Combinatorial Approach to Find Nanoparticle Assemblies with Maximum Surface-Enhanced Raman Scattering.

Plasmonic nanoparticles exhibit unique properties that distinguish them from other nanomaterials, including vibrant visible colors, the generation of local electric fields, the production of hot charge carriers, and localized heat emission. These properties are particularly enhanced in the narrow nanogaps formed between nanostructures. Therefore, creating nanogaps in a controlled fashion is the key to achieving a fundamental understanding of plasmonic phenomena originating from the nanogaps and developing advanced nanomaterials with enhanced performance for diverse applications. One of the most effective approaches to creating nanogaps is to assemble individual nanoparticles into a clustered structure. In this study, we present a fast, facile, and highly efficient method for preparing core@satellite (CS) nanoassembly structures using gold nanoparticles of various shapes and sizes, including nanospheres, nanocubes (AuNCs), nanorods, and nanotriangular prisms. The sequential assembly of these building blocks on glass substrates allows us to obtain CS nanostructures with a 100% yield within 4 h. Using 9 different building blocks, we successfully produce 16 distinct CS nanoassemblies and systematically investigate the combinations to search for the highest Raman enhancement. We find that the surface-enhanced Raman scattering (SERS) intensity of AuNC@AuNC CS nanoassemblies is 2 orders of magnitude larger than that of other CS nanoassemblies. Theoretical analyses reveal that the intensity and distribution of the electric field induced in the nanogaps by plasmon excitation, as well as the number of molecules in the interfacial region, collectively contribute to the unprecedentedly large SERS enhancement observed for AuNC@AuNC. This study not only presents a novel assembly method that can be extended to produce many other nanoassemblies but also identifies a highly promising SERS material for sensing and diagnostics through a systematic search process.

Mode-Selective Plasmon Coupling between Au Nanorods and Au Nanospheres.

Plasmons play a central role in the properties of gold nanoparticles (AuNPs). Plasmons in a AuNP are influenced by neighboring ones, resulting in hybridized bonding dipole modes and red-shifted resonance peaks in the extinction spectra. Previous studies have mainly focused on plasmon coupling among spherical AuNPs (AuNSs). Here, we explore plasmonic interactions between AuNSs and anisotropic gold nanorods (AuNRs), which have longitudinal (LO) and transverse (TR) plasmon modes. We successfully assemble AuNSs around AuNRs ("AuNR@AuNS"), observing shifts in both the LO and TR modes in the extinction spectra due to directional coupling. Selectively binding AuNSs to the ends of AuNRs ("AuNR═AuNS") leads to predominant plasmon coupling along the LO direction. Our simulation studies reveal that exclusive LO or TR coupling occurs only when AuNSs attach to the center of either the end or the side of AuNRs. This study provides a valuable guideline for selectively exciting plasmons in desired nanogaps when multiple nanogaps are present.

SERS-ELISA using silica-encapsulated Au core-satellite nanotags for sensitive detection of SARS-CoV-2.

The sensitive detection of viruses is key to preventing the spread of infectious diseases. In this study, we develop a silica-encapsulated Au core-satellite (CS@SiO2) nanotag, which produces a strong and reproducible surface-enhanced Raman scattering (SERS) signal. The combination of SERS from the CS@SiO2 nanotags with enzyme-linked immunosorbent assay (ELISA) achieves a highly sensitive detection of SARS-CoV-2. The CS@SiO2 nanotag is constructed by assembling 32 nm Au nanoparticles (AuNPs) on a 75 nm AuNP. Then the core-satellite particles are encapsulated with SiO2 for facile surface modification and stability. The SERS-ELISA technique using the CS@SiO2 nanotags provides a great sensitivity, yielding a detection limit of 8.81 PFU mL-1, which is 10 times better than conventional ELISA and 100 times better than lateral flow assay strip method. SERS-ELISA is applied to 30 SARS-CoV-2 clinical samples and achieved 100% and 55% sensitivities for 15 and 9 positive samples with cycle thresholds < 30 and > 30, respectively. This new CS@SiO2-SERS-ELISA method is an innovative technique that can significantly reduce the false-negative diagnostic rate for SARS-CoV-2 and thereby contribute to overcoming the current pandemic crisis.

