Au Nanocups Research Articles

Fucoidan‐Modified Au Nanocups With Tumor Targeting Inhibits CD24‐Mediated Immune Escape and Epithelial Mesenchymal Transition Through Precise Controlled Release of Anti‐CD24 Antibodies

Fucoidan‐Modified Au Nanocups With Tumor Targeting Inhibits CD24‐Mediated Immune Escape and Epithelial Mesenchymal Transition Through Precise Controlled Release of Anti‐CD24 Antibodies

Orientation-Dependent Interaction between the Magnetic Plasmons in Gold Nanocups and the Excitons in WS2 Monolayer and Multilayer.

The integration of two-dimensional transition metal dichalcogenides with plasmonic nanostructures is extremely attractive for the investigation of the resonance coupling between plasmons and excitons, which offers a framework for the study of cavity quantum electrodynamics and is of great potential for exploring diverse quantum technologies. Herein we report on the coupling between the magnetic plasmons supported by individual asymmetric Au nanocups and the excitons in WS2 monolayer and multilayer. Resonance coupling with the strength varying from weak to strong regimes is realized by adjusting the orientation of the individual Au nanocups on WS2 monolayer. Different energy detunings between the magnetic plasmons and the excitons are achieved by varying the size of the Au nanocup. The Rabi splitting energies extracted at zero detuning are up to 106 meV. The anticrossing feature is observed in the measured scattering spectra and simulated absorption spectra, which indicates that the resonance coupling between the magnetic plasmons in the Au nanocup and the excitons in WS2 monolayer enters the strongly coupled regime. A dependence of the coupling strength on the layer number is further observed when the Au nanocups are coupled with WS2 multilayer. Our study suggests a promising approach toward the realization of different coupling regimes in a simple hybrid system made of individual Au nanocups and two-dimensional materials.

Toroidal dipole-modulated dipole-dipole double-resonance in colloidal gold rod-cup nanocrystals for improved SERS and second-harmonic generation.

Colloidal metal nanocrystals (NCs) show great potential in plasmon-enhanced spectroscopy owing to their attractive and structure-depended plasmonic properties. Herein, unique Au rod-cup NCs, where Au nanocups are embedded on the one or two ends of Au nanorods (NRs), are successfully prepared for the first time via a controllable wet-chemistry strategy. The Au rod-cup NCs possess multiple plasmon modes including transverse and longitudinal electric dipole (TED and LED), magnetic dipole (MD), and toroidal dipole (TD) modulated LED resonances, producing large extinction cross-section and huge near-field enhancements for plasmon-enhanced spectroscopy. Particularly, Au rod-cup NCs with two embedded cups show excellent surface-enhanced Raman spectroscopy (SERS) performance than Au NRs (75.6-fold enhancement excited at 633 nm) on detecting crystal violet owing to the strong electromagnetic hotspots synergistically induced by MD, LED, and TED-based plasmon coupling between Au cup and rod. Moreover, the strong TD-modulated dipole-dipole double-resonance and MD modes in Au rod-cup NCs bring a 37.3-fold enhancement of second-harmonic generation intensity compared with bare Au NRs, because they can efficiently harvest photoenergy at fundamental frequency and generate large near-field enhancements at second-harmonic wavelength. These findings provide a strategy for designing optical nanoantennas for plasmon-enhanced applications based on multiple plasmon modes.Electronic Supplementary MaterialSupplementary material (SEM image of Au rod-one-cup NCs; TEM image of Au/PbS hybrids; SEM image of Au rod-two-cup NCs; low-amplification SEM image of Au rod-two-cup NCs; experimental extinction and calculated electric field distributions of Au NR excited at different wavelengths; calculated absorption and scattering spectra of Au rod-one-cup NCs; schematic illustration of the cut plane and the corresponding magnetic field distribution under L3 excitation; Raman spectra of CV (10−6 M) adsorbed on Au rod-cup NCs with different cup sizes; calculated magnetic field distribution of Au rodcup NCs excited at 532 and 633 nm; calculated electric field distributions of Au rod-one-cup NC excited at 600 nm along TE and LE; the models of Au rod-cup NCs used in the simulations) is available in the online version of this article at 10.1007/s12274-022-4562-5.

Selective Deposition of Catalytic Metals on Plasmonic Au Nanocups for Room-Light-Active Photooxidation of o-Phenylenediamine.

