Plasmonic Metal Nanoparticles Research Articles

Highly Monodisperse Stable Gold Nanorod Powder for Optical Sensor.

Gold nanorods (GNRs) as plasmonic metal nanoparticles are valuable for optical applications due to their tunable plasmonic properties. However, conventional colloidal GNRs face significant optical instability during storage, which limits their practical use. In this work, we developed a highly dispersible GNR powder using an octadecyl trimethylammonium bromide (C18TAB)-assisted freeze-drying method, preserving the optical and chemical sensing properties of GNRs for over 4 months. Compared with C16TAB, C18TAB significantly enhances the GNRs dispersibility even at lower concentrations. Our study demonstrates that C18TAB forms a sponge-like crystal structure that prevents aggregation during the freeze-drying process. The resulting GNR powder retains its plasmonic features and water dispersibility, achieving near-identical optical properties to those of fresh GNR solutions. This stability enabled creation of a liquid-free colorimetric test kit with a long shelf life. This work marks a significant step forward in the use of GNRs as standard analytical reagents, opening new avenues for real-world applications.

Streamlined Flow Synthesis of Plasmonic Nanoparticles and SERS Detection of Uremic Toxins with Trace-Level Liquid Volumes in a Microchamber.

Rapid detection of uremic toxins is crucial due to their severe health risks, including oxidative stress, inflammation, neurotoxicity, cardiovascular complications, and progression of chronic kidney disease. Surface-enhanced Raman spectroscopy (SERS) may provide sensitive, fast, and clinical-grade real-time monitoring of these toxins, enabling effective management with timely dialysis treatments. This study introduces a 3D-printed microchamber that integrates the fabrication of plasmonic metal nanoparticles for the in-flow detection of biological toxins and pharmaceutical drugs using SERS, making it ideal for on-site diagnostics in clinical settings. The microchamber supports quantitative and highly reproducible detection with liquid volumes under 100 μL, which is crucial for trace-level biomarker detection and minimizing cross-contamination. It employs a tunable solvent exchange method for the in situ synthesis of silver nanoparticles (AgNPs) on flexible PDMS or rigid Si wafer substrates, avoiding costly nanofabrication techniques. Ultralow detection limits were achieved for two model compounds and three pharmaceutical drugs: 10-11 M for rhodamine 6G, 10-7 M for adenine, and 10-6 M for the pharmaceutical drugs. A total of 13 biological toxins, including three neurotransmitters, one neuromodulator, five amino acids, two polyamines, and two urea cycle metabolites, were detected with quantitative limits ranging from 10-3 to 10-6 M, all below permissible levels and aligning with physiological conditions. SERS detection within microchambers facilitates rapid on-site analysis, proving ideal for personalized health monitoring, point-of-care diagnostics, and environmental pollution assessment.

Plasmon-Exciton Strong Coupling in Colloidal Au Nanocubes with Layered Molecular J-Aggregates.

Strong coupling between light and matter forms hybrid states, such as exciton-polaritons, which are crucial for advancements in quantum science and technology. Plasmonic metal nanoparticles, with their ultrasmall mode volumes, are effective for generating these states, but the coupling strength is often limited by surface saturation of excitonic materials. Additionally, cubic nanoparticles, which can generate strong local fields, have not been systematically explored. This study investigates strong coupling in Au nanocubes (AuNCs) coupled with J-aggregates, observing spectral splitting in both extinction and scattering spectra. Our findings suggest that smaller AuNCs, with higher-quality resonances and reduced mode volumes, achieve stronger coupling. Furthermore, a layer-by-layer (LBL) coating of J-aggregates on AuNCs results in a ∼21% increase in coupling strength. Simulations reveal the mechanism behind the enhanced coupling and confirm that the layering method effectively increases coupling, surpassing the limitations of the finite surface area of nanoparticles.