Core-satellite-satellite hierarchical nanostructures: assembly, plasmon coupling, and gap-selective surface-enhanced Raman scattering.

The plasmonic properties of gold nanoparticles (AuNPs), such as color tunability, electric field generation, hot carrier generation, and localized heating, are significantly enhanced in the nanogaps between AuNPs. Therefore, the creation and control of nanogaps are key to developing advanced plasmonic nanomaterials. Most AuNP nanoassemblies, including dimers, trimers, and core-satellites, have a single type of nanogap within the assembly. In this study, we construct core-satellite-satellite (CSS) hierarchical, fractal-like nanostructures featuring two types of nanogaps, namely first generation nanogaps (Gap1) between the core and first satellite (Sat1) AuNPs and second generation nanogaps (Gap2) between Sat1 and second satellite (Sat2) AuNPs. The sequential and alternating immersion of glass slides in different-sized AuNPs and linkers forms CSS with perfect yield. The UV-vis spectroscopy, combined with charge density distribution calculations, reveals the nature of the plasmon coupling between the AuNPs that constitute CSS nanoassemblies. The plasmon coupling can be tuned by independently varying Gap1 and Gap2. Furthermore, we explore the electric field amplification in Gap1 and Gap2 by comparing the surface-enhanced Raman scattering signal intensity selectively from each nanogap. This new type of nanostructure provides a great flexibility to control and enhance the plasmonic properties of noble metal nanoparticles.

Effect of Nanoparticle Size on Plasmon-Driven Reaction Efficiency.

Hot electron chemistry is of paramount significance because of its applicability to photocatalytic reactions, solar energy conversion, and waste decomposition. The nonradiative decay of excited plasmons in gold nanoparticles (AuNPs) generates highly energetic nonthermal electrons and holes that can induce chemical reactions when transferred to nearby molecules. In this study, we explore the relationship between AuNP size (26-133 nm) and the plasmon-induced reaction yield. To isolate the size from other structural parameters, we prepare perfectly round gold nanospheres (AuNSs) with narrow size distributions. The use of a nanoparticle-on-mirror configuration, in which the reactant molecules (4-mercaptobenzoic acid) are positioned in nanogaps between the AuNSs and a Au film, promotes the generation of hot carriers and allows the highly sensitive detection of the reaction products (benzenethiol) using surface-enhanced Raman spectroscopy. We show that the reaction yield increases as the AuNS size increases up to 94 nm and then decreases for larger AuNSs. This peculiar Λ-shaped size-dependent reactivity can be explained by considering both the plasmonic absorption efficiency of AuNSs and the decay rate of plasmons via electron-surface scattering. The product of the calculated absorption cross section and the inverse of the AuNS size reproduces our experimental results remarkably well. These findings will contribute to the design of highly efficient plasmonic photocatalysts and photovoltaic devices.

Strain-Induced Modulation of Localized Surface Plasmon Resonance in Ultrathin Hexagonal Gold Nanoplates.

Anisotropic gold nanoplates (NPLs) have raised the interesting possibility that their reduced geometrical symmetry allows fine tuning of their optical properties associated with the excitation of localized surface plasmon resonances (LSPRs). Recent developments have greatly improved LSPR tunability by utilizing the spatial distribution of LSPR modes. However, the nanoscale interplay between defect-induced mechanical strain and the spatial variation of LSPR modes remains poorly understood. In this work, the combination of high spatial- and spectral-resolution mapping of LSPR modes and nanoscale strain mapping using aberration-corrected transmission electron microscopy are applied to investigate the nanoscale distribution of LSPR modes in an ultrathin single hexagonal gold NPL and the effect of defect-induced strains on its LSPR properties. The electron energy-loss spectral maps reveal four distinct LSPR components and intensity distributions of all LSPR modes in a hexagonal gold NPL. Furthermore, the strain maps provide experimental evidence that the tensile strain field induced by a Z-shaped faulted dipole is responsible for the asymmetric distribution of LSPR intensity in a hexagonal gold NPL.

