Surface Plasmon Coupling Effect Research Articles

Cu NCs@MXene-luminescent Faraday cage and Cu Nanocone/Bi NPs array-based saliva exosome assay for asthma evaluation

In this work, a novel nano-sensing system with luminescent Faraday cage mode has been developed to detect miRNA-221-5p in clinic saliva exosomes to evaluate asthma. Firstly, copper nanoclusters (Cu NCs) were synthesized in situ on the defects in Ti3CN nanosheets based on the nanoconfinement effect. Due to the Electronic metal-support interactions (EMSI) between MXene and the anchored Cu NCs, Cu NCs@MXene displayed the strong luminescence performance, high electrochemical activity and good stability properties. Furthermore, MXene nanosheets with good conductivity and flexibility was used to expand the outer Helmholtz plane and improve the sensing ability. Meanwhile, Cu nanocone/Bi nanoparticles (NPs) arrays were constructed by step-by-step electrodeposition. Due to the surface plasmon coupling effect, the Cu nanocone/Bi NPs arrays can convert the electrochemiluminescence (ECL) signal of Cu NCs@MXene-Faraday cage into the directional emission with 13.4-fold enhancement. Finally, a thin phospholipid film and capture DNA were modified on the surface of the Cu nanocone/Bi NPs array as the sensing interface to detect miRNA-221-5p in saliva exosomes. The designed nano-sensing system had a detection range was 1.0 × 10-16 ∼ 1.0 × 10-8 mol/L with the detection limit of 34 aM. Finally, the biosensor has been successfully employed to evaluate asthma in the clinical analysis.

Magnetoplasmonic Metasurface-Modulated Electrochemiluminescence Strategy for Extracellular Vesicle Detection.

Due to the ideal optical manipulation ability, the metasurface has broad prospects in the development of novel optical research. In particular, an active metasurface can control optical response through external stimulus, which has attracted great research interest. However, achieving effective modulation of the optical response is a significant challenge. In this work, we have developed a novel electrochemiluminescence (ECL) signal modulation strategy by an active magnetoplasmonic metasurface under an external magnetic field. The magnetoplasmonic metasurface was assembled based on yolk-shell Fe3O4@Au nanoparticles (Fe3O4@Au YS-NPs). On the one hand, the yolk-shell structure of Fe3O4@Au YS-NPs possessed the surface plasmon coupling effect and cavity-based Purcell effect, which provided high-intensity electromagnetic hot spots in the magnetoplasmonic metasurface. On the other hand, due to the strong magnetic response of the Fe3O4 core, the local magnetic field was induced by the external magnetic field, which further generated Lorentz force acting on the free electrons of Au nanoshells with strong optical anisotropy. The plasmon frequency of the metasurface can be effectively modulated by the Lorentz force effect. As a result, the ECL signal of nitrogen dots (N dots) was dynamically modulated and significantly enhanced at a specific polarization angle by the magnetoplasmonic metasurface under the variable external magnetic field. Based on the luminescence modulation ability and structure feature, the magnetoplasmonic metasurface was further established successfully as a sensing interface for gastric cancer (GC) extracellular vesicle (EV) detection. This study illustrated that the electromagnetic response of the active metasurface can effectively improve the optical modulation ability and luminescence sensing performance.

One-pot synthesized Au@Pt nanostars-based lateral flow immunoassay for colorimetric and photothermal dual-mode detection of SARS-CoV-2 nucleocapsid antibody

