Plasmon Coupling Research Articles

Effective plasmonic spectroscopic amplifiers for hyper-Raman scattering process

In an asymmetric Au cubic trimer, influence of the rotation angle (θ) and side length (w) on both plasmonic coupling features and corresponding enhancement factor of hyper-Raman scattering (HRS) process have been investigated comprehensively under the illumination of a longitudinally polarized light. The finite-difference time-domain (FDTD) electrodynamic simulation tool has been employed to calculate the optical cross-section and associated nearfield intensity of the irradiated coupled resonators. As θ increases, the polarization state that dominates the coupling phenomenon is gradually switched from facing sides into facing edges which results in (1) a dramatic change in the spectral response of the trimer and (2) a significant improvement in the nearfield intensity that is directly related to the improvement of HRS signal. Breaking size symmetry of the cubic trimer provides a novel approach to reach the desired spectral response that permits such trimer to be used as an active substrate for HRS procedures. After optimizing both the orientation angle and size of the interacting plasmonic characters forming of the trimer, the enhancement factor of HRS process can reach a value never reported before as high as 1 × 1021.

Radiative volume plasmon and phonon-polariton resonances in TiN-based plasmonic/polar-dielectric hyperbolic optical metamaterials

Ferrell and Berreman modes are absorption resonances in thin metal films and polar-dielectric media that arise from radiative bulk plasmon-polariton and phonon-polariton excitations. Compared to surface polaritons, Ferrell and Berreman modes occur due to volume charge oscillations across the medium and provide a unique pathway for light–matter interactions. Though the resonances are studied individually, stringent polarization and material requirements have prevented their observation in one host medium. Here, we show simultaneous excitation of Ferrell and Berreman absorption resonances in refractory epitaxial TiN/Al0.72Sc0.28N plasmonic metal/polar-dielectric hyperbolic metamaterials in the visible and far-infrared spectral ranges. The nanoscale periodicity of the superlattices enables the coupling of bulk plasmons (and longitudinal optical phonons) across different TiN (and Al0.72Sc0.28N) layers and allows polarization matching with free-space light that results in Ferrell (and Berreman) mode excitations. Ferrell and Berreman absorption resonances can be used for strong light confinement in radiative cooling, thermophotovoltaics, and other dual-band applications.

Multipole polarization assisted optical bistability in a semiconductor quantum dot/metal nanoparticle hybrid molecule

We theoretically study the optical bistability assisted by multipole polarizations in a semiconductor quantum dot (SQD)/metal nanoparticle (MNP) hybrid molecule. We map out bistability phase diagrams within the parameter subspace spanned by (the pumping intensity Ipu, interparticle distance, d) under dipole and multipole approximations. It is shown that the Ipu-correlated bistable region will be broadened greatly in the strong exciton–plasmon coupling regime, and the corresponding lower (upper) bistable threshold is enlarged significantly due to multipole polarization (N = 10) in comparison to that in the dipole approximation (N = 1). However, under the same conditions, the d-correlated bistable region is shrunk at high pump intensities. Our contribution not only offers a better understanding of exciton–plasmon coupling systems but also expands the application of SQD/MNP hybrid molecules in the field of optical bistable nanodevices.

Promoting spintronic terahertz radiation via Tamm plasmon coupling

Spectral fingerprint and terahertz (THz) field-induced carrier dynamics demands the exploration of broadband and intense THz signal sources. Spintronic THz emitters (STEs), with high stability, a low cost, and an ultrabroad bandwidth, have been a hot topic in the field of THz sources. One of the main barriers to their practical application is lack of an STE with strong radiation intensity. Here, through the combination of optical physics and ultrafast photonics, the Tamm plasmon coupling (TPC) facilitating THz radiation is realized between spin THz thin films and photonic crystal structures. Simulation results show that the spectral absorptance can be increased from 36.8% to 94.3% for spin THz thin films with TPC. This coupling with narrowband resonance not only improves the optical-to-spin conversion efficiency, but also guarantees THz transmission with a negligible loss (∼4%) for the photonic crystal structure. According to the simulation, we prepared this structure successfully and experimentally realized a 264% THz radiation enhancement. Furthermore, the spin THz thin films with TPC exhibited invariant absorptivity under different polarization modes of the pump beam and weakening confinement on an obliquely incident pump laser. This approach is easy to implement and offers possibilities to overcome compatibility issues between the optical structure design and low energy consumption for ultrafast THz opto-spintronics and other similar devices.

