Plasmonic Annular Nanotrenches with 1 nm Nanogaps for Detection of SARS-CoV-2 Using SERS-Based Immunoassay.

This study represents the synthesis of a novel class of nanoparticles denoted as annular Au nanotrenches (AANTs). AANTs are engineered to possess embedded, narrow circular nanogaps with dimensions of approximately 1 nm, facilitating near-field focusing for detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) via a surface-enhanced Raman scattering (SERS)-based immunoassay. Notably, AANTs exhibited an exceedingly low limit of detection (LOD) of 1 fg/mL for SARS-CoV-2 spike glycoproteins, surpassing the commercially available enzyme-linked immunosorbent assay (ELISA) by 6 orders of magnitude (1 ng/mL from ELISA). To assess the real-world applicability, a study was conducted on 50 clinical samples using an SERS-based immunoassay with AANTs. The results revealed a sensitivity of 96% and a selectivity of 100%, demonstrating the significantly enhanced sensing capabilities of the proposed approach in comparison to ELISA and commercial lateral flow assay kits.

Plasmonic Dodecahedral-Walled Elongated Nanoframes for Surface-Enhanced Raman Spectroscopy.

Here, elongated pseudohollow nanoframes composed of four rectangular plates enclosing the sides and two open-frame ends with four ridges pointing at the tips for near-field focusing are reported. The side facets act as light-collecting domains and transfer the collected light to the sharp tips for near-field focusing. The nanoframes are hollow inside, allowing the gaseous analyte to penetrate through the entire architecture and enabling efficient detection of gaseous analytes when combined with Raman spectroscopy. The resulting nanostructures are named Au dodecahedral-walled nanoframes. Synthesis of the nanoframes involves shape transformation of Au nanorods with round tips to produce Au-elongated dodecahedra, followed by facet-selective Pt growth, etching of the inner Au, and regrowth steps. The close-packed assembly of Au dodecahedral-walled nanoframes exhibits an attomolar limit of detection toward benzenethiol. This significant enhancement in SERS is attributed to the presence of a flat solid terrace for a large surface area, sharp edges and vertices for strong electromagnetic near-field collection, and open frames for effective analyte transport and capture. Moreover, nanoframes are applied to detect chemical warfare agents, specifically mustard gas simulants, and 20 times higher sensitivity is achieved compared to their solid counterparts.

Plasmonic Double-Walled Nanoframes with Face-to-Face Nanogaps for Strong SERS Activity.

A synthesis method for plasmonic double-walled nanoframes was developed, where single-walled truncated octahedral nanoframes with (111) open facets and (100) solid flat planes are nested in a core-shell manner. By applying multiple chemical toolkits to Au cuboctahedrons as a starting template, Au double-walled nanoframes with controllable face-to-face nanogaps were successfully synthesized in high homogeneity in size and shape. Importantly, when the gap distance between inner and outer flat walled frames became closer, augmentation of electromagnetic near-field focusing was achieved, leading to generation of hot-zones, which was verified by surface-enhanced Raman spectroscopy. The unique optical property of Au double-walled nanoframes with high structural intricacy was carefully investigated and the SERS substrates comprising Au double-walled nanoframes with the narrowest nanogaps exhibited much improved near-field enhancement toward strongly and/or weakly adsorbing analytes, allowing for gas phase detection in chemical warfare agents, which is a huge challenge in early warning systems.

Multi-Layered PtAu Nanoframes and Their Light-Enhanced Electrocatalytic Activity via Plasmonic Hot Spots.

Here, the rational design of complex PtAu double nanoframes (DNFs) for plasmon-enhanced electrocatalytic activity toward the methanol oxidation reaction (MOR) is reported. The synthetic strategy for the DNFs consists of on-demand multiple synthetic chemical toolkits, including well-faceted Au growth, rim-on selective Pt deposition, and selective Au etching steps. DNFs are synthesized by utilizing Au truncated octahedrons (TOh) as a starting template. The outer octahedral (Oh) nanoframes (NFs) nest the inner TOh NFs, eventually forming DNFs with a tunable intra-nanogap distance. Residual Au adatoms on Pt skeletons act as light entrappers and produce plasmonic hot spots between inner and outer frames through localized surface plasmon resonance (LSPR) coupling, which promotes enhanced electrocatalytic activity for the MOR. Importantly, the correlation between the gap-induced hot carriers and electrocatalytic activity is evaluated. The highest catalytic activity is achieved when the gap is the narrowest. To further harness their light-trapping capability, hierarchically structured triple NFs (TNFs) are synthesized, wherein three NFs are entangled in a single entity with a high density of hot regions, exhibiting superior electrocatalytic activity toward the MOR with a sixfold larger current density under light irradiation compared to the dark conditions.