Enhanced efficiency of carbon based all perovskite tandem solar cells via cubic plasmonic metallic nanoparticles with dielectric nano shells

This study investigates a carbon-based all-perovskite tandem solar cell (AP-TSC) with the structure ITO, SnO₂, Cs₀.₂FA₀.₈Pb(I₀.₇Br₀.₃)₃, WS₂, MoO₃, ITO, C₆₀, MAPb₀.₅Sn₀.₅I₃, PEDOT: PSS, Carbon. The bandgap configuration of the cell is 1.75 eV/1.17 eV, which is theoretically limited to 36% efficiency. The effectiveness of embedding cubic plasmonic metallic nanoparticles (NPs) made of Gold (Au) and Silver (Ag) within the absorber layers to eliminate the requirement for thicker absorber layers, decrease manufacturing costs and Pb toxicity is demonstrated in our analysis. This analysis was conducted using 3D Finite Element Method (FEM) simulations for both optical and electrical calculations. Prior to delving into the primary investigation of the tandem structure, a validation simulation was conducted to demonstrate the accuracy and reliability of the simulations. Notably, the efficiency mismatch observed during the validation simulation, specifically in relation to the incorporation of metallic nanoparticles (NPs), amounted to a mere 0.01%. To mitigate the potential issues of direct contact between metallic NPs and perovskite materials, such as increased thermal and chemical instability and recombination at the NP surface, a 5 nm dielectric shell was applied to the NPs. The incorporation of cubic core-shell Ag NPs resulted in a 15.32% enhancement in short-circuit current density, from 16.39 mA/cm² to 18.90 mA/cm², and a 15.68% increase in overall efficiency, from 26.9 to 31.12%. This research paves the way for the integration of core-shell metallic NPs in AP-TSCs, highlighting a significant potential for efficiency and stability improvements. In a dedicated section the band alignment of the sub-cell was addressed. Additionally, a thermal investigation of the proposed tandem structure was conducted, demonstrating the robustness of the proposed AP-TSC. Finally, the sensitivity analyses related to input parameters and the challenges associated with large-scale fabrication of the proposed AP-TSC were extensively discussed.

Highly Sensitive Determination of Copper Ions as MnO2 Etching Inhibitor in Single-Particle Nanoplasmonic Imaging.

Dark-field microscopy (DFM) imaging based on plasmonic metal nanoparticles has garnered significant attention. Here, we exploit the susceptibility of MnO2 to reduction to modulate the local dielectric environment of an Au nanoparticle core through the etching/antietching effects of specific targets on the encapsulated MnO2 shell. The presence of d-penicillamine promotes MnO2 etching, while the chelation of d-penicillamine with Cu2+ effectively inhibits this etching. By recording the Cu2+-induced color shift of scattered light from orange to bright green at the single-particle level and performing the statistical analysis of the green-to-red (G/R) values in DFM images, we achieved quantitative determination of Cu2+ with a wide linear range (0.1-10 μM) and a low limit of detection (4.55 nM). With the facile and reliable Cu2+ assay in real-world samples exemplifying the practicality of the single-particle nanoplasmonic imaging method, this work may inspire future DFM-based investigations of nanoshell etching inhibition processes.

Plasmonic Coacervate as a Droplet-Based SERS Platform for Rapid Enrichment and Microanalysis of Hydrophobic Payloads.

A novel and simple coacervate microdroplet-based detection platform for the quantification of trace hydrophobic analytes is presented. Herein, taking advantage of the effective encapsulation and enrichment performance of the condensed coacervates, plasmonic metallic silver nanoparticles (AgNPs) and target hydrophobic analytes are simultaneously concentrated into a single microdroplet. The coencapsulation of AgNPs within coacervates promotes the formation of aggregates with a lot of "hot spots" for surface-enhanced Raman scattering (SERS) enhancement, facilitating the sensitive analysis of hydrophobic analytes by SERS technology. Such plasmonic coacervates are easily prepared and exhibit good reproducibility and signal uniformity. Optimized SERS performance by modulating the volume of encapsulated AgNPs enables quantitative determination of hydrophobic analytes of Nile Red, chlorpyrifos, benzo[e]pyrene, 20 and 50 nm polystyrene nanoplastics with low detection limits of 10-12 M, 10-9 M, 10-10 M, 0.05 ppb, and 0.5 ppb, and an approximately linear correlation between SERS signals and the analytical concentrations. This study opens a new convenient SERS platform for the ultrasensitive detection of hydrophobic hazardous substances, potentially becoming a rapid analysis method for extensive applications ranging from food safety to environment monitoring.