Localized surface plasmon resonance biosensor chip surface modification and signal amplifications toward rapid and sensitive detection of COVID-19 infections

We developed a multi-pronged approach to enhance the detection sensitivity of localized surface plasmon resonance (LSPR) sensor chips to detect SARS-CoV-2. To this end, poly(amidoamine) dendrimers were immobilized onto the surface of LSPR sensor chips to serve as templates to further conjugate aptamers specific for SARS-CoV-2. The immobilized dendrimers were shown to reduce surface nonspecific adsorptions and increase capturing ligand density on the sensor chips, thereby improving detection sensitivity. To characterize the detection sensitivity of the surface-modified sensor chips, SARS-CoV-2 spike protein receptor-binding domain was detected using LSPR sensor chips with different surface modifications. The results showed that the dendrimer-aptamer modified LSPR sensor chip exhibited a limit of detection (LOD) of 21.9 pM, a sensitivity that was 9 times and 152 times more sensitive than the traditional aptamer- or antibody-based LSPR sensor chips, respectively. In addition, detection sensitivity was further improved by combining rolling circle amplification product and gold nanoparticles to further amplify the detection signals by increasing both the target mass and plasmonic coupling effects. Using pseudo SARS-CoV-2 viral particles as detection targets, we demonstrated that this combined signal intensification approach further enhanced the detection sensitivity by 10 folds with a remarkable LOD of 148 vp/mL, making it one of the most sensitive SARS-CoV-2 detection assays reported to date. These results highlight the potential of a novel LSPR-based detection platform for sensitive and rapid detection of COVID-19 infections, as well as other viral infections and point-of-care applications.

Multi-dimensional plasmonic coupling system for efficient enrichment and ultrasensitive label-free SERS detection of bilirubin based on graphene oxide-Au nanostars and Au@Ag nanoparticles

Rapid and sensitive detection of free bilirubin (BR) is essential for early diagnosis of jaundice and other hepatobiliary diseases. Inspired by sandwich immunoassay strategy, a multi-dimensional plasmonic coupling SERS platform composed of graphene oxide-Au nanostars nanocomposites (GANS NCs) and Au@Ag nanoparticles (NPs) was designed for label-free detection of BR. Specifically, GANS NCs were first prepared, and their excellent SERS activity was ascribed to synergistic enhancement effect of electromagnetic enhancement and chemical enhancement. Furthermore, SERS spectroscopy was used to monitor the adsorption process of BR. Subsequently, secondary reinforcing Au@Ag NPs were directly added, ultimately resulting in a multi-dimensional plasmonic coupling effect. The SERS enhancing mechanism of coupled system was discussed through electromagnetic field simulations. Interestingly, the high-density hotspots generated by strong plasmonic coupling in GANS-Au@Ag substrate could lead to more extraordinary SERS enhancing behavior compared to GANS NCs. Sensing efficiency of the SERS platform was examined by BR with a detection limit down to 10−11 M. Besides, GANS-Au@Ag NCs performed high uniformity and reproducibility. This work not only opens up a new avenue for construction of multi-dimensional plasmonic coupling system, but also offers a new biosensing technology for label-free diagnosis of BR-related diseases, thereby expecting to be applied in clinical diagnosis.