Plasmonic hotspots can enhance hot charge carrier generation, offering new opportunities for improving the photocatalytic activity. In this work, eight types of heteronanostructures are synthesized by selectively depositing catalytic metals at the different sites of highly asymmetric Au nanocups for the photocatalytic oxidation of o-phenylenediamine. The oxidation of this molecule has so far mainly relied on the use of H2O2 as an oxidizing agent in the presence of an appropriate catalyst. The photocatalytic oxidation under visible light has not been reported before. The Au nanocups with AgPt nanoparticles grown at the opening edge and bottom exhibit the highest photocatalytic activity. The generated hot electrons and holes both participate in the reaction. The hot carriers from the interband and intraband transitions are both utilized. The optimal catalyst shows a favorable activity even under room light. Simulations reveal that the profound electric field enhancement at the hotspots boosts the hot-carrier density in the catalytic nanoparticles, explaining the overwhelming photocatalytic activity of the optimal catalyst.

Control of the emission from electric and magnetic dipoles by gold nanocup antennas.

The control of the emission from electric and magnetic dipoles is highly desired for the development of optic chips. Although the emission of electric dipole has been successfully controlled by plasmonic nanoantenna, the control of magnetic dipole emission is relatively difficult. Here, we systematically study the effect of electric and magnetic modes of Au nanocups on the emission of electric and magnetic dipoles. The emission of electric dipole can be enhanced by both the electric and magnetic mode of the Au nanocup, while the emission of the magnetic dipole is only increased by the magnetic mode. The enhancement exhibits wavelength dependence. The wavelength of the largest enhancement is determined by the resonance wavelength of electric and magnetic modes. The enhancement values for electric and magnetic dipoles are determined by the near-field electric and magnetic field enhancements, respectively. More importantly, the emission pattern of magnetic dipole is greatly modified by the magnetic mode of Au nanocup. The directional emission of magnetic dipole is first time realized by use of the magnetic mode of the Au nanocup. Our findings deepen the understanding of the plasmon-controlled emission of electric and magnetic dipoles and will be very helpful to the development of the nanophotonic chips.

Magnetic Plasmon-Enhanced Second-Harmonic Generation on Colloidal Gold Nanocups

The magnetic plasmons of three-dimensional nanostructures have unique optical responses and special significance for optical nanoresonators and nanoantennas. In this study, we have successfully synthesized colloidal Au and AuAg nanocups with a well-controlled asymmetric geometry, tunable opening sizes, and normalized depths ( h/ b, where h is depth and b is the height of the templating PbS nanooctahedrons), variable magnetic plasmon resonance, and largely enhanced second-harmonic generation (SHG). The most-efficient SHG of the bare Au nanocups is experimentally observed when the normalized depth h/ b is adjusted to ∼0.78-0.79. We find that the average magnetic field enhancement is maximized at h/ b = ∼0.65 and reveal that the maximal SHG can be attributed to the joint action of the optimized magnetic plasmon resonance and the "lightning-rod effect" of the Au nanocups. Furthermore, we demonstrate for the first time that the AuAg heteronanocups prepared by overgrowth of Ag on the Au nanocups can synergize the magnetic and electric plasmon resonances for nonlinear enhancement. By the tailoring of the dual resonances at the fundamental excitation and second-harmonic wavelengths, the far-field SHG intensity of the AuAg nanocups is enhanced 21.8-fold compared to that of the bare Au nanocups. These findings provide a strategy for the design of nonlinear optical nanoantennas based on magnetic plasmon resonances and can lead to diverse applications ranging from nanophotonics to biological spectroscopy.

Au Nanobottles with Synthetically Tunable Overall and Opening Sizes for Chemo-Photothermal Combined Therapy.