Hydrogen Boride Sheets and Copper Nanoparticle Composites as a Visible‐Light‐Sensitive Hydrogen Release System

AbstractHydrogen boride (HB) sheet is a new class of 2D materials comprising hydrogen and boron, synthesized through ion‐exchange and exfoliation techniques. HB sheets can release hydrogen (H2) under light irradiation and is predicted to be a promising H2 storage material. However, its application is limited to the UV region. One approach to enable a visible‐light‐driven system is the utilization of plasmonic metallic nanoparticles. The present study reports H2 release from copper (Cu) nanoparticle‐modified HB sheet (HB/Cu) under visible‐light irradiation. Copper nanoparticles possess unique and strong plasmonic responses in the visible‐light range, making them ideal light absorbers in this system. HB/Cu nanocomposites are synthesized using a simple mixture of copper acetate and HB sheets in acetonitrile, where HB sheets reduced copper ions to metal copper nanoparticles. The photoirradiation results shows that HB/Cu nanocomposites released more H2 than the bare HB sheets under visible‐light irradiation. This is probably due to the plasmonic photothermal effect of copper metal, which enhances H2 generation from the HB sheets. This material offers a viable and cost‐effective approach for developing visible‐light‐sensitive systems.

( General Student Poster Award Winner, 2nd Place) Template-Assisted Fabrication of Transparent SERS Sensor with Uniform Au-Ag Nanoparticle Electrodeposition

Surface-enhanced Raman spectroscopy (SERS) is a very powerful tool for analyzing molecular interactions and provides unique spectral fingerprint information about chemical bondings.[1] SERS enhances weak Raman scattering signals through surface-localized plasmon resonance (LSPR) of the plasmonic metal nanoparticles. Arbitrarily distribution of plasmonic metal nanoparticles can result in a non-uniform SERS enhancement effect (EF) and low reproducibility, which hinders the practical application of this ultra-sensitive analysis technology.[2] The development of a cost-effective, highly reliable, and highly reproducible SERS sensor with precisely controlled nanoparticle size and distribution is still a challenge.[3] Electron beam lithography (EBL) is commonly used to achieve well-controlled nanoscale patterns, which can be used as a top-down SERS sensor fabrication technique.[2] However, the time-consuming and extremely costly method makes the SERS sensor not easily accessible.In this research, we propose a template-assisted fabrication process by electrodepositing nanoparticles into nanoarrays on a transparent ITO surface. This method precisely controls the surface morphology and provides high reproducibility without relying on EBL techniques. For the fabrication process, first, a layer of sol-gel SiO2 solution was spin-coated onto the ITO surface, and an array of nano-pillars was used to imprint the nanopattern to the sol-gel solution layer, to realize the nano-ordered uniformly distributed nanoarrays. (Fig.1) For the plasmonic material, Au-Ag alloy was deposited into the nanoarray due to its high durability and high SERS EF.[4] The use of a pulse current deposition, additives, and self-assembled monolayer (SAM) was also discussed from the perspective of altering the surface property of the ITO surface, to achieve dense and smooth filling of deposits in the nanoarray. The SERS sensor fabricated was tested with Janus Green B (JGB) and demonstrated a good SERS EF and good signal uniformity. We believe this sensor is widely applicable for different systems, further optimization and application of this sensor can bring us one step closer to the quantitative analysis by SERS. The fabricated sensor should be especially useful in electrochemical reaction analysis and biomolecular sensing.[1] Fleishmann et al., Phys. Lett., 26, 163(1974)[2] Lee et al., Chemical Society reviews., 48, 731(2019)[3] Shi et al., 66, 6525(2018)[4] B. Liu et al., 55 , 117104(2016) Figure 1

Hot carriers from intra- and interband transitions in gold-silver alloy nanoparticles