An anisotropic nanobox based core-shell-satellite nanoassembly of multiple SERS enhancement with heterogeneous interface for stroke marker determination

Herein, A novel gold-silver alloy nanobox (AuAgNB)@SiO2-gold nanosphere (AuNP) nanoassembly based on core–shell-satellite structure is fabricated and applied to the surface-enhanced Raman scattering (SERS) detection of S100 calcium-binding protein B protein (S100B). It contains an anisotropic hollow porous AuAgNB core with rough surface, an ultrathin silica interlayer labeled with reporter molecules, and AuNP satellites. The nanoassemblies were systematically optimized by tuning the reporter molecules concentration, silica layer thickness, AuAgNB size, and the size and number of AuNP satellite size. Remarkably, AuNP satellites are adjacent to AuAgNB@SiO2, developing AuAg-SiO2-Au heterogeneous interface. With the strong plasmon coupling between AuAgNB and AuNP satellites, chemical enhancement from heterogeneous interface, and the tip “hot spots” of AuAgNB, the SERS activity of the nanoassemblies was multiply enhanced. Additionally, the stability of nanostructure and Raman signal was significantly improved by the silica interlayer and AuNP satellites. Eventually, the nanoassemblies were applied for S100B detection. It demonstrated satisfactory sensitivity and reproducibility with a wide detection range of 10 fg/mL-10 ng/mL and a limit of detection (LOD) of 1.7 fg/mL. This work based on the AuAgNB@SiO2-AuNP nanoassemblies with multiple SERS enhancements and favorable stability demonstrates the promising application in stroke diagnosis.

Quaternization-Assisted Assembly of Polymer-Tethered Gold Nanoparticles into Superlattices with a Tunable Structure

Programmable organization of functional inorganic nanoparticles (NPs) into well-defined hierarchical superstructures has raised considerable concern due to the enhanced magnetic, electronic, and optical properties arising from the strong plasmonic coupling effect. However, the spontaneous self-assembly of inorganic NPs into uniform superlattices with the desired or tunable shape remains a formidable challenge. Herein, we report the quaternization-assisted hierarchical assembly of gold nanoparticles (AuNPs) tethered with polystyrene (PS) and quaternized poly(2-vinylpyridine) (P2VP) ligands into controllable superstructures in emulsion droplets. The quaternization interaction between bromoalkyl molecular additives (e.g., CnH2n+1Br) and P2VP ligands results in the increase of the hydrophilicity degree of quaternized P2VP ligands and triggers the interfacial instability of emulsion droplets, achieving the continuous transformation of generated superstructures from solid assemblies to hollow colloidosomes and then to the multilayer sheet-like superlattices. Furthermore, the degree of quaternization can be readily tuned by the added content of additives and the length of the alkyl chain, providing a unique and promising approach to prepare contrivable superstructures and functional materials.

Nanoplasmonic Decoration of Sacrificial Bacteria: Directing Interparticle Coupling Toward Multiplex Analysis of Antiseptic Alcohols

Engineering interparticle plasmon coupling through controlling the assembly of plasmonic NPs onto the surface of sacrificial substrates is quite promising for establishing inherently absent selectivity or sensitivity toward a particular analyte. Herein, we introduce a robust sensor array strategy based upon the assembly of gold nanoparticles (AuNPs) on the cysteamine-modified surface of two Gram-positive probiotic bacteria, i.e., Lactobacillus reuteri (LBR) and Bifidobacterium lactis (BFL), as potential sacrificial substrates, for discrimination and quantification of antiseptic alcohols (AAs) comprising methanol, ethanol, and isopropanol. In fact, the damage of the bacterial membrane upon exposure to the foregoing alcohols inhibits the assembly of AuNPs, thereby precluding color variations from red to blue. Unequal resistance of the bacterial membranes against damage by the alcohols underlies independent response patterns for each analyte. The supervised classification of visible spectra and RGB data by Linear Discriminant Analysis (LDA) revealed the remarkable potential of the designed sensor array in differentiating single-component and multicomponent samples of AAs. Moreover, the Partial Least Square Regression (PLSR) technique exhibited excellent applicability to multivariate calibration of both spectral and RGB data. The intriguing attributes of the implemented approach not only hold great potential in the authentication and quality assessment of alcohol-based products but open up a new prospect for deployment of sacrificial substrates in the design of interparticle coupling-based sensors.