In addition to confirming virus infection, quantitative identification of the antibodies to severe acute respiratory syndrome coronavirus 2(SARS-CoV-2) also evaluates persons immunity to guide personal protection. However, portable assays for fast and accurate quantification of SARS-CoV-2 antibodies remain challenging. In this work, we synthesized Au@Pt star-like nanoparticles (NPs) quickly and easily by a one-pot wet-chemical approach, allowing the stellate Au core to be partially decorated by Pt nanoshells. The nanoparticles were used as probe in a lateral flow immunoassay (LFIA) that operated in both colorimetric and photothermal dual modes, which could detect the antibodies to the SARS-CoV-2 nucleocapsid (N) protein with high sensitivity. Due to the sharp tips on the external region of nanostars and surface plasmon coupling effect between the Au core and Pt shell, the NIR absorption capacity and photothermal performance of these NPs were exceptional. Under optimal conditions, the colorimetric mode's detection limit for SARS-CoV-2 N protein antibody was 1 ng mL−1, which is significantly lower by 2-order of magnitude compared to commercially available colloidal gold strips. And the detection limit for the photothermal mode was as low as 24.91 pg mL−1, which was approximately 40-fold more sensitive than colorimetric detection. Moreover, the method demonstrated favorable specificity, reproducibility and stability. Finally, the approach was employed for the successful identification of actual serum samples. Therefore, the dual-mode LFIA can be applied for screening and tracking the early immunological reaction to SARS-CoV-2, and it has great promise for clinical application.

Asymmetric Heterodimer-Regulated Surface Plasmon Coupling ECL Polarization Strategy for MiRNA-182 Detection.

In this work, a novel plasmonic heterodimer with controllable hot spot was designed and applied to regulate surface plasmon coupling electrochemiluminescence (SPC-ECL) polarization sensing system. The heterodimer nanostructure consisted of individual Au-Ag core-shell nanocubes (Au@Ag NC) and Au nanospheres (Au NS), which were precisely assembled by thiol-DNA and biotin-streptavidin. The asymmetric nanostructure can significantly modulate the ECL intensity and emission polarization angle based on the synergy of the surface plasmon coupling (SPC) effect and the lightning rod effect with extraordinary field enhancement in the hot spot region. As a result, the isotropic ECL signal of zinc-doped nitrogen dots (Zn-N dots) was regulated in the directional emission. Furthermore, the SPC-ECL biosensor was successfully applied to detect miRNA-182 in triple-negative breast cancer (TNBC) tissues. The research on the established relationship between ECL polarization analysis and plasmonic heterodimers can provide a new pathway for the development of ECL sensing platforms.

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.

Surface plasmon coupling effects on the behaviors of radiative and non-radiative recombination in an InGaN/GaN quantum well

Although surface plasmon (SP) coupling has been widely used for enhancing the emission efficiency of an InGaN/GaN quantum well (QW) structure, the interplay of the carrier transport behavior in the QW with SP coupling, which is a crucial mechanism controlling the SP-coupling induced QW emission enhancement, is still an issue not well explored yet. To understand the effects of SP coupling on the radiative and non-radiative recombination behaviors of carriers in a QW structure, the temperature-dependent time-resolved photoluminescence spectroscopies of two QW samples of different indium contents with surface Ag nanoparticles are studied. A two-single-exponential model is used for calibrating their radiative and non-radiative decay times. The SP coupling process, which transfers carrier energy from a QW into the SP resonance mode for effective radiation and increases the effective radiative recombination rate, produces energy-dependent carrier depletion and, hence, disturbs the quasi-equilibrium condition of carrier distribution. In this situation, a strong carrier transport process occurs targeting a new quasi-equilibrium condition that enhances non-radiative recombination and, hence, reduces the benefit of using the SP coupling technique. To alleviate this problem of SP-coupling induced energy loss, a weak energy-dependent or broad-spectrum SP coupling process is recommended.