Hot electrons and holes generated from the decay of localised surface plasmons in metallic nanoparticles can be harnessed for applications in solar energy conversion and sensing. In this paper, we study the generation of hot carriers in large spherical gold-silver alloy nanoparticles using a recently developed atomistic modelling approach that combines a solution of Maxwell’s equations with large-scale tight-binding simulations. We find that hot-carrier properties depend sensitively on the alloy composition. Specifically, nanoparticles with a large gold fraction produce hot carriers under visible light illumination while nanoparticles with a large silver fraction require higher photon energies to produce hot carriers. Moreover, most hot carriers in nanoparticles with a large gold fraction originate from interband transitions which give rise to energetic holes and ‘cold’ electrons near the Fermi level. Increasing the silver fraction enhances the generation rate of hot carriers from intraband transitions which produce energetic electrons and ‘cold’ holes. These findings demonstrate that alloy composition is a powerful tuning parameter for the design of nanoparticles for applications in solar energy conversion and sensing that require precise control of hot-carrier properties.

Stearic acid-coated plasmonic Ag nanoparticles as a dual catalyst for enhanced NiO chemo and photo catalysis

The phenomenon of Localized Surface Plasmon Resonance (LSPR) in plasmonic metal nanoparticles causes a strong absorption of visible light and leads to the generation of hot electrons on the surface and the creation of localized electromagnetic fields near the surface. This characteristic enhances the catalytic performance of a plasmonic metal Ag–NiO nanocomposite (NiO-SNP) when exposed to low-flux visible light irradiation. The NiO-SNP was synthesized using a simple and cost-effective ultrasonication method. Its structural, morphological, and optical properties were analyzed, confirming the formation of nanocomposites. The proximity of stearic acid-coated Ag nanoparticles (SNP) acts as visible light-harvesting antennas, promoting NiO's activity for effectively reducing paracetamol (PM) drugs. The improved catalytic property is attributed to an electron relay effect, while the strong electromagnetic fields generated by irradiated Ag nanoparticles facilitate the concentration of PM molecules at active sites, leading to accelerated reaction rates. NiO-SNP2 demonstrates remarkable PM degradation: 97 % in tap water and 82.6 % in deionized water within 10 min, demonstrating its catalytic effectiveness. The plasmonic SNP mechanism in NiO-SNP1 nanocomposites enhances photocatalytic efficiency by up to 90 %, owing to efficient charge separation and transfer, resulting in a notable 1.5-fold increase in PM degradation. The degradation kinetics follow a pseudo-first-order model, with rate constants (k) ranging from approximately 0.059 to 0.6104 min⁻1, underscoring the crucial role of Ag nanoparticles in enhancing photocatalytic activity and degradation efficiency. Catalysis and visible light photocatalysis are significantly improved with increasing concentrations of NiO and SNP, respectively. This research could inspire a new approach to transforming traditional metal catalysis into plasmonic-metal catalysis.

Time-dependent Kohn-Sham electron dynamics coupled with nonequilibrium plasmonic response via atomistic electromagnetic model.

Computational modeling of plasmon-mediated molecular photophysical and photochemical behaviors can help us better understand and tune the bound molecular properties and reactivity and make better decisions to design and control nanostructures. However, computational investigations of coupled plasmon-molecule systems are challenging due to the lack of accurate and efficient protocols to simulate these systems. Here, we present a hybrid scheme by combining the real-time time-dependent density functional theory (RT-TDDFT) approach with the time-domain frequency dependent fluctuating charge (TD-ωFQ) model. At first, we transform ωFQ in the frequency-domain, an atomistic electromagnetic model for the plasmonic response of plasmonic metal nanoparticles (PMNPs), into the time-domain and derive its equation-of-motion formulation. The TD-ωFQ introduces the nonequilibrium plasmonic response of PMNPs and atomistic interactions to the electronic excitation of the quantum mechanical (QM) region. Then, we combine TD-ωFQ with RT-TDDFT. The derived RT-TDDFT/TD-ωFQ scheme allows us to effectively simulate the plasmon-mediated "real-time" electronic dynamics and even the coupled electron-nuclear dynamics by combining them with the nuclear dynamics approaches. As a first application of the RT-TDDFT/TD-ωFQ method, we study the nonradiative decay rate and plasmon-enhanced absorption spectra of two small molecules in the proximity of sodium MNPs. Thanks to the atomistic nature of the ωFQ model, the edge effect of MNP on absorption enhancement has also been investigated and unveiled.