Extraordinary upconversion enhancement in mono-dispersed plasmonic resonant nanocavity coupling with lanthanide doped upconversion nanoparticles

In this work, we reported a monodispersed MDM (metal–dielectric-metal) type upconversion composite material with ultrahigh emission enhancement for the first time. Different from the planar configuration of traditional MDM systems, the proposed materials here consisting of silver nanoparticles as the metallic core, upconversion nanoparticles(UCNPs) as the intermediate dielectric layer, and silver layer as the metallic shell. The structural characteristics were investigated to explore the spectral band match between the plasmonics and UCNPs. The sandwich structure can create high density hot carriers at the nearfield region around the UCNPs, leading to the remarkable excitation enhancement. According to the proper structure design, the upconversion intensity can be enhanced by over five orders of magnitude. The outer metallic layer thickness, the diameter of attached UCNPs and the ambient refractive index were found responsible for the intensity enhancement. Such upconversion materials combined the merit of monodispersity and the high emission efficiency, which can improve their performance in bioimaging and photovoltaic device.

Black Gold-Based “Antenna–Reactor” To Activate Non-Plasmonic Nickel: Photocatalytic Hydrodechlorination and Hydrogenation Reactions

Activation of organic chlorides is a challenging reaction due to their chemical inertness, while hydrogenation of alkene and alkynes faces poor selectivity. In this work, we have demonstrated the use of nickel-loaded black gold (black Au–Ni) that absorbs broadband light from visible to near-infrared of the sunlight due to plasmonic coupling between Au NPs, for photocatalytic hydrodechlorination and propene and acetylene hydrogenation reactions. Hot carriers, the polarizing electric field, and the photothermal effect generated in these catalysts enabled photocatalytic bond activation of these two challenging reactions using visible light at lower temperatures and atmospheric pressure. The black Au–Ni catalyst showed a multifold increase in its activity as compared to black Au. The plasmon-assisted reaction mechanism of hydrodechlorination was supported by intensity-dependent catalysis, kinetic isotope effect (KIE), competitive C–Cl bond activation with one-electron ferricyanide reduction, finite-difference time-domain (FDTD) simulations, and quantum chemical studies. Cluster model-based density functional theory studies show that the reactions have substantial barriers, which were bypassed via an excited state accessed through plasmonic excitations. FDTD studies indicate substantial enhancement of the electric field at the hotspots, iron reduction competed for hot carriers when run in conjunction with C–Cl bond activation, KIE was marginally higher in light as compared to the dark, and the catalyst showed power-dependent activity. These observations indicated the hot carrier involvement in the hydrodechlorination reactions in addition to the photothermal effect.

A Novel SPR Immunosensor Based on Dual Signal Amplification Strategy for Detection of SARS-CoV-2 Nucleocapsid Protein

Since the global outbreak of coronavirus disease 2019 (COVID-19), it has spread rapidly around the world. The nucleocapsid (N) protein is one of the most abundant SARS-CoV-2 proteins. Therefore, a sensitive and effective detection method for SARS-CoV-2 N protein is the focus of research. Here, we developed a surface plasmon resonance (SPR) biosensor based on the dual signal-amplification strategy of Au@Ag@Au nanoparticles (NPs) and graphene oxide (GO). Additionally, a sandwich immunoassay was utilized to sensitively and efficiently detect SARS-CoV-2 N protein. On the one hand, Au@Ag@Au NPs have a high refractive index and the capability to electromagnetically couple with the plasma waves propagating on the surface of gold film, which are harnessed for amplifying the SPR response signal. On the other hand, GO, which has the large specific surface area and the abundant oxygen-containing functional groups, could provide unique light absorption bands that can enhance plasmonic coupling to further amplify the SPR response signal. The proposed biosensor could efficiently detect SARS-CoV-2 N protein for 15 min and the detection limit for SARS-CoV-2 N protein was 0.083 ng/mL, with a linear range of 0.1 ng/mL~1000 ng/mL. This novel method can meet the analytical requirements of artificial saliva simulated samples, and the developed biosensor had a good anti-interference capability.