All-Hot-Spot Bulk Surface-Enhanced Raman Scattering (SERS) Substrates: Attomolar Detection of Adsorbates with Designer Plasmonic Nanoparticles.

Here we report a synthetic pathway toward Au truncated octahedral dual-rim nanoframes wherein two functional facets are formed including (1) eight hot nanogaps formed by hexagonal nanoframes embracing core circular nanorings for near-field focusing and (2) six flat squares that facilitate the formation of well-ordered arrays of nanoframes through self-assembly. The existence of intra-nanogaps in a single entity enables strong electromagnetic near-field focusing, allowing single-particle surface-enhanced Raman spectroscopy. Then, we built "all-hot-spot bulk SERS substrates" with those entities, wherein the presence of truncated terraces with high homogeneity in size and shape facilitate spontaneous self-assembly into a highly ordered and uniform superlattice, exhibiting a limit of detection of attomolar concentrations toward 2-naphthalenethiol, which is 6 orders lower than that of monorim counterparts. The observed low limit of detection originates from the combined synergic effect from both inter- and intraparticle coupling in a superlattice, which we dubbed "all-hot-spot bulk SERS substrates".

Au Nanorings with Intertwined Triple Rings.

We designed complex Au nanorings with intertwined triple rings (ANITs) in a single entity to amplify the efficacy of near-field focusing. Such a complex and unprecedented morphology at the nanoscale was realized through on-demand multistepwise reactions. Triangular nanoprisms were first sculpted into circular nanorings, followed by a series of chemical etching and deposition reactions eventually leading to ANITs wherein thin metal bridges hold the structure together without any linker molecules. In the multistepwise reaction, the well-faceted growth pattern of Au, which induces the growth of two distinctive flat facets in a lateral direction, is important to evolve the morphology from single to multiple nanorings. Although our synthesis proceeds through multiple steps in one batch without purification steps, it shows a remarkably high yield (>∼90%) at the final stage. The obtained high degree of homogeneity (in both shape and size) of the resulting ANITs allowed us to systematically investigate the corresponding localized surface plasmon resonance (LSPR) coupling with varying nanoring arrangements and observe their single-particle surface enhanced Raman scattering (SERS). Surprisingly, individual ANITs exhibited an enormously large enhancement factor (∼109), which confirms their superior near-field focusing relative to other reported nanoparticles.

Web-above-a-Ring (WAR) and Web-above-a-Lens (WAL): Nanostructures for Highly Engineered Plasmonic-Field Tuning and SERS Enhancement.

Synthetic strategies of web-above-a-ring (WAR) and web-above-a-lens (WAL) nanostructures are reported. The WAR has a controllable gap between the nanoring core and a nanoweb with nanopores for the effective confinement of electromagnetic field in the nanogap and subsequent surface-enhanced Raman scattering (SERS) of Raman dyes inside the gap with high signal reproducibility, which are attributed to the generation of circular 3D hot zones along the rim of Pt@Au nanorings with wrapping nanoweb architecture. More specifically, Pt@Au nanorings are adopted as a plasmonic core for structural rigidity and built porous nanowebs above them through a controlled combination of galvanic exchange and the Kirkendall effect. Both nanoweb and nanolens structures are also formed on Pt@Au nanoring, which is WAL. structure. Remarkably, plasmonic hot zone, nanopores, and hot lens are formed inside a single WAL nanostructure, and these structural components are orchestrated to generate stronger SERS signals.

Synthesis and Surface Plasmonic Characterization of Asymmetric Au Split Nanorings.