A Real-Time LSPR-Based Study of Metal-Organic Framework (MOF) Growth.

MOFs are known for their absorption properties and widely used for accumulation, filtering, sensorics, photothermal, catalytical and other applications. Their combination with plasmonic metal nanoparticles leads to hybrid structures that profit from the stabilizing effect and high porosity of the MOF as well as the optical and electronic properties of the nanoparticles. The growth of MOFs on plasmonic nanoparticles can be monitored in-situ using LSPR spectroscopy, simultaneously applying microfluidic reaction conditions for the fabrication of NP@MOF structures. Here, a systematic study is conducted using LSPR spectroscopy for the monitoring of the Layer-by-Layer deposition of twelve different MOFs, determining the suitability of LSPR spectroscopy for this purpose. In addition to some well-investigated materials like HKUST-1, other MOFs such as MIL-53, MIL-88 A and Cu-BDC are deposited successfully. For some MOFs such as Zn-Fum, the LSPR experiment indicates that no deposition had taken place. The results are confirmed with AFM, SEM and XPS measurements. This work shows that LSPR spectroscopy is suitable for the in-situ monitoring of LbL MOF growth and the microfluidic setup is a very promising method for the controlled manufacturing of NP@MOF hybrid structures. Further studies may include the optimization of the synthesis process or the transfer to other materials.

Self-powered poly(3-hexylthiophene)/ZnO heterojunction ultraviolet photodetectors decorated by silver nanoparticles

Self-powered poly (3-hexylthiophene)/zinc oxide (P3HT/ZnO) heterojunction ultraviolet photodetectors decorated by silver nanoparticles (Ag NPs) were fabricated by sol-gel and spin-coating techniques. The ultraviolet photoresponse performance of the P3HT/ZnO heterojunction photodetectors influenced by the position of plasmonic Ag NPs was investigated. The responsivity and detectivity of the P3HT/Ag/ZnO photodetector with placed Ag NPs at the interface of ZnO and P3HT layers enhanced to 1.92 and 1.15 times compared to the reference devices. When the Ag NPs embedded into ZnO layer, the responsivity, detectivity and external quantum efficiency were 16.42 mA/W, 5.97 × 1011 Jones, and 5.36 %, respectively, which were 5.77 times, 4.64 times and 5.77 times to that of the pristine P3HT/ZnO photodetector. The enhancement mechanism of plasmonic metallic nanoparticles to the performance of the photodetectors was discussed in details. This study presents a simple route to high performance self-powered photodetectors.

Type-dependent hot carrier behavior in photoelectrochemical reduction and oxidation of Au/GaN junction photoelectrodes

In junctions with semiconductors, plasmonic metal nanoparticles (NPs) can be utilized to efficiently harness solar energy by collecting hot carriers. However, the behavior of hot carriers at the interfaces between semiconductors with opposite doping types is not fully elucidated. Here, Au NPs are attached to n-doped (Au/n-GaN) or p-doped gallium nitrides (Au/p-GaN) to examine the photoelectrochemical performance regarding hot carrier behavior. Direct surface potential measurements revealed that electrons are collected in n-type GaN (n-GaN) when illuminated, while hot holes remain in Au NPs for oxidation reactions via the plasmonic process. Conversely, holes are collected in p-type GaN (p-GaN), thereby promoting the reduction reaction by the electrons left in Au NPs. Specifically, the change in surface potential difference induced by green light illumination in Au/p-GaN is four times greater than that observed in Au/n-GaN. Conversely, the changes in open-circuit potential and photocurrent density under light illumination are approximately six times more significant in Au/n-GaN compared to Au/p-GaN. This difference in efficiency can be attributed to the more favorable oxidation reaction occurring in Au NPs at the interface with GaN materials, as opposed to the reduction reaction, due to the difference in band alignment between the Au/GaN junction systems.