Strong coupling of localized surface plasmons and intermolecular vibration mode at terahertz frequencies

Organic molecular vibrations, typically occurring in the terahertz (THz) regime, can resonate with a metastructure. A hallmark Rabi splitting occurs when the coupling strength is sufficiently strong. In this work, we observe the strong coupling of localized surface plasmons (LSPs) and intermolecular vibration mode at THz on a metasurface spin-coated with organic molecule α-lactose monohydrate. Excited by transverse-electric THz waves, dispersive localized surface plasmons interact with nondispersive intermolecular vibrations and form two vibro-polariton modes. The angle-resolved transmission spectra of the coupled system are detected by using a terahertz time-domain spectrometer, demonstrating an anti-crossing effect with a clear Rabi splitting. By retrieving the coupling strength and Hopfield coefficients of polariton bands from the measured data, we further verify that these two bands originate from the strong coupling between LSPs and molecular vibration mode. Moreover, we show that it is possible to implement molecular concentration sensing based on this strong coupling effect. This study demonstrates a unique approach to investigate vibro-polaritons at the terahertz regime and provides a testbed for future applications of strong coupling effects in chemical detection and biosensing.

Enhancement of Fluorescence Mediated by Silver Nanoparticles: Implications for Cell Imaging.

In this study, we report the surface enhanced fluorescence (SEF) of a biologically important organic dye, fluorescein (FL), by silver nanoparticles (Ag NPs) in an aqueous medium and its implications for human cell imaging. The as-synthesized Ag NPs were characterized by dynamic light scattering (DLS), zeta potential, transmission electron microscopy (TEM), and UV-vis absorption spectroscopic studies. The interaction and aggregation of FL dye with Ag NPs and a cationic surfactant, namely, cetyltrimethylammonium bromide (CTAB), were explored by UV-vis absorption and steady-state and time-resolved fluorescence spectroscopic methods. The distance-dependent fluorescence enhancement of FL due to Ag NPs in the solution was also theoretically correlated by three-dimensional finite-difference time-domain (3D-FDTD) simulation. The plasmonic coupling between neighboring NPs facilitated the augmentation of the local electric field, thereby producing various "hotspots" that influence the overall fluorescence of the emitter. J-type aggregates of FL in the presence of the CTAB micelles and Ag NP mixed solution were confirmed by electronic spectroscopy. The density functional theoretical (DFT) study revealed the electronic energy levels associated with different forms of FL dye in the aqueous solution. Most interestingly, the Ag NP/FL mixed system used in fluorescence imaging of human lung fibroblast cells (WI 38 cell line) showed a significantly stronger green fluorescence signal compared to that of FL after an incubation period of only 3 h. This study confirms that the Ag NP mediated SEF phenomenon of the FL dye is also manifested in the intracellular medium of human cells giving a brighter and more intense fluorescence image. The cell viability test after exposure to the Ag NP/FL mixed system was confirmed by the MTT assay method. The proposed study may have an implication as an alternate approach for human cell imaging with higher resolution and more contrast.

FEM investigation of Cu@SiO2 core-shell nanoparticle for a sensitive and low-cost SERS and SEF substrate

We theoretically investigate the plasmon coupling properties of Cu@SiO2 core-shell system that supports the measurement of surface enhanced Raman spectroscopy (SERS) and surface enhanced fluorescence (SEF) technology. The roles of Cu core and SiO2 shell in tuning LSPR have been quantitatively discussed by calculating the localized electric field enhancement factor (EF), fluorescent quantum yield, SERS and SEF EF in the nanogap based on finite element simulations. In this work, we demonstrate that the SERS and SEF effect strongly depend on the core size, shell thickness and dimer distance. The larger size of Cu core, ultrathin thickness of SiO2 shell and shorter dimer distance could be considered as the ideal substrate. Meanwhile, the strong localized excitation enhancement is a vital contribution to fluorescence spectral. By comparison, it is found that the enhancement effect of the Cu, Au and Ag cores are very close in order of magnitude in the red and near infrared regions, and thus the low-cost Cu core may act as an active substrate in these regions. At the excitation wavelength of 630 nm, the optimized core size of 60 nm and shell thickness of 1 nm provide the maximum Raman and fluorescence EF as high as 9 and 4 orders of magnitude. Our theoretical results not only help understanding the underlying enhancement mechanism for the core-shell SERS and SEF effect, but also contribute to develop the low-cost and sensitive detection technology.