In this Letter, a rational and stepwise method for the solution-phase synthesis of asymmetric Au split nanorings by adopting Au nanoprisms as a template has been demonstrated. The selective chemical etching of Au nanoprism tips activated the surface reactivity of edges and led to the selective deposition of Pt at the periphery of Au nanoplates. By controlling the total amount of Pt on the edges, different degrees of split Au@Pt nanorings were obtained; the subsequent Au coating around the Au@Pt scaffold eventually resulted in asymmetric Au hexagonal split nanorings. Their surface plasmonic features as a function of split degrees were investigated, including straight nanorods, bent nanorods, split nanorings, and full nanorings. The electrical field focusing using single-particle surface-enhanced Raman spectroscopy was evaluated under different polarization angles of the incident light for two different structures with the point gap and line gap between two arms.

Three-Dimensional Gold Nanosphere Hexamers Linked with Metal Bridges: Near-Field Focusing for Single Particle Surface Enhanced Raman Scattering.

Herein, we report the novel strategy for the synthesis of complex 3-dimensional (3D) nanostructures, mimicking the linker molecule-free 3D arrangement of six Au nanospheres at the vertices of octahedrons. We utilized 3D PtAu skeleton for the structural rigidity and deposited Au around the PtAu skeleton in a site-selective manner, allowing us to investigate their surface plasmonic coupling phenomenon and near-field enhancement as a function of sizes of nanospheres, which are directly related to the intrananogap distance and interior volume size. The resulting 3D Au hexamer structures with octahedral arrangement were realized through precise control of the Au growth pattern. The complex 3D Au hexamers were composed of six Au nanospheres connected by thin metal conductive bridges. The standard deviation of the metal conductive bridges and Au nanospheres was within ca. 10%, exhibiting a high degree of homogeneity and precise structural tunability. Interestingly, charge transfer among the six Au nanospheres occurred along the metal conductive bridges leading to surface plasmonic coupling between Au nanospheres. Accordingly, electric near fields were strongly and effectively focused at the vertices, intrananogap regions between Au nanospheres, and interior space, exhibiting well-resolved single-particle surface-enhanced Raman spectroscopy signals of absorbed analytes.

Silver Double Nanorings with Circular Hot Zone.

Silver double nanorings with circular intra-nanogaps between two nanorings of different diameters were synthesized without a linker molecule to confine an incident electromagnetic field in a single entity. We used on-demand, rational, and systematic multi-stepwise reactions consisting of (1) selective etching of gold, (2) rim-on deposition of platinum, (3) eccentric growth of gold, and (4) concentric growth of silver. The resulting silver double nanorings exhibited a high degree of homogeneity in both shape and size, with strongly coupled circular hot zones (or "hot halos", referring to the circular intra-nanogaps capable of focusing the near electromagnetic field) resulting from strong surface plasmon coupling between the inner and outer nanorings. Remarkably, these silver double nanorings exhibited strong, stable, and reproducible single-particle surface-enhanced Raman scattering signals without blinking. The signals appeared independently of polarization directions, which is a unique feature of a circular hot halo. The estimated enhancement factor was between 2 × 108 and 7 × 108. The measured limit of detection was 10-7 M in bulk concentration, and the signal appeared 570 s after sample exposure.

Ready-to-Use Free-Standing Super-Powder Made with Complex Nanoparticles for SERS.

This study presents a straightforward and efficient synthetic approach for producing high-yield, ready-to-use, free-standing super-powder. The synthesis protocol demonstrates versatility, enabling the creation of assemblies from various nanoparticle morphologies and compositions without the need for specific substrates. Au nanorings are employed as building blocks for fabricating the super-powder, which can be used in surface-enhanced Raman spectroscopy (SERS). The distinctive aspect ratio of the ring nanoframes allows the formation of densely packed columnar assemblies on the substrate, aligning the exposed gaps perpendicular to the laser beam. This arrangement significantly enhances the charge separation among nanorings, leading to a highly focused near-field that is applicable to SERS analysis. The SERS detection feasibility of this powder in both pre- and post-contamination conditions is demonstrated. Using a wide range of building blocks, encompassing various shapes (for instance, rods, hexagons, cubes, cuboctahedrons, elongated dodecahedrons, triangular rings, double-rings, elongated dodecahedra frames, cuboctahedra frames, and double-walled frames), the generalizability of the process for synthesizing super-powders with diverse morphologies is substantiated.