Programmable Assembly of Colloidal Nanoparticles Controlled by Electrostatic Potential Well

Compared with the individual colloidal nanoparticles, programmable nanoassemblies with well‐defined configurations exhibit more prominent coupling effects and collective behaviors. The full realization of the unique superiority of these nano assemblies requires the development of feasible approaches to assemble colloidal nanoparticles into an organized nanostructure on substrates, which remains a major challenge in nanotechnology at present. Herein, a facile strategy is developed to programmatically design diversified nanostructures through the rational capture of nanoparticles with flexibly adjustable particle types, including their sizes, shapes, or components. Importantly, such a strategy takes advantage of a bowl‐shaped electrostatic potential well that forms based on the combination of a positively charged nanoparticle and a negatively charged substrate, where theory and simulation are employed to reveal the notable role of the substrate potential. As a demonstration, a series of nanostructures with customized geometries and locations have been successfully fabricated, especially the asymmetric dimer structures, which bring about distinct localized surface plasmon resonance hybridization and coupling effects. Therefore, the joint computational–experimental showcase paves the way toward the preparation of ideal nanostructures, providing valuable insight into the development of optical encryption, smart sensing, sensitive bio‐detection, and so on.

Covalent and noncovalent hybrids of di-amino porphyrin functionalized graphene oxide and their interaction with gold nanoparticles

Porphyrin functionalization of graphene oxide (GO) influenced the plasmonic effect of gold nanoparticles (AuNP). The former was achieved by modification of GO with 5,10-bis(4-aminophenyl)-15,20-diphenylporphyrin, P(NH2)2,adj, by noncovalent interactions as well as by covalent association, following standard chemistry. The success of the chemical functionalization of GO with P(NH2)2,adj, was confirmed by FTIR. Steady-state and time-resolved fluorescence showed a strong fluorescence quenching of porphyrin in the presence of GO, indicative of a photoinduced electron transfer process from porphyrin units to GO, which acts as an electron acceptor. The surface plasmon coupling effect promoted by the AuNP@GO hybrids, proved to be effective only in the case of the noncovalent hybrid, detected through the decrease of the porphyrin fluorescence lifetime and increase in the emission intensity in solution, in good agreement with FLIM results on deposited samples.

A polarization-resolved ECL strategy based on the surface plasmon coupling effect of orientational Au nanobipyramids patterned structures

Here, we developed a polarization-resolved surface plasmon coupling electrochemiluminescence (ECL) strategy based on orientational Au nanobipyramids (Au NBPs) patterned structures. As the surface plasmonic materials, the Au NBPs with large localized electromagnetic field enhancement were used to construct the different patterned structures through the droplet evaporation induced assembly. The distinct morphology of the horizontal and vertical Au NBPs patterned structures provided the different plasmonic properties reflecting on resonance peak positions and polarized absorbance. As a result, the variations of the polarized ECL emission of SnS2 QDs have been regulated by the Au NBPs patterned structures via the surface plasmon coupling progress. Because of the superior polarization-resolved ECL performances, the sensing system was used to analyze the miRNA-21 and miRNA-205 expression level in tumor tissues of triple negative breast cancer patients. The satisfactory results indicated this polarization-resolved sensing strategy possessed great potential for clinical analysis.

Gold Nanorod Vertical Array-Based Electrochemiluminescence Polarization Assay for Triple-Negative Breast Cancer Detection.

In this work, a polarization-resolved electrochemiluminescence (ECL) sensor for microRNA-155 (miRNA-155) detection has been constructed based on the surface plasmon coupling effect. In the sensing system, nitrogen dots (N dots) were employed as ECL emitters. As a surface-enhanced structure, a gold nanorod vertical array was constructed on the electrode surface by the volatilization-induced self-assembly. The coupling of the adjacent gold nanorods in the array can generate significant local electromagnetic fields. Due to the anisotropy of gold nanorods and the hot spot effect of the vertical array, the ECL signal of N dots was greatly improved at a specific polarization angle. In addition, the catalytic hairpin self-assembly strategy was used to amplify the nucleic acid analyte signal. As a result, the polarization-resolved ECL sensor can detect miRNA-155 sensitively, which is related to triple-negative breast cancer.