LoC-SERS Platform Integrated with the Signal Amplification Strategy toward Parkinson's Disease Diagnosis.

Multiplexed detection of Parkinson's disease (PD) biomarkers is of great significance for early diagnosis and personalized treatment. In this study, we fabricated a robust surface-enhanced Raman scattering-enabled lab-on-a-chip (LoC-SERS) platform for simultaneous quantification of α-synuclein, phosphorylated tau protein 181, osteopontin, and osteocalcin. Herein, the antibody-DNA conjugate was designed to introduce the catalytic hairpin self-assembly (CHA) amplification into the protein detection. Au nano-stars (AuNSs) modified with Raman reporter molecules and hairpin-structure DNA 1 were applied as the SERS nanotags. Au-coated silicon nanocone array (Au/SiNCA) fabricated based on the maskless plasma etching-prepared high-density Si nanocone array (SiNCA) and surface ion sputtering was used as the capture substrate after the modification of hairpin-structure DNA 2. Benefitting from the antibody-DNA conjugate-induced CHA amplification, numerous AuNSs can be connected to the Au/SiNCA surface, which significantly amplify the plasmonic coupling effect for ultrasensitive SERS detection, and the limit of detection was less than the pg/mL level. The application of highly uniform Au/SiNCA and antibody-DNA conjugate endows the LoC-SERS platform excellent analytical performance, including superior reproducibility, satisfactory universality, and high sensitivity. In addition, a 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)-induced PD mice model was established, and satisfactory results were obtained in real sample analysis with the LoC-SERS platform, which may be enlightening for exploiting protein biomarkers in PD monitoring.

Surface plasmon coupling effects on the photon color conversion behaviors of colloidal quantum dots in a GaN nanoscale hole with a nearby quantum-well structure.

To improve color conversion performance for color display application, we study the near-field-induced nanoscale-cavity effects on the emission efficiency and Förster resonance energy transfer (FRET) under the condition of surface plasmon (SP) coupling by inserting colloidal quantum dots (QDs) and synthesized Ag nanoparticles (NPs) into surface nano-holes fabricated on a GaN template and an InGaN/GaN quantum-well (QW) template. In the QW template, the inserted Ag NPs are close to either QWs or QDs for producing three-body SP coupling to enhance color conversion. Time-resolved and continuous-wave photoluminescence (PL) behaviors of the QW- and QD-emitting lights are investigated. The comparison between the nano-hole samples and the reference samples of surface QD/Ag NP shows that the nanoscale-cavity effect of the nano-hole leads to the enhancements of QD emission, FRET between QDs, and FRET from QW into QD. The SP coupling induced by the inserted Ag NPs can enhance the QD emission and FRET from QW into QD. Its result is further enhanced through the nanoscale-cavity effect. The relative continuous-wave PL intensities among different color components also show the similar behaviors. By introducing SP coupling to a color conversion device with the FRET process in a nanoscale cavity structure, we can significantly improve the color conversion efficiency. Simulation results confirm the basic observations in experiment.

Drug-Free Antimicrobial Nanomotor for Precise Treatment of Multidrug-Resistant Bacterial Infections.