Elastic scattering of gold and silver colloids: Difference between spherical and nonspherical nanoparticles

Light scattering of noble metal nanoparticles was widely used in solar cells, sensing and spectroscopy, so the research on the light scattering itself will be beneficial for their increasing applications. In this paper, gold and silver nanoparticles with different sizes and shapes were synthesized and their elastic scattering was investigated. The results demonstrate that the elastic scattering of metal nanoparticles is influenced by their size and shape, and the scattering behavior has a specific correlation with the surface plasmon resonance. The elastic scattering spectra of gold and silver nanospheres basically cover the extinction spectra, indicating plasmon resonance enhanced scattering of spherical nanoparticles. The elastic scattering spectra of nonspherical gold nanorods and silver nanoprisms only overlap the extinction peaks at short wavelengths. The elastic scattering is considered to be enhanced by the transverse resonance bands at short wavelengths for nonspherical gold or silver nanoparticles, but it cannot be contributed by the longitudinal resonance bands at the corresponding long wavelengths. This result will be helpful in selecting size and shape in the scattering application of plasmonic metal nanoparticles.

Unraveling a Concerted Proton-Coupled Electron Transfer Pathway in Atomically Precise Gold Nanoclusters.

Metal nanoclusters (MNCs) represent a promising class of materials for catalytic carbon dioxide and proton reduction as well as dihydrogen oxidation. In such reactions, multiple proton-coupled electron transfer (PCET) processes are typically involved, and the current understanding of PCET mechanisms in MNCs has primarily focused on the sequential transfer mode. However, a concerted transfer pathway, i.e., concerted electron-proton transfer (CEPT), despite its potential for a higher catalytic rate and lower reaction barrier, still lacks comprehensive elucidation. Herein, we introduce an experimental paradigm to test the feasibility of the CEPT process in MNCs, by employing Au18(SR)14 (SR denotes thiolate ligand), Au22(SR)18, and Au25(SR)18- as model clusters. Detailed investigations indicate that the photoinduced PCET reactions in the designed system proceed via an CEPT pathway. Furthermore, the rate constants of gold nanoclusters (AuNCs) have been found to be correlated with both the size of the cluster and the flexibility of the Au-S framework. This newly identified PCET behavior in AuNCs is prominently different from that observed in semiconductor quantum dots and plasmonic metal nanoparticles. Our findings are of crucial importance for unveiling the catalytic mechanisms of quantum-confined metal nanomaterials and for the future rational design of more efficient catalysts.

Development of excitation power-responsive anti-stokes emission wavelength switching and their energy saving induced by localized surface plasmon resonance

We designed an external stimulus-responsive anti-Stokes emission switching using dual-annihilator-based triplet–triplet annihilation upconversion systems. This system, which was constructed by incorporating a palladium porphyrin derivative as a sensitizer and 9,10-diphenylanthracene (DPA) and 9,10-bis(triisopropylsilyl)ethynylanthracene (TIPS) as annihilators into polymer thin films, produced TIPS- and DPA-based anti-Stokes emission under low and high excitation powers, respectively. The mechanism involves the following: under low excitation power, triplet energy transfer from triplet-excited PdOEP to DPA is induced, followed by relay to TIPS. This results in the generation of triplet-excited TIPS, and the subsequent triplet–triplet annihilation between them produces TIPS-based anti-Stokes emission. Conversely, under high excitation power, the high-density triplet-excited DPA, generated through triplet energy transfer from PdOEP, undergoes triplet–triplet annihilation among themselves, resulting in the generation of DPA-based anti-Stokes emission. Additionally, we achieved energy savings by reducing the required excitation power for switching through the utilization of plasmonic metal nanoparticles. The strong local electromagnetic fields associated with the localized surface plasmon resonance of metal nanoparticles enhance the photoexcitation efficiency of PdOEP, subsequently increasing the density of triplet-excited DPA. As a result, anti-Stokes emission switching becomes feasible at lower excitation powers.