Surface plasmon coupling effects on the förster resonance energy transfer from quantum dot into rhodamine 6G

Rhodamine 6G (R6G) molecules linked CdZnSeS/ZnS green-emitting quantum dots (QDs) are self-assembled onto Ag nanoparticles (NPs) for studying the surface plasmon (SP) coupling effect on the Förster resonance energy transfer (FRET) process from QD into R6G. SP coupling can enhance the emission efficiency of QD such that FRET has to compete with QD emission for transferring energy into R6G. It is found that FRET efficiency is reduced under the SP coupling condition. Although R6G emission efficiency can also be enhanced through SP coupling when it is directly linked onto Ag NP, the enhancement decreases when R6G is linked onto QD and then the QD-R6G complex is self-assembled onto Ag NP. In particular, R6G emission efficiency can be reduced through SP coupling when the number of R6G molecules linked onto a QD is high. A rate-equation model is built for resembling the measured photoluminescence decay profiles and providing us with more detailed explanations for the observed FRET and SP coupling behaviors.

Förster resonance energy transfer in surface plasmon coupled color conversion processes of colloidal quantum dots.

Förster resonance energy transfer (FRET) from a green-emitting quantum dot (GQD) into a red-emitting quantum dot (RQD) is an important mechanism in a multiple-color conversion process, particularly under the surface plasmon (SP) coupling condition for enhancing color conversion efficiency. Here, the dependencies of FRET efficiency on the relative concentrations of GQD and RQD in their mixtures and their surface molecule coatings for controlling surface charges are studied. Also, the SP coupling effects induced by two kinds of Ag nanoparticles on the emission behaviors of GQD and RQD are demonstrated, particularly when FRET is involved in the coupling process. FRET efficiency is reduced under the SP coupling condition. SP coupling can enhance the color conversion efficiency of either GQD or RQD. The combination of SP coupling and FRET can be used for controlling the relative converted light intensities in a multiple-color conversion process.

Combined effects of surface plasmon coupling and Förster resonance energy transfer on the light color conversion behaviors of colloidal quantum dots on an InGaN/GaN quantum-well nanodisk structure

By forming nanodisk (ND) structures on a blue-emitting InGaN/GaN quantum-well (QW) template, the QWs become close to the red-emitting quantum dots (QDs) and Ag nanoparticles (NPs) attached onto the sidewalls of the NDs such that Förster resonance energy transfer (FRET) and surface plasmon (SP) coupling can occur to enhance the efficiency of blue-to-red color conversion. With a larger ND height, more QWs are exposed to open air on the sidewall for more QD/Ag NP attachment through QD self-assembly and Ag NP drop casting such that the FRET and SP coupling effects, and hence the color conversion efficiency can be enhanced. A stronger FRET process leads to a longer QD photoluminescence (PL) decay time and a shorter QW PL decay time. It is shown that SP coupling can enhance the FRET efficiency.

Influence of nonlocal dielectric response on the Au tip-enhanced fluorescence effect

Tip-enhanced fluorescence (TEF) with ultra-high detection sensitivity and spatial resolution has been a powerful characterization technique in the study of surface science and life science. Herein, a systematically theoretical investigation in the visible range had been performed to study TEF properties of a single molecule located inside a nanogap formed by Au tip and substrate. In the strong localized surface plasmon coupling effect, the contribution of nonlocal dielectric response to the fluorescence quantum yield as well as radiative and energy dissipated decay rates were calculated. It is found that the nonlocal dielectric effects become comparable to the radiative and energy dissipated decay rates with the increasing of the tip-molecule distance, as a result, the nonlocal dielectric effect significantly suppresses the fluorescence process. The huge excitation enhancement at the shorter tip-molecule distance can efficiently compensate the low quantum yield, leading to the great fluorescence enhancement. The results show that the maximum enhancement obtained from the calculations can reach as high as four orders of magnitude by optimizing the tip-molecule distance. These results are not only helpful to our understanding of the TEF mechanism but also valuable for its further applications.

Tunable plasmon-assisted electrochemiluminescence strategy for determination of the rapidly accelerated fibrosarcoma B-type (BRAF) gene using concave gold nanocubes.

