Electromagnetic Enhancement Effect Research Articles

Gold nanostars and nanourchins for enhanced photothermal therapy, bioimaging, and theranostics.

Photothermal therapy (PTT), a recently emerging method for eradicating tumors, utilizes hyperthermia induced by photo-absorbing materials to generate heat within cancer cells. Gold nanoparticles (AuNPs) have gained reliability for in vitro and in vivo applications in PTT due to their strong light absorbance, stability, and biocompatibility. Yet, their potential is limited by their spherical shape, impacting their size capabilities, electromagnetic enhancement effects, and localized surface plasmon resonance (LSPR). Anisotropic shapes have been tested and implemented in this treatment to overcome the limitations of spherical AuNPs. Nanostars (AuNSs) and nanourchins (AuNUs) offer unique properties, such as increased local electron density, improved catalytic activity, and an enhanced electromagnetic field, which have proven to be effective in PTT. Additionally, these shapes can easily reach the NIR-I and NIR-II window while exhibiting improved biological properties, including low cytotoxicity and high cellular uptake. This work covers the critical characteristics of AuNS and AuNUs, highlighting rough surface photothermal conversion enhancement, significantly impacting recent PTT and its synergy with other treatments. Additionally, the bioimaging and theranostic applications of these nanomaterials are discussed, highlighting their multifaceted utility in advanced cancer therapies.

Plasmonic Nanostars: Unique Properties That Distinguish Them from Spherical Nanoparticles from a Biosensing Perspective

AbstractOver the past three decades, plasmonic nanostructures, particularly spherical ones, have seen remarkable advancements. Recently, attention has shifted toward anisotropic nanoparticles, especially star‐shaped/branched structures such as plasmonic nanostars (PNS), due to their distinct properties. PNS offers superior electromagnetic enhancement effects, larger surface areas, and as well as non‐linear and unusual photothermal properties, setting them apart from spherical counterparts. Despite significant progress in synthetic methods and characterization of the particles, challenges remain in transitioning PNS technology into practical use. In this perspective article, the distinctive attributes of PNS in biosensing applications are discussed, beginning with an exploration of synthesis methodologies. Their optoelectronic properties are examined and discussed how these properties influence their interaction with different molecules from a biosensing perspective. With a focus on PNS, detailed insights are offered into their unique properties, current applications, and future potential. By fostering discussion and understanding of PNS development, this article aims to facilitate the translation of PNS technology into practical applications, encouraging targeted improvements and advancements.

Apt-Conjugated PDMS-ZnO/Ag-Based Multifunctional Integrated Superhydrophobic Biosensor with High SERS Activity and Photocatalytic Sterilization Performance.

Sensitive detection and efficient inactivation of pathogenic bacteria are crucial for halting the spread and reproduction of foodborne pathogenic bacteria. Herein, a novel Apt-modified PDMS-ZnO/Ag multifunctional biosensor has been developed for high-sensitivity surface-enhanced Raman scattering (SERS) detection along with photocatalytic sterilization towards Salmonella typhimurium (S. typhimurium). The distribution of the electric field in PDMS-ZnO/Ag with different Ag sputtering times was analyzed using a finite-difference time-domain (FDTD) algorithm. Due to the combined effect of electromagnetic enhancement and chemical enhancement, PDMS-ZnO/Ag exhibited outstanding SERS sensitivity. The limit of detection (LOD) for 4-MBA on the optimal SERS substrate (PZA-40) could be as little as 10-9 M. After PZA-40 was modified with the aptamer, the LOD of the PZA-40-Apt biosensor for detecting S. typhimurium was only 10 cfu/mL. Additionally, the PZA-40-Apt biosensor could effectively inactivate S. typhimurium under visible light irradiation within 10 min, with a bacterial lethality rate (Lb) of up to 97%. In particular, the PZA-40-Apt biosensor could identify S. typhimurium in food samples in addition to having minimal cytotoxicity and powerful biocompatibility. This work provides a multifunctional nanoplatform with broad prospects for selective SERS detection and photocatalytic sterilization of pathogenic bacteria.