Manufacturing heteronanostructures with specific physicochemical characteristics and tightly controllable designs is very appealing. Herein, we reported NIR-II light-driven dual plasmonic (AuNR-SiO2-Cu7S4) antimicrobial nanomotors with an intended Janus configuration through the overgrowth of copper-rich Cu7S4 nanocrystals at only one high-curvature site of Au nanorods (Au NRs). These nanomotors were applied for photoacoustic imaging (PAI)-guided synergistic photothermal and photocatalytic treatment of bacterial infections. Both the photothermal performance and photocatalytic activity of the nanomotors are dramatically improved owing to the strong plasmon coupling between Au NRs and the Cu7S4 component and enhanced energy transfer. The motion behavior of nanomotors promotes transdermal penetration and enhances the matter-bacteria interaction. More importantly, the directional navigation and synergistic antimicrobial activity of the nanomotors could be synchronously driven by NIR-II light. The marriage of active motion and enhanced antibacterial activity resulted in the expected good antibacterial effects in an abscess infection mouse model.

Understanding Metal-Semiconductor Plasmonic Resonance Coupling through Surface-Enhanced Raman Scattering.

Although there has been intense research on plasmon-induced charge transfer within metal/semiconductor heterostructures, previous studies have all focused on the surface plasmonic resonance (SPR) of only noble metals. Herein and for the first time, we observe and take into account the plasmonic coupling between SPR of both noble-metal and semiconductor nanostructures. A W18O49/Ag heterostructure composed of metallic Ag nanoparticles (Ag NPs) and semiconducting W18O49 nanowires (W18O49 NWs) is designed and fabricated, which exhibits a broad and strong SPR absorption in the visible wavelength range. This SPR band is attributed to the SPR coupling between the SPR of both Ag NPs and W18O49 NWs. Surface-enhanced Raman scattering (SERS) is then used to reveal the interactions between the metal SPR, semiconductor SPR, and the heterostructure's charge transfer (CT) process, demonstrating that such coupled SPR enhanced the heterostructure's internal CT and SERS signals. Finally, we proposed a new coupled-plasmon-induced charge transfer mechanism to interpret the improved CT efficiency between the SERS substrate and molecules. Our work provides insight for further studies on plasmonic effects and interfacial charge transfer in metal/semiconductor heterostructures.

One-Step, On-Site Chemical Printing of a 3D Plasmon-Coupled Silver Nanocoral Substrate toward SERS-Based POCT

Surface-enhanced Raman scattering (SERS) with the advantages of high sensitivity, nondestructive analysis, and a unique fingerprint effect shows great potential in point-of-care testing (POCT). However, SERS faces challenges in rapidly constructing a substrate with high repeatability, homogeneity, and sensitivity, which are the key factors that restrict its practical applications. In this study, we propose a one-step chemical printing strategy for synthesizing a three-dimensional (3D) plasmon-coupled silver nanocoral (AgNC) substrate (only need about 5 min) without any pretreatments and complex instruments. The galvanic replacement between AgNO3 and Cu sheets will provide both Ag0 for the formation of silver nanostructures and Cu2+ for the polymerization of fish sperm DNA (FSDNA). The protection of AgNCs is facilitated by the crosslinked FSDNA, which can improve the stability of the substrate and promote the control of its coral-like morphology. The obtained substrate displays excellent capacity of signal enhancement due to the 3D plasmon coupling both between nanocoral tentacles and between nanocorals and Cu sheets as well. Therefore, the AgNC substrates display high activity (enhancement factor = 1.96 × 108) and uniformity (RSD < 6%). Food colorants have been widely used in various foods to improve their color, but the inevitable toxicity of colorants seriously threatens food safety. Therefore, the proposed AgNC substrates were used to directly quantify three kinds of weak-affinity food colorant molecules including Brilliant Blue, Allura Red, and Sunset Yellow assisted by the capture by cysteamine hydrochloride (CA), showing the detection limits (S/N = 3) of 0.053, 0.087, and 0.089 ppm, respectively. The SERS method has been further applied in the detection of the three kinds of food colorants in both complex food samples and urine with recoveries of 91-119%. The satisfactory detection results suggest that the facile preparation strategy of AgNC substrates will be widely used in SERS-based POCT to promote the development of food safety and on-site healthcare.