Highly asymmetric Au nanostructures, such as split Au nanorings and Au nanocups, exhibit attractive plasmonic properties because of their asymmetric geometries. To facilitate their plasmonic applications, effective and facile synthetic methods for producing asymmetric Au nanostructures with controllable sizes and uniform shapes are highly desirable. Herein, we report on an approach for the synthesis of largely asymmetric colloidal Au nanobottles with synthetically tunable overall and opening sizes. Au nanobottles with overall sizes in the range of ∼100-230 nm are obtained through sacrificial templating with differently sized PbS nano-octahedra. The opening sizes of the produced Au nanobottles can be tailored from ∼10 to ∼120 nm by either adjusting the Au/PbS molar ratio in the growth process or controlling the oxidation degree. The achieved size tunability allows the plasmon resonance wavelength of Au nanobottles to be varied in the range of ∼600-900 nm. Our uniform Au nanobottles, which possess controllable sizes, large cavity volumes, and tunable plasmon resonance wavelengths in the visible to near-infrared range, have been further applied for anticancer drug delivery and photothermal therapy. The effects of surface coating and the opening size of Au nanobottles on the drug encapsulation efficiency (EE) and initial burst drug release are systemically evaluated. A high doxorubicin EE and low initial burst drug release are realized with the dense silica-coated Au nanobottles having an opening size of 44 nm. In addition, chemo-photothermal combined therapy has been demonstrated with the doxorubicin-loaded Au nanobottles. Our results will be helpful for the design of Au nanobottles with different sizes and plasmonic properties as well as provide ample opportunities for exploring various plasmon-enabled applications of Au nanobottles.

Flexible and Tunable 3D Gold Nanocups Platform as Plasmonic Biosensor for Specific Dual LSPR-SERS Immuno-Detection

Early medical diagnostic in nanomedicine requires the implementation of innovative nanosensors with highly sensitive, selective, and reliable biomarker detection abilities. In this paper, a dual Localized Surface Plasmon Resonance - Surface Enhanced Raman Scattering (LSPR- SERS) immunosensor based on a flexible three-dimensional (3D) gold (Au) nanocups platform has been implemented for the first time to operate as a relevant “proof-of-concept” for the specific detection of antigen-antibody binding events, using the human IgG - anti-human IgG recognition interaction as a model. Specifically, polydimethylsilane (PDMS) elastomer mold coated with a thin Au film employed for pattern replication of hexagonally close-packed monolayer of polystyrene nanospheres configuration has been employed as plasmonic nanoplatform to convey both SERS and LSPR readout signals, exhibiting both well-defined LSPR response and enhanced 3D electromagnetic field. Synergistic LSPR and SERS sensing use the same reproducible and large-area plasmonic nanoplatform providing complimentary information not only on the presence of anti-human IgG (by LSPR) but also to identify its specific molecular signature by SERS. The development of such smart flexible healthcare nanosensor platforms holds promise for mass production, opening thereby the doors for the next generation of portable point-of-care devices.

Nanostructures: Controllable Fabrication of Au Nanocups by Confined-Space Thermal Dewetting for OCT Imaging (Adv. Mater. 26/2017)

Nanostructures: Controllable Fabrication of Au Nanocups by Confined-Space Thermal Dewetting for OCT Imaging (Adv. Mater. 26/2017)

Controllable Fabrication of Au Nanocups by Confined-Space Thermal Dewetting for OCT Imaging.

Here, this study reports a novel confined-space thermal dewetting strategy for the fabrication of Au nanocups with tunable diameter, height, and size of cup opening. The nanocup morphology is defined by the cup-shaped void space created by a yolk-shell silica template that spontaneously takes an eccentric configuration during annealing. Thermal dewetting of Au, which is sandwiched between the yolk and shell, leads to the desired nanocup morphology. With strong scattering in near infrared, the Au nanocups exhibit superior efficiency as contrast agents for spectral-domain optical coherence tomography imaging. This confined-space thermal dewetting strategy is scalable and general, and can be potentially extended to the synthesis of novel anisotropic nanostructures of various compositions that are difficult to produce by conventional wet chemical or physical methods, thus opening up opportunities for many new applications.

Biocompatible Cup‐Shaped Nanocrystal with Ultrahigh Photothermal Efficiency as Tumor Therapeutic Agent

As an emerging treatment for cancer, phototherapy has received much clinical attention. Here, a multifunctional Au nanocup (Au NC) for the targeted computed tomographic and photoacoustic imaging of cancerous tumors and phototherapy is reported. The Au NC has an intrinsic photothermal conversion efficiency of 38.5% and offers a tumor‐specific targeted computed tomographic and photoacoustic imaging system. Furthermore, when treated with nontoxic Au NC‐Ce6, cancer cells and tumors are obliterated with low doses of irradiation and safe power levels, with both photothermal and photodynamic therapeutic effects, in vitro and vivo. These data provide a solid foundation for the clinical application of Au NC.