SERS Detection of Trace Carcinogenic Aromatic Amines Based on Amorphous MoO3 Monolayers.

Aromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a-MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot-electron fast decay component of a-MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon-induced hot-electron transfer (PIHET) process from a-MoO3 to MO. Therefore, a-MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM-PIHET synergistic mechanism in a-MoO3. In addition, a-MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c-MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o-aminoazotoluene (o-AAT) is 10-9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a-MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates.

SERS Detection of Trace Carcinogenic Aromatic Amines Based on Amorphous MoO3 Monolayers

AbstractAromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a‐MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot‐electron fast decay component of a‐MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon‐induced hot‐electron transfer (PIHET) process from a‐MoO3 to MO. Therefore, a‐MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM‐PIHET synergistic mechanism in a‐MoO3. In addition, a‐MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c‐MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o‐aminoazotoluene (o‐AAT) is 10−9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a‐MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates.

Synergistic enhancement mediated sensitive SERS-based immunoassay of PSA using versatile PDMS@AgNPs@ZIF-67 biomimetic substrates

Among various biomimetic polymer materials, polydimethylsiloxane (PDMS) stands out as an ideal matrix for surface-enhanced Raman scattering (SERS) due to its unique intrinsic Raman signal and tenacity. In order to realize the precise detection of prostate-specific antigen (PSA), we proposed a sandwich-type SERS-active immunostructure composed of PDMS@silver nanoparticles (Ag NPs)@ZIF-67 biomimetic film as the immunosubstrate and gold nanorods (Au NRs) as immunoprobes. Due to the synergistic effect of electromagnetic enhancement facilitated by biomimetic surfaces and chemical enhancement achieved by ZIF-67, this structure enabled an ultrasensitive and selective detection of PSA across a broad range from 10−3 to 10−9 mg/mL. The achieved limit of detection was as low as 3.0 × 10−10 mg/mL. Particularly, the intrinsic Raman signal of PDMS matrix at 2905 cm−1 was employed as a potential internal standard (IS) in the detection, achieving a high coefficient of determination (R2) value of 0.996. This multifunctional SERS substrate-mediated immunoassay holds vast potential for early diagnosis of prostate cancer, offering promising prospects for clinical applications.

Optofluidic SERS based on Ag nanocubes with high sensitivity for detecting a prevalent water pollutant.

To enhance the integration and practical applicability of the Raman detection system, silver nanocubes (Ag NCs) were synthesized using a polyol method. A liquid-liquid interface approach was employed to transfer a monolayer of Ag NCs "film" onto a SiO2 substrate, resulting in the fabrication of a highly sensitive and uniform surface-enhanced Raman scattering (SERS) substrate denoted as "Ag NCs@SiO2." The electromagnetic field distribution of various dimers on the Ag NCs@SiO2 was analyzed using finite difference time domain (FDTD) software. The results reveal that the electromagnetic enhancement effect is most pronounced in cube-cube dimers, indicating that Ag NCs exhibit superior localized surface plasmon resonance (LSPR) response due to their well-defined geometric regularity and sharp geometric angles. For Rhodamine 6G (R6G) probe molecules, the Ag NCs@SiO2 shows ultrahigh sensitivity, with a limit of detection (LOD) of 10-12 mol/L, and the enhancement factor (EF) can reach 1.4 × 1010. The relative standard deviation (RSD) at the main characteristic peaks is below 10%, demonstrating good consistency in substrate performance. In addition, the Ag NCs@SiO2 modified with hexanethiol exhibits high sensitivity, uniformity, and repeatability in detecting for pyrene, with the LOD of 10-8 mol/L and a minimum RSD of 6.09% at the main characteristic peak, and effective recognition capabilities for pyrene and anthracene in mixed solutions. Finally, chemisorption and physisorption strategies were prepared in optofluidic channels and experimentally compared, enabling real-time detection of the pyrene solution. This method can achieve a rapid detection and precise differentiation of polycyclic aromatic hydrocarbons in a water pollutant.