Atunable plasmon-assisted electrochemiluminescence (ECL) strategy is reportedusing concave Au nanocubes (Au CBs) for rapidly accelerated fibrosarcoma B-type (BRAF) detection. Concave Au CBs exhibit a strong surface plasmon coupling (SPC) effect between its sharp apexes and edges. The high spectral overlap with graphite phase carbon nitride quantum dots (g-C3N4 QDs) is achieved by tuning surface plasmon absorption peak of the concave Au CBs. It maximizes the SPC effect and enhances the ECL signal of g-C3N4 QDs 3-fold. The SPC effect of Au CBs is twice as high as with Au NPs. We also employed a toehold-mediated strand displacement (TMSD) strategy for sensitive target recycling amplification. Under optimal conditions, this sensor can determine BRAF gene from 1pM to 1nM with a detection limit of 3.06 × 10-5nM (S/N = 3) and RSD 3.67%. With the aid of the TMSD strategy and tunable plasmon-assisted ECL sensing mode, this sensor also exhibits goodanalytical performance in human serum with satisfactory recovery of 90.2~109%. The proposed strategyprovides a promising method to effectively enhance spectral overlap and detect BRAF gene.

Magnetic-plasmonic yolk-shell nanostructure-based plasmon-enhanced electrochemiluminescence sensor

In this work, plasmon-enhanced electrochemiluminescence (ECL) nanosensor based on magnetic-plasmonic Fe3O4 yolk/Au shell (M@Au) is designed for Kirsten rat sarcoma (K-RAS) gene detection. K-RAS is a mouse sarcoma virus oncogene, which mutation occurs in the initial phase of malignant tumor transformation. Thus, the detection of KAS is meaningful for the diagnosis of early cancer. Graphite phase carbon nitride quantum dots (g-C3N4 QDs) have low toxicity, and stable chemical properties. However, the low ECL intensity of g-C3N4 QDs limits its sensing application. Herein, a sandwich-typed sensor with a combination of M@Au and g-C3N4 QDs is constructed. In yolk-shell M@Au, the internal Fe3O4 nanoparticle (NP) has good magnetic property. The outer Au shell has better surface plasmon coupling (SPC) effect than conventional Au NPs. Furthermore, the middle cavity in the yolk-shell nanostructure solves the problem of electron transfer between Fe3O4 NP and Au shell. Therefore, the yolk-shell M@Au shows strong surface SPC effect, which amplifies the ECL signal of g-C3N4 QDs 2.8-fold. Based on the plasmon-enhanced ECL mode, this sensor performs well with a wide range (1 fM−1 nM) for nucleic acid detection. It also shows the high stability and selectivity of the sensing system in human serum test.

Emission behaviors of colloidal quantum dots linked onto synthesized metal nanoparticles

With two different residual surfactants, four different metal nanoparticles (NPs), including two Au NPs and two Ag NPs are synthesized for linking with red-emitting CdZnSeS/ZnS colloidal quantum dots (QDs) to enhance QD emission efficiency. Those metal NPs are first connected with amino polyethylene glycol thiol of different molecular weights to avoid aggregation and make them positively charged. They can attract negatively charged QDs for inducing surface plasmon (SP) coupling such that either QD absorption or emission and hence overall color conversion efficiency can be enhanced. The enhancement of QD emission efficiency is evaluated through the comparison of time-resolved photoluminescence behaviors under different QD linkage conditions. Such results are confirmed by the measurement of the emission quantum efficiency of QD. It is found that by linking QDs onto Ag NPs, the QD emission efficiency is more enhanced, when compared with Au NPs. Also, depending on the synthesis process, the residual surfactant of citrate leads to a relatively large increment in QD emission efficiency, when compared to the surfactant of cetrimonium chloride. A more enhanced QD emission efficiency is caused by a higher QD linkage capability and a stronger SP coupling effect.

Controllable "Clicked-to-Assembled" Plasmonic Core-Satellite Nanostructures and Its Surface-Enhanced Fluorescence in Living Cells.