Plasmon-driven protodeboronation reactions in nanogaps.

Boronic acids are the key compounds in Suzuki coupling reactions and in the detection of monosaccharides. The C-B bond cleavage deboronation is an important side reaction that lowers the Suzuki coupling reaction yield and even disables saccharide detection. Here, we report that protodeboronation occurs for 4-mercaptophenylboronic acid (MPBA) within narrow nanogaps between gold nanoparticles (AuNPs) and planar gold substrates. The irradiation of such nanoparticle-on-mirror (NPoM) systems at 785 nm drives the protodeboronation reaction to form benzenethiol (BT). Wavelength-dependence experiments, combined with dark-field single-particle scattering spectroscopy, reveal that excitation of the bonding dipole plasmon mode of the NPoM leads to the best efficiency. Among the excited plasmon decay pathways, the generation of hot charge carriers induces the protodeboronation of MPBA. The possibility of plasmonic thermal reactions is ruled out because external heating of the substrates does not cause the reaction to take place. A comparison of the reaction yield under ambient, Ar, and oxygen gas conditions reveals that hot charge carriers directly transfer to MPBA, which subsequently produces BT, but the presence of oxygen promotes the reaction by opening another hot-electron transfer channel. The protodeboronation reaction of MPBA is an important addition to the catalog of plasmon-driven chemical reactions, not only because the reaction is relevant to organic and analytical chemistry but also because it deepens our understanding of the hot carrier dynamics at the interface between plasmonic nanoparticles and molecules.

Effect of Nanogap Morphology on Plasmon Coupling.

Plasmon coupling is the fundamental principle by which the optical resonances in nanoparticle assemblies are tuned. Interactions of plasmons among nanoparticles in close proximity create plasmon coupling modes whose energies are sensitive to the nanogap parameters. Whereas many studies have focused on the gap distances, we herein probe the effect of gap morphology on plasmon coupling. Dimers that are prepared by adsorbing perfectly round ultrauniform Au nanospheres (AuNSs) onto the faces, edges, and vertices of Au nanocubes (AuNCs) present distinctly different nanogap morphologies. Dark-field single-particle scattering spectroscopy reveals that the longitudinal plasmon coupling mode shifts to lower energies as the AuNS forms a nanogap with parts of the AuNC with higher curvature. Simulation spectra are also consistent with this observation. Our calculations indicate that the much larger charge density at the vertex or edge of a AuNC lowers the plasmon coupling energy through the contribution of the Coulomb interaction when the AuNC combines with the AuNS. In comparison, the plasmon energies or anisotropic polarizability along the face, edge, and vertex directions of a AuNC differ only slightly and thus do not cause a shift in the plasmon coupling mode.

How Does a Plasmon-Induced Hot Charge Carrier Break a C-C Bond?

Hot-electron chemistry at gold nanoparticle (AuNP) surfaces has received much attention recently because its understanding provides a basis for plasmonic photocatalysis and photovoltaics. Nonradiative decay of excited surface plasmons produces energetic hot charge carriers that transfer to adsorbate molecules and induce chemical reactions. Such plasmon-driven reactions, however, have been limited to a few systems, notably the dimerization of 4-aminobenzenethiol to 4,4'-dimercaptoazobenzene. In this work, we explore a new class of plasmon-driven reactions associated with a unimolecular bond cleavage process. We unveil the mechanism of the decarboxylation reaction of 4-mercaptobenzoic acid and extend the mechanism to account for the ß-cleavage reaction of 4-mercaptobenzyl alcohol. Combining the construction of well-controlled nanogap systems and sensitive Raman spectroscopy with methodical changes of experimental conditions (laser wavelengths, interface materials, pH, ambient gases, etc.), we track the hot charge carriers from the formation to the transfer to reactants, which provides insights into how plasmon excitation eventually leads to the C-C bond cleavage of the molecules in the nanogap.