Construction of an Au/g-C3N4/GO/Au substrate by a layer-by-layer assembly approach for surface-enhanced Raman spectroscopy

In this work, an Au/g-C3N4/GO/Au hybrid nanofilm for surface-enhanced Raman scattering (SERS) substrate application was prepared by a facile layer-by-layer assembly technique using nanosheet-structured graphitic carbon nitride (g-C3N4), graphene oxide (GO) and 40 nm-gold nanoparticles (Au NPs). The effects of composition, assembly sequence and assembly cycles on the SERS performance were optimized to achieve the SERS-active substrate. The detection limit of Au/g-C3N4/GO/Au substrate for crystal violet and rhodamine 6 G probe molecules reached as high as 10−8 M, with good stability and uniformity. Its further application in food colorants detection (erythrosine, carmine and temptation red) had successfully met the national food safety standards and the quantitative detection for erythrosine and temptation red had also been established. Based on finite-difference time-domain element simulation and density functional theory quantum chemical calculation, the mechanism of the SERS effect of the substrate was unveiled, which is attributed to the combination of electromagnetic enhancement effect of Au nanoparticle aggregates and chemical enhancement effect of GO and g-C3N4. Notably, water droplet evaporation induced Raman enhancement was observed on the Au/g-C3N4/GO/Au substrate. This can be ascribed to the inhomogeneous evaporation of the droplet that promotes the enrichment of the probe molecules into the center of the droplet. This novel enhancement strategy provides a new idea for further improving detection sensitivity of SERS substrate materials.

Silver nanostars arrayed on GO/MWCNT composite membranes for enrichment and SERS detection of polystyrene nanoplastics in water

Nanoplastic water contamination has become a critical environmental issue, highlighting the need for rapid and sensitive detection of nanoplastics. In this study, we aimed to prepare a graphene oxide (GO)/multiwalled carbon nanotube (MWCNT)–silver nanostar (AgNS) multifunctional membrane using a simple vacuum filtration method for the enrichment and surface-enhanced Raman spectroscopy (SERS) detection of polystyrene (PS) nanoplastics in water. AgNSs, selected for the size and shape of nanoplastics, have numerous exposed Raman hotspots on their surface, which exert a strong electromagnetic enhancement effect. AgNSs were filter-arrayed on GO/MWCNT composite membranes with excellent enrichment ability and chemical enhancement effects, resulting in the high sensitivity of GO/MWCNT–AgNS membranes. When the water samples flowed through the portable filtration device with GO/MWCNT–AgNS membranes, PS nanoplastics could be effectively enriched, and the retention rate for 50 nm PS nanoplastics was 97.1 %. Utilizing the strong SERS effect of the GO/MWCNT–AgNS membrane, we successfully detected PS nanoparticles with particle size in the range of 50–1000 nm and a minimum detection concentration of 5 × 10−5 mg/mL. In addition, we detected 50, 100, and 200 nm PS nanoplastics at concentrations as low as 5 × 10−5 mg/mL in real water samples using spiking experiments. These results indicate that the GO/MWCNT–AgNS membranes paired with a portable filtration device and Raman spectrometer can effectively enrich and rapidly detect PS nanoplastics in water, which has great potential for on-site sensitive water quality safety evaluation.

One-step fabrication of flexible polyamide@Ag-dodecanethiol membranes for highly sensitive SERS detection of thiram

The surface-enhanced Raman scattering (SERS) is an effective spectral technology based on Raman scattering, but in practice, the commonly used SERS substrates suffer from low sensitivity and poor stability. In order to overcome these limitations, the SERS substrates were prepared from hydrophobic modification of dodecanethiol (C12) coupled with a flexible substrate, which was then used for pesticides detection in water. A flexible PA@Ag-C12 substrate with surface functionalization has been obtained. This work aims to investigate the self-assembly of Ag NPs modified with C12 onto polyamide (PA) membranes. Initially, transmission electron microscopy and scanning electron microscopy were used to analyze the substrate’s morphology. Then with the help of an energy-dispersive spectrometer, sulfur content of C12-modified Ag NPs was analyzed. In order to determine the hydrophobicity of the modified Ag NPs, the contact angle was used. The results indicate that the gap between Ag NPs on PA membrane can be effectively controlled in order to prevent Ag NPs from aggregating. Furthermore, the finite-difference time-domain analysis indicated that the PA@Ag-C12 substrate exhibited a stronger electromagnetic enhancement effect than the PA@Ag substrate. By reducing NPs gaps on the PA membrane, the number of ‘hot spots’ increased, and the SERS performance of the substrate was improved as a result. According to the results of this study, this method can greatly reduce the manufacturing costs and time costs of the SERS substrate while maintaining the original uniformity. The SERS performance of PA@Ag-C12 was found to be three orders of magnitude better than that of PA@Ag direct self-assembled substrate, and the detection limit for Rhodamine 6G (R6G) was approximately 8.47 × 10−14 M. On the basis of the PA@Ag-C12 substrate, thiram is detectable at a detection limit of 5.88 × 10−11 M with a high degree of sensitivity and repeatability.