Step-by-Step Nanoscale Top-Down Blocking and Etching Lead to Nanohexapods with Cartesian Geometry.

In this research, we designed a stepwise synthetic method for Au@Pt hexapods where six elongated Au pods are arranged in a pairwise perpendicular fashion, sharing a common point (the central origin in a Cartesian-coordinate-like hexapod shape), featured with tip-selectively decorated Pt square nanoplates. Au@Pt hexapods were successfully synthesized by applying three distinctive chemical reactions in a stepwise manner. The Pt adatoms formed discontinuous thin nanoplates that selectively covered six concave facets of a Au truncated octahedron and served as etching masks in the succeeding etching process, which prevented underlying Au atoms from being oxidized. The subsequent isotropic etching proceeded radially, starting from the bare Au surface, carving the central nanocrystal in a concave manner. By controlling the etching conditions, Au@Pt hexapods were successfully fabricated, wherein the core Au domain is connected to six protruding arms, which hold Pt nanoplates at the ends. Due to their morphology, Au@Pt hexapods feature distinctive optical properties in the near-infrared region, as a proof of concept, allowing for surface-enhanced Raman spectroscopy (SERS)-based monitoring of in situ CO electrooxidation. We further extended our synthetic library by tailoring the size of the Pt nanoplates and neck widths of Au branches, demonstrating the validity of selective blocking and etching-based colloidal synthesis.

Photoluminescence of MoS2 on Plasmonic Gold Nanoparticles Depending on the Aggregate Size.

Transition metal dichalcogenides (TMDs) are promising candidates for ultrathin functional semiconductor devices. In particular, incorporating plasmonic nanoparticles into TMD-based devices enhances the light-matter interaction for increased absorption efficiency and enables control of device performance such as electronic, electrical, and optical properties. In this heterohybrid structure, manipulating the number of TMD layers and the aggregate size of plasmonic nanoparticles is a straightforward approach to tailoring device performance. In this study, we use photoluminescence (PL) spectroscopy, which is a commonly employed technique for monitoring device performance, to analyze the changes in electronic and optical properties depending on the number of MoS2 layers and the size of the gold nanoparticle (AuNP) aggregate under nonresonant and resonant excitation conditions. The PL intensity in monolayer MoS2/AuNPs increases as the size of aggregates increases irrespective of the excitation conditions. The strain induced by AuNPs causes a red shift, but as the aggregates grow larger, the effect of p-doping increases and the blue shift becomes prominent. In multilayer MoS2/AuNPs, quenched PL intensity is observed under nonresonant excitation, while enhancement is noted under resonant excitation, which is mainly contributed by p-doping and LSPR, respectively. Remarkably, the alteration in the spectral shape due to resonant excitation is evident solely in small aggregates of AuNPs across all layers.

Bimetallic alloy Ag@Au nanorings with hollow dual-rims focus near-field on circular intra-nanogaps.

Here, we report a highly sensitive and reliable surface enhanced Raman scattering (SERS)-based immunoassay using bimetallic alloy Ag@Au hollow dual-rim nanorings (DRNs) where two hollow nanorings with different diameters are concentrically overlapped and connected by thin metal ligaments, forming circular hot-zones in the intra-nanogaps between the inner and outer rims. Pt DRNs were first prepared, and then Ag was deposited on the surface of the Pt skeleton, followed by Au coating, resulting in alloy Ag@Au hollow DRNs. The chemical stability of Au and the high optical properties of Ag are incorporated into a single entity, Ag@Au hollow DRNs, enabling strong single-particle SERS activity and biocompatibility through surface modification with thiol-containing functionalities. When Ag@Au hollow DRNs were utilized as nanoprobes for detecting human chorionic gonadotropin (HCG) hormone through a SERS-based immunoassay, a very low limit of detection of 10 pM with high reliability was achieved, strongly indicating their advantage as ultrasensitive SERS nanoprobes.

Plasmonic All-Frame-Faceted Octahedral Nanoframes with Eight Engraved Y-Shaped Hot Zones.