Colour and SERS patterning using core-satellite nanoassemblies.

We explore spatial control of the formation of core-satellite nanoassemblies on glass substrates. UV irradiation leads to the photooxidative desorption of thiol linkers from gold nanoparticles deposited on the substrates, thereby prohibiting further assembly in the irradiated region. The distribution of assemblies and monomers yields a pattern with stark contrasts in colour and Raman enhancement. Our findings can be utilised in the fabrication of microfluidic SERS sensors, colour displays, photonic devices, and metamaterials.

The Chemical Fluctuation Theorem governing gene expression.

Gene expression is a complex stochastic process composed of numerous enzymatic reactions with rates coupled to hidden cell-state variables. Despite advances in single-cell technologies, the lack of a theory accurately describing the gene expression process has restricted a robust, quantitative understanding of gene expression variability among cells. Here we present the Chemical Fluctuation Theorem (CFT), providing an accurate relationship between the environment-coupled chemical dynamics of gene expression and gene expression variability. Combined with a general, accurate model of environment-coupled transcription processes, the CFT provides a unified explanation of mRNA variability for various experimental systems. From this analysis, we construct a quantitative model of transcription dynamics enabling analytic predictions for the dependence of mRNA noise on the mRNA lifetime distribution, confirmed against stochastic simulation. This work suggests promising new directions for quantitative investigation into cellular control over biological functions by making complex dynamics of intracellular reactions accessible to rigorous mathematical deductions.

Plasmon coupling between silver nanoparticles: Transition from the classical to the quantum regime.

We explore plasmon coupling between silver nanoparticles (AgNPs) as two AgNPs approach each other within a subnanometer distance. We prepare AgNP dimers with two 21-nm AgNPs separated by alkanedithiol linkers in high yield. Changing the length of the alkanedithiol linkers enables us to control the interparticle distance down to the subnanometer level on the molecular scale. We observe that the longitudinal plasmon coupling band, which is sensitive to the interaction between AgNPs, gradually redshifts as the interparticle distance decreases. This observation is fully consistent with the classical electromagnetic model. The redshift of the plasmon coupling, however, undergoes a drastic change when the interparticle distance reaches ∼1nm. The longitudinal plasmon coupling band vanishes and a new intense band appears at a shorter wavelength. This band redshifts as the nanogap further narrows, but crosses over to a blueshift at ∼0.7nm. A comparison of our observation with finite-difference time-domain simulations reveals that this band arises from quantum effects. Controlled assembly of AgNP dimers in combination with simulations allows us to observe the transition of the plasmon coupling from the classical to the quantum regime at the ensemble level.

Bridging the Nanogap with Light: Continuous Tuning of Plasmon Coupling between Gold Nanoparticles.

The control of nanogaps lies at the heart of plasmonics for nanoassemblies. The plasmon coupling sensitively depends on the size and the shape of the nanogaps between nanoparticles, permitting fine-tuning of the resonance wavelength and near-field enhancement at the gap. Previously reported methods of molecular or lithographic control of the gap distance are limited to producing discrete values and encounter difficulty in achieving subnanometer gap distances. For these reasons, the study of the plasmon coupling for varying degrees of interaction remains a challenge. Here, we report that by using light, the interparticle distance for gold nanoparticle (AuNP) dimers can be continuously tuned from a few nanometers to negative values (i.e., merged particles). Accordingly, the plasmon coupling between the AuNPs transitions from the classical electromagnetic regime to the contact regime via the nonlocal and quantum regimes in the subnanometer gap region. We find that photooxidative desorption of alkanedithiol linkers induced by UV irradiation causes the two AuNPs in a dimer to approach each other and eventually merge. Light-driven control of the interparticle distance offers a novel means of exploring the fundamental nature of plasmon coupling as well as the possibility of fabricating nanoassemblies with any desired gap distance in a spatially controlled manner.

Probing quantum plasmon coupling using gold nanoparticle dimers with tunable interparticle distances down to the subnanometer range.