The assembly of noble-metal core–satellite (CS) nanostructures is an appealing means to control their plasmonic properties for their applications such as surface-enhanced fluorescence or Raman scattering. However, till now there is a lack of some rapid or convenient methods to construct stable CS nanostructures. Here, we proposed a “clicked-to-assembly” strategy based on the fast and specific “click chemistry” reaction between trans-cyclooctene (TCO) and 1,2,4,5-tetrazine (Tz). The CS nanostructures were constructed within 8 min by simple mixing of TCO- or Tz-modified nanoparticles (TCO-NPs or Tz-NPs) without any catalysts or heating required. Transmission electron microscopy experiments show that the constructed CS nanostructures are uniform, and particularly the number of “satellite” nanoparticles in the core surface is controllable by simply adjusting the feeding ratio of TCO-NPs or Tz-NPs in the reaction. The strong surface plasmon coupling effect (SPCE) was observed in these CS nanostructures, which was dependent on the coverage degree, size and composition of the satellite, and core NPs. The nanostructures with tuned surface plasmon resonance (SPR) effect were tried for the surface-enhanced fluorescence in living cells. Such well-defined CS nanostructures could potentially serve as efficient SPR-enhanced fluorescent probes as diagnostics or biomedical imaging agents in nanomedicine.

Using lactosylated cysteine functionalized gold nanoparticles as colorimetric sensing probes for rapid detection of thericin B chain.

A new colorimetric method that can be used to rapidly detect toxic ricin is demonstrated. Lactosylated cysteine-functionalized gold nanoparticles (Au@LACY NPs) were prepared by a one-pot reaction and employed as optical probes for determination of ricin B chain. It is found that the Au@LACY NPs undergoaggregation in the presence of ricin B chain. This leads to surface plasmon coupling effects of the particles and a color change from red to blue, with absorption maxima at 519 and 670nm, respectively. The feasibility of using the current approach for quantitative analysis of ricin B chain is also demonstrated. The calibration plot is generated by plotting the ratio of the absorbance at the wavelength of 634 to 518nm versus the concentration of thericin B chain. The spectrophotometric method has a ~29 pM (~ 0.91ng·mL-1) detection limit, and the sample with the concentration of ~ 400 pM (~ 13ng·mL-1) can be detected visually. Graphical abstractSchematic representation of using lactosylated cysteine capped gold nanoparticles (Au@LACY NPs) as colorimetric probes for the ricin B chainthrough surface plasmon coupling effects. Sample solution turns from red to blue in the presence of ricin Bchain.

Wavelength-Dependent Surface Plasmon Coupling Electrochemiluminescence Biosensor Based on Sulfur-Doped Carbon Nitride Quantum Dots for K-RAS Gene Detection.

Although graphite phase carbon nitride quantum dots (GCN QDs) showed some advantages in the electrochemiluminescence (ECL) analytical research, the low ECL efficiency limited the potential sensing application. Herein, we synthesized sulfur-doped graphite phase carbon nitride quantum dots (S-GCN QDs) to fabricate a sandwich sensor based on amplified surface plasmon coupling ECL (SPC-ECL) mode. Sulfur doping can change the surface states of QDs effectively and produced new element vacancy. As a result, the ECL efficiency of S-GCN QDs was 2.5× over GCN QDs. Furthermore, compared with the big gap between the ECL peak of GCN QDs (620 nm) and the absorption peak of Au NPs, the doped sulfur elements in S-GCN QDs generated new ECL emission peaks at 555 nm, which was closed to the absorption peak of Au NPs at 530 nm. Due to the wavelength-dependent surface plasmon coupling effect, the ECL peak of S-GCN QDs at 555 nm had greater amplitude of enhancement in the sensing system. The proposed biosensor can quantify the K-RAS gene from 50 fM to 1 nM with a limit of detection (LOD) of 16 fM. We were the first to provide insight into the role of wavelength-dependent surface plasmon coupling in enhancing the sensitivity of ECL biosensor.