We report the synthesis of all-frame-faceted octahedral nanoframes containing eight Y-shaped hot zones in a single entity where electromagnetic near-field focusing can be maximized. To realize such state-of-the-art complex nanoframes, a series of multiple stepwise bottom-up processes were executed by exploiting Au octahedral nanoparticles as the initial template. By rationally controlling the chemical reactivity of different surface facets (i.e., vertexes, edges, and terraces), the Au octahedral nanoparticles went through controlled shape transformations, leading to Au-engraved nanoparticles wherein 24 edges wrap the octahedral Au nanoparticle core. Those edges were then selectively decorated with Pt, leading to the formation of eight Pt tripods in a single entity. After etching the central Au, 3D Pt tripod frame-faceted octahedral nanoframes were achieved with high integrity. By harnessing the obtained Pt nanoframes as a scaffold, AuAg alloy-based plasmonic all-frame-faceted nanoframes were obtained after the co-reduction of Ag and Au, which generated multiple hot zones within multiple surface intra-nanogaps, creating a single-particle, surface-enhanced Raman spectroscopy enhancer platform.

Synthesis of Pt Double-Walled Nanoframes with Well-Defined and Controllable Facets.

In this paper, we demonstrate the synthesis of morphologically complex nanoframes wherein a mixture of frames and thin solid planes, which we refer to as walled-nanoframes, are present in a single particle. By applying multiple chemical steps including shape evolution of Au nanocrystals and controlling chemical potential of solution for selective deposition, we successfully designed a variety of Pt nanoframes including Pt cuboctahedral nanoframes and Pt single-walled nanoframes. The rationale for on-demand chemical steps with well-faceted Au overgrowth allowed for the synthesis of double-walled nanoframes where two Pt single-walled nanoframes are concentrically overlapped in a single entity with a clearly discernible gap between the two nanoframes. Given the coexistence of an open structure of nanoframe and thin plates within one entity, the double-walled nanoframes showed a dramatic increase in catalytic activity toward the methanol oxidation reaction, acting as high-surface area, carbon-free, and volume-compact nanocatalysts.

Three-dimensional nanoframes with dual rims as nanoprobes for biosensing.

Three-dimensional (3D) nanoframe structures are very appealing because their inner voids and ridges interact efficiently with light and analytes, allowing for effective optical-based sensing. However, the realization of complex nanoframe architecture with high yield is challenging because the systematic design of such a complicated nanostructure lacks an appropriate synthesis protocol. Here, we show the synthesis method for complex 3D nanoframes wherein two-dimensional (2D) dual-rim nanostructures are engraved on each facet of octahedral nanoframes. The synthetic scheme proceeds through multiple executable on-demand steps. With Au octahedral nanoparticles as a sacrificial template, sequential processes of edge-selective Pt deposition and inner Au etching lead to Pt octahedral mono-rim nanoframes. Then, adlayers of Au are grown on Pt skeletons via the Frank-van der Merwe mode, forming sharp and well-developed edges. Next, Pt selective deposition on both the inner and outer boundaries leads to tunable geometric patterning on Au. Finally, after the selective etching of Au, Pt octahedral dual-rim nanoframes with highly homogeneous size and shape are achieved. In order to endow plasmonic features, Au is coated around Pt frames while retaining their geometric shape. The resultant plasmonic dual-rim engraved nanoframes possess strong light entrapping capability verified by single-particle surface-enhanced Raman scattering (SERS) and show the potential of nanoprobes for biosensing through SERS-based immunoassay.

Plasmon-exciton couplings in the MoS2/AuNP plasmonic hybrid structure.

The understanding and engineering of the plasmon-exciton coupling are necessary to control the innovative optoelectronic device platform. In this study, we investigated the intertwined mechanism of each plasmon-exciton couplings in monolayer molybdenum disulfide (MoS2) and plasmonic hybrid structure. The results of absorption, simulation, electrostatics, and emission spectra show that interaction between photoexcited carrier and exciton modes are successfully coupled by energy transfer and exciton recombination processes. Especially, neutral exciton, trion, and biexciton can be selectively enhanced by designing the plasmonic hybrid platform. All of these results imply that there is another degree of freedom to control the individual enhancement of each exciton mode in the development of nano optoelectronic devices.