The assembly of noble metal nanoparticles is an appealing means to control the plasmonic properties of nanostructures. Dimers are particularly interesting because they are a model system that can provide fundamental insights into the interactions between nanoparticles in close proximity. Here, we report a highly efficient and facile assembly method for dimers and other forms of assemblies. Gold nanoparticles (AuNPs) adsorbed on aminosilanized glass surfaces protect the silanes underneath the nanoparticles from hydrolysis. This masked desilanization allows us to prepare AuNP homodimers on glass slides with remarkably high yield (∼90%). The interparticle distance and, accordingly, the surface plasmon coupling are readily tuned at the molecular level using self-assembled monolayers of alkanedithiols. As the interparticle distance is reduced, the resonance surface plasmon coupling progressively redshifts, following the classical electromagnetic model. When the interparticle distance enters the subnanometer regime, however, the resonance band begins to blueshift and significantly broadens. The comparison of our observations with theoretical studies reveals that quantum tunneling effects play a significant role in the plasmonic response of AuNP dimers in the subnanometer gap region. The assembly method based on the masked desilanization is extendable to the formation of various other forms of nanoassemblies and, thus, will further our understanding of plasmonic interactions in nanoassemblies.

Influence of the molecular-scale structures of 1-dodecanethiol and 4-methylbenzenethiol self-assembled monolayers on gold nanoparticles adsorption pattern.

In an effort to understand the effects of the molecular structures of self-assembled monolayers on the patterns formed by immobilized Au nanoparticles (AuNPs), we characterized and compared the morphologies and properties of AuNPs adsorbed onto self-assembled monolayers formed by 1-dodecanethiol (DDT-SAM) or 4-methylbenzenethiol (MBT-SAM) assembled on Au(111) surfaces. The AuNP adsorption pattern on the MBT-SAM surface was well-dispersed and characterized by a low degree of corrugation. By contrast, an aggregated and highly corrugated AuNP pattern was observed on the surface of the DDT-SAM. This difference was attributed to the retention or removal of citrate anions present on the AuNPs during adsorption onto the SAM surface. Direct interactions between the AuNPs and the highly corrugated hydrophobic surfaces of the DDT-SAMs could strip the citrate layers from the AuNP surfaces, leading to aggregated adsorption. The water molecules appeared to mediate the adsorption of the AuNPs by reducing the hydrophobicity of the MBT-SAM surface and promoting a more dispersed adsorption configuration.

Probing interfacial interactions using core-satellite plasmon rulers.

Understanding molecular interactions at the interfaces of nanoparticles is fundamentally important because they determine the stability, affinity, functionality, and assembly of nanoparticles. However, probing the governing intermolecular forces at the interfaces, particularly for the nanoparticles dispersed in solution, remains challenging. Here, we demonstrate that the interfacial interactions between citrate-capped gold nanoparticles and various molecular functional groups can be probed using a plasmon ruler, based on a well-defined core-satellite nanoassembly structure. Different nature of the interactions causes a subtle change in the interparticle distance, and the change is sensitively measured as a shift in the plasmon coupling band of the core-satellite nanoassemblies. Molecular interactions including covalent bonding, hydrogen bonding, electrostatic interactions, and van der Waals interactions are explored.

Surface Plasmon Coupling of Compositionally Heterogeneous Core-Satellite Nanoassemblies.

Understanding plasmon coupling between compositionally heterogeneous nanoparticles in close proximity is intriguing and fundamentally important because of the energy mismatch between the localized surface plasmons of the associated nanoparticles and interactions beyond classical electrodynamics. In this Letter, we explore surface plasmon coupling between silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs), assembled in the form of core-satellite structures. A recently developed assembly method allows us to prepare ultrapure core-satellite nanoassemblies in solution, where 50 nm AgNPs are surrounded by 13 nm AuNPs via alkanedithiol linkers. We observe changes in the plasmon coupling between the AgNP core and AuNP satellites as the core-to-satellite gap distance varies from 2.3 to 0.7 nm. Comparison with theoretical studies reveals that the traditional hybridized plasmon modes are abruptly replaced by charge-transfer plasmons at a ∼1 nm gap. Changes with the number of satellites are also discussed.

