNRs and the coating agents nor the diameter of GNRs has significant effect on the morphology. At a certain combination of GNRs-coating agent interaction strength with GNRs diameter, the mixture of CTAB and DMPC on the surface of GNRs undergoes a gradual change in morphology as the CTAB/DMPC molar ratio increases, including the forming of intact bilayer membrane, cracked bilayer membrane, long patches of micelles, and short wormlike micelles winding GNRs in spiral shape. The morphology of intact bilayer membrane verifies the experimental guess, while the other three morphologies are brand-new discoveries. We also find that when the GNR’s diameter becomes smaller, or the CTAB/DMPC molar ratio is larger, or the interaction strength is greater, the agents cap the ends of GNRs, meanwhile the membrane thickness becomes thinner. The multiple morphologies of the assembled complexes can be qualitatively explained by the shape energy of a membrane adsorbed on a solid surface. When the surface tension of the membrane (which is proportional to the spontaneous curvature of the membrane) exceeds a critical value (which is equal to the adhesion energy density of the membrane), the membrane dissociates from the solid surface and its shape changes. The change trend is related to the spontaneous curvature of the free membrane. As a result of the synergy and competition among the inherent curvatures of GNRs, the spontaneous curvature of CTAB/DMPC membrane or micelle, as well as the adhesion energy, various interesting morphologies are produced. Our simulations and analyses directly characterize the morphological structures of CTAB and lipid coated GNRs, which allow us to in depth understand the self-assembling behaviors of GNRs at a molecular level. This is also conductive to achieving the controlled assemblies of GNRs.

Development of Gold Nanorods-Insulin Amyloid Fibril Assemblies: A Hybrid Nanoscaffold with Enhanced Conductivity

Gold nanoparticles are metallic nanostructures with wide range of applications in biomedicine and biosensing. Among diverse morphologies of gold nanostructures, gold nanorods have attracted much more attention for their outstanding structure, optical property and function. The unique characteristic of these nanostructures encourages their integration with biomolecules of interest for versatile biomedical proposes. In this effort, amyloid fibrils with well-known mechanical strength and chemical stability have been used as biotemplates for assembly of gold nanorods to exploit dual property of both nano and bio counterparts in a hybrid nanoscaffold. To maximize the interaction of the nanostructures with the biotemplate, surface of the gold nanorods was modified with biocompatible polystyrene sulfonate (PSS). Spectroscopic and microscopic techniques including UV–Vis, CD, ThT and TEM were used to characterize formation of insulin amyloid fibrils, gold nanorods and their assemblies on the biotemplate. Morphology of gold nanorods was also monitored upon interaction with amyloid fibrils. Electrochemical impedance spectroscopy of the hybrid nanoscaffold showed that increase in the concentration of the assembled nanostructures on the biotemplate has clearly led to enhancement of conductivity. Results of this investigation highlight gold nanorods as promising candidates in design and fabrication of novel hybrid nanoscaffolds of enhanced conductivity, especially for biosensing and tissue engineering purposes.

Fine-tunable fluorescence quenching properties of core-satellite assemblies of gold nanorod-nanosphere: Application in sensitive detection of Hg2.

In this work, we developed a simple, effective fluorescence method to detect Hg2+ by inhibiting core-satellite assemblies of gold nanorods (AuNRs) and gold nanospheres (AuNPs). The fluorescence of Rhodamine 6G (Rh6G), which was simply mixed with the nanoassemblies, was efficiently quenched by the inner filter effect (IFE). When the heterogenous core-satellite nanostructures were assembled, the corresponding local surface plasmon resonance (LSPR) absorption shifts and broadens which results in the increase of the spectral overlap between the emission peak and the absorption band and more efficient energy transfer from Rh6G to nanoparticles. Fluorescence quenching efficiency is related to the size and number density of satellite nanoparticles. It is interesting that the AuNR-AuNP assemblies with the moderate size and high density of AuNPs have the best fluorescence quenching efficiency. In the presence of Hg2+, p-aminothiophenol (p-ATP) breaks away from the surface of AuNRs and competitively bounds to Hg2+, resulting in a low yield of the AuNR-AuNP assemblies, which further leads to the decrease of fluorescence quenching efficiency. Under the optimum conditions, the limit of detection (LOD) for Hg2+ was 0.18 nM, with an excellent linear response from 0.6 to 800 nM. Interference experiment and real samples detection indicate that these nanosensors endowed with higher sensitivity and selectivity for the detection of Hg2+ in the real samples. Compared with the conventional Hg2+ detection techniques, this method based on Hg2+ induced inhibition of core-satellite AuNR-AuNP assemblies has better performance and is suitable for the detection of Hg2+.

Directed Assembly of Gold Nanorods by Microwrinkles

Gold nanorod patterns made with microwrinkle substrate were investigated. The wide range and uniform patterning of gold nanorods are useful for the various applications. By changing the width of th...

Controlling the end-to-end assembly of gold nanorods to enhance the plasmonic response in near infrared

In the current paper, we report an efficient approach to produce in a controllable manner electromagnetic hot-spots localized in linear assemblies of gold nanorods (AuNRs) that can be further exploited as highly active surface-enhanced Raman scattering (SERS) sites. The process of the AuNRs self-assembling was initiated in an aqueous solution at pH = 3.1 in the presence of L-cysteine (Cys) molecules and was monitored in real-time for minutes up to hours. The recorded sequential extinction spectra featuring a well-defined isosbestic point at 834 nm is consistent with the first-order like reaction between individual and end-to-end assembled AuNRs as final products. Moreover, the dynamic of the self-assembling process was examined by correlating the extinction spectra with the average number of AuNRs in the chains as provided from the transmission electron microscopy (TEM) pictures. Noteworthy, the average number of connected AuNRs can be fixed at any moment in solution, depending of the desired plasmonic response, by blocking the assembling process with a negative layer of poly (sodium-p-styrenesulfonate) (PSS) polyelectrolyte. The high electric field in the hot-spots in between the linked nanoparticles was proved by SERS experiments using as target analyte para-aminothiophenol (p-ATP) and conducted to clear the demonstration of a higher enhancement factor relative to the individual AuNRs. Finally, all experimental findings and, especially, the far and near-field optical properties of such fabricated plasmonic nanoassemblies were supported by finite-difference time-domain (FDTD) simulations.