Directional light scattering from individual Au nanocup

We investigate the optical scattering properties of gold nanocup with different orientation and fractional height by full vector finite element method. All of the scattering cross section, the distribution of electric field intensity, and the ability of directional light scattering are simulated, respectively. It is demonstrated that the scattering cross section of Au nanocup is a superposition of scattering spectrum of a transverse mode and an axial mode. The wavelength and the intensity of the maximum value of the scattering cross section increase initially then reduce with the fractional height increasing for transverse mode, while they increase monotonously with the fractional height increasing for axial mode. Furthermore, the calculation results show that the ability of redirecting incident light of Au nanocup mainly depends on the transverse mode. And the deflected angle of scattering increases with the fractional height of Au nanocup decreasing. These results indicate that Au nanocup has a promising application in the planar plasmon devices.

Gold Nanocups: Colloidal Gold Nanocups with Orientation-Dependent Plasmonic Properties (Adv. Mater. 30/2016).

On page 6322, J. F. Wang and co-workers report a wet-chemistry method for the preparation of colloidal Au nanocups and their plasmonic properties. The Au nanocups are prepared through single-vertex-initiated Au deposition on PbS nano-octahedrons and subsequent selective dissolution of PbS. Owing to the orientation-dependent coupling strengths, the obtained Au nanocups display orientation-dependent plasmonic properties and Raman enhancements when deposited on substrates.

Colorimetric Effect of Gold Nanocup Arrays on Fluorescence Amplification

Without changing underlying plasmonic substrate designs, tunable fluorescence enhancement is achieved by varying surrounding fluidic refractive indices on a colorimetric plasmonic substrate of periodic Au nanocup arrays. When comparing the emission characteristics of two fluorophores on the plasmonic surface, HEX with green emission and TEX with red emission, tuning the plasmonic resonance wavelength matched with the emission band of fluorophores is verified as a key factor for the largest fluorescence amplification. Even though the plasmonic nanocup array substrate is already capable of enhancing fluorescence emission compared to that on the Au film, further enhancement by 6.93-fold for HEX at 1.36 refractive index unit (RIU) and 7.12-fold for TEX at 1.45 RIU, both from 1 RIU, is accomplished on the same nanoplasmonic device. The numerical calculations of the quantum efficiency and the radiative decay rate show the same response with the experimental fluorescence emission variations under fluidic refract...

Fabrication and Optical Properties of Inclined Au Nanocup Arrays

We fabricated inclined Au nanocup arrays by using the nanosphere lithography method combined with dichloromethane etching and investigated their optical properties. The transmittance spectra of these Au nanocup arrays under different polarizations and incident angles were detected and discussed. Surface plasmon resonance was employed to explain the peaks in the spectra. These inclined Au nanocup arrays may be useful for the potential applications in plasmonic devices.

Facile synthesis of functional Au nanopatches and nanocups

This communication describes a one-step strategy for the facile synthesis of polymer-Au patchy particles (PPs) and Au nanocups using the interfacial reactions.

Angle- and Spectral-Dependent Light Scattering from Plasmonic Nanocups

As optical frequency nanoantennas, reduced-symmetry plasmonic nanoparticles have light-scattering properties that depend strongly on geometry, orientation, and variations in dielectric environment. Here we investigate how these factors influence the spectral and angular dependence of light scattered by Au nanocups. A simple dielectric substrate causes the axial, electric dipole mode of the nanocup to deviate substantially from its characteristic cos(2) θ free space scattering profile, while the transverse, magnetic dipole mode remains remarkably insensitive to the presence of the substrate. Nanoscale irregularities of the nanocup rim and the local substrate permittivity have a surprisingly large effect on the spectral- and angle-dependent light-scattering properties of these structures.

Light-Bending Nanoparticles

Metallic nanostructures with their geometry-dependent optical resonances are a topic of intense current interest due to their ability to manipulate light in ways not possible with conventional optical materials. A particularly fascinating aspect of these systems is the recently realized possibility of creating optical frequency "magnetic plasmon" responses of comparable magnitude to the "electric plasmon" response. Here we show that Au nanocups at their magnetoinductive resonance have the unique ability to redirect scattered light in a direction dependent on cup orientation, as a true three-dimensional nanoantenna.