Controlled assembly and plasmonic properties of asymmetric core-satellite nanoassemblies.

The assembly of noble metal nanoparticles offers an appealing means to control and enhance the plasmonic properties of nanostructures. However, making nanoassemblies with easily modifiable gap distances with high efficiency has been challenging. Here, we report a novel strategy to assemble gold nanoparticles (AuNPs) into Janus-type asymmetric core-satellite nanostructures. Markedly different desorption efficiency between large and small AuNPs in ethanol allows us to prepare the asymmetric core-satellite nanoassemblies in a dispersed colloidal state with near 100% purity. The resulting nanoassemblies have well-defined structures in which a core AuNP (51 nm) is covered by an average of 13 ± 3 satellite AuNPs (13 nm) with part of the core surfaces left unoccupied. Strong surface plasmon coupling is observed from these nanoassemblies as a result of the close proximity between the core and the satellites, which appears significantly red-shifted from the surface plasmon resonance frequencies of the constituting nanoparticles. The dependence of the surface plasmon coupling on a gap distance of less than 3 nm is systematically investigated by varying the length of the alkanedithiol linkers. The asymmetric core-satellite nanoassemblies also serve as an excellent surface-enhanced Raman scattering substrate with an enhancement factor of ~10(6). Finally, we demonstrate that the presented assembly method is extendible to the preparation of compositionally heterogeneous core-satellite nanoassemblies.

Photoisomerization of azobenzene derivatives confined in gold nanoparticle aggregates.

Photoisomerization is an important reaction that confers photoresponsive functionality on nanoparticles. Although photoisomerization of molecules forming self-assembled monolayers on two-dimensional surfaces or three-dimensional clusters has been studied, a detailed picture of interactions of molecules undergoing isomerization with nanoparticles is not available. In this paper, we report on the photoisomerization of azobenzene derivatives spatially confined in gold nanoparticle (AuNP) aggregates. AuNP aggregates allow us to simultaneously probe the structural changes of molecules via surface-enhanced Raman spectroscopy (SERS) and the accompanying changes in interparticle interactions via surface plasmon couplings. AuNP aggregates are formed by the adsorption of synthesized azobenzene-derivatized sulfides (Az) onto the surfaces of AuNPs. The photoisomerization of the adsorbed Az from trans to cis by excitation at 365 nm causes the AuNPs to move close to each other in the aggregates, leading to a redshift of the surface plasmon coupling band in the UV-vis spectra and a concomitant rise in SERS intensity. SERS spectra reveal that the vibrational modes containing the N=N stretching character redshift upon irradiation, suggesting that the N=N bond is significantly weakened when Az is in the cis form in the AuNP aggregates. The weakening of the N=N bond is attributed to the interaction of the N=N bond, which is more exposed to the outside in the cis conformation, with the nearby AuNPs that have come closer by the isomerization of adsorbed Az. We find that backisomerization from cis to trans occurs much faster in the AuNP aggregates (k = 1.9 × 10(-2) min(-1)) than in solution (k = 1.3 × 10(-3) min(-1)) because of the reduced N=N bond order of cis-Az in the aggregates.

Spatially controlled SERS patterning using photoinduced disassembly of gelated gold nanoparticle aggregates.

Controlling the assembly of the nanoparticles is important because the optical properties of noble metal nanoparticles, such as the surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS), are critically dependent on interparticle distances. Among many approaches available, light-induced disassembly is particularly attractive because it enables spatial modification of the optical properties of nanoparticle assemblies. In this study, we prepare gold nanoparticle (AuNP) aggregates in a gel matrix. Irradiation of the gelated AuNP aggregates at 532 nm leads to the disassembly of the aggregates, changing the color (SPR) from dark blue to red and extinguishing the SERS signal along the irradiated pattern, which opens the possibility of facile fabrication of spatially controlled SERS-generating microstructures. The photoinduced disassembly of the AuNP aggregates in solution is also investigated using UV-vis spectroscopy and transmission electron microscopy.