Plasmon-enhanced multi-photon excited photoluminescence of Au, Ag, and Pt nanoclusters

In this work, we have studied the multi-photon excited photoluminescence from metal nanoclusters (NCs) of Au, Ag and Pt embedded in Al2O3 matrix by ion implantation. The thermal annealing process allows to obtain a system composed of larger plasmonic metal nanoparticles (NPs) surrounded by photoluminescent ultra-small metal NCs. By exciting at 1064 nm, visible emission, ranging from 450 to 800 nm, was detected. The second and fourth-order nature of the multiphoton process was verified in a power-dependent study measured for each sample below the damage threshold. Experiments show that Au and Ag NCs exhibit a four-fold enhanced multiphoton excited photoluminescence with respect to that observed for Pt NCs, which can be explained as a result of a plasmon-mediated near-field process that is of less intensity for Pt NPs. These findings provide new opportunities to combine plasmonic nanoparticles and photoluminescent nanoclusters inside a robust inorganic matrix to improve their optical properties. Plasmon-enhanced multiphoton excited photoluminescence from metal nanoclusters may find potential application as ultrasmall fluorophores in multiphoton sensing, and in the development of solar cells with highly efficient energy conversion modules.

A hybrid quantum-classical theory for predicting terahertz charge-transfer plasmons in metal nanoparticles on graphene.

Metal nanoparticle (NP) complexes lying on a single-layer graphene surface are studied with a developed original hybrid quantum-classical theory using the Finite Element Method (FEM) that is computationally cheap. Our theory is based on the motivated assumption that the carrier charge density in the doped graphene does not vary significantly during the plasmon oscillations. Charge transfer plasmon (CTP) frequencies, eigenvectors, quality factors, energy loss in the NPs and in graphene, and the absorption power are aspects that are theoretically studied and numerically calculated. It is shown the CTP frequencies reside in the terahertz range and can be represented as a product of two factors: the Fermi level of graphene and the geometry of the NP complex. The energy losses in the NPs are predicted to be inversely dependent on the radius R of the nanoparticle, while the loss in graphene is proportional to R and the interparticle distance. The CTP quality factors are predicted to be in the range ∼10-100. The absorption power under CTP excitation is proportional to the scalar product of the CTP dipole moment and the external electromagnetic field. The developed theory makes it possible to simulate different properties of CTPs 3-4 orders of magnitude faster compared to the original FEM or the finite-difference time domain method, providing possibilities for predicting the plasmonic properties of very large systems for different applications.

SERS aptasensor utilizing aptamer-conformation-mediated regulation of Au dumbbell dimers for the ultrasensitive detection of β-phenethylamine in foods

Surface-enhanced Raman spectroscopy (SERS) is a powerful tool for the detection of target analytes in foods, with the realization of “hot spots” between plasmonic metal nanoparticles (NPs) being critical for ultrasensitive detection. Herein, we proposed a new aptamer conformation-mediated SERS “hot spots” strategy. Au NPs were functionalized with strands of complementary DNA containing β-phenethylamine aptamers and the Raman reporter 4-mercaptobenzonitrile (4-MBN). This allowed DNA-driven self-assembly of an Au dumbbell dimer-based SERS aptasensor for the detection of the β-phenethylamine. After selective recognition of β-phenethylamine by the aptamer, the aptamer folded, bringing AuNPs in the dimers close together to create SERS “hot spots”. This produced an intense SERS signal in the “biologically silent” region for 4-MBN (2225 cm−1), the intensity of which increased linearly with the logarithm of the β-phenethylamine concentration. Under the optimized conditions, the linear range of SERS aptasensor was 10−6 to 10−2 mg L−1, with a low limit of detection of 3.8 × 10−7 mg L−1. Further, the developed SERS aptasensor was successfully employed to determine the β-phenethylamine in a range of food samples, with the results being identical to those obtained using a high-performance liquid chromatography method.