Development of highly sensitive plasmonic biosensors encoded with gold nanoparticles on M13 bacteriophage networks

In this study, a novel nanoplasmonic substrate is developed for biomedical applications. In nanoplasmonic biosensors, a substrate that can induce strong hot spots by forming uniform nanogaps smaller than 10 nm is required to implement a device capable of detecting biomarkers at low concentrations. Herein, gold nanoparticles-encoded M13 bacteriophage (AuNPs@M13) substrate was developed by immobilizing 60 nm AuNPs onto the surface of an M13 bacteriophage scaffold with a network assembly structure. The plasmonic characteristics of the proposed AuNPs-M13 were evaluated by assessing the nanogap distribution, electromagnetic enhancement effects, and reproducibility of the fabricated substrate. Additionally, an immunoassay for severe acute respiratory syndrome coronavirus 2 was performed to confirm the clinical applicability of the proposed AuNPs@M13 substrate. When the AuNPs@M13 was used as a nanoplasmonic substrate, it was possible to achieve better sensitivity (limit of detection [LoD] = 1.21 PFU/mL) than that with the commercially available lateral flow assay strip (LoD = 300–500 PFU/mL) or enzyme-linked immunoassay (LoD = 48 PFU/mL). The proposed AuNPs@M13 in this study is expected to be used as an innovative biomedical device for the high-sensitivity detection of various biomarkers.

Molybdenum disulfide-loaded multilayer AuNPs with colorimetric-SERS dual-signal enhancement activities for flexible immunochromatographic diagnosis of monkeypox virus

The sudden outbreak of monkeypox in 2022 suggests the importance of developing a rapid but sensitive virus detection technology. Herein, we report a colorimetric/surface-enhanced Raman scattering (SERS) dual-signal co-enhanced immunochromatographic assay (ICA) for the flexible, ultrasensitive, and accurate detection of monkeypox virus (MPXV) in various complex samples. A thickness-controlled polyethyleneimine interlayer (1 nm) is coated onto two-dimensional molybdenum disulfide (MoS2) nanosheet to enable the electrostatic adsorption of two layers of dense 30 nm AuNPs, which not only improves colorimetric ability but also creates numerous efficient SERS hotspots. Moreover, the SERS activity of film-like dual-signal tag (MoS2@Au–Au) is drastically enhanced by combining the chemical enhancement effect of MoS2 sheets and the electromagnetic enhancement effect of Au–Au hotspots. The introduction of MoS2@Au–Au greatly broadens the application range of existing ICA methods, in which the colorimetric signal supports the quick identification of the target virus and the SERS signal allows the quantitative detection of MPXV with detection limits of as low as 0.2 and 0.002 ng/mL. Given its rapid detection ability (< 20 min), high accuracy in real samples (RSD < 9.89 %), and superior sensitivity than traditional AuNP-based colorimetric ICA (> 500 times), the proposed assay has great potential for field application.

Visible light‐enhanced and degradable SERS substrates based on g‐C3N4/Au NP hybrid structures

AbstractIn this study, a visible light‐activated and degradable surface‐enhanced Raman spectroscopy (SERS) substrate was fabricated based on graphite carbon nitride (g‐C3N4) and gold nanoparticle (Au NP) hybrid structures. By using porous structure of g‐C3N4 as the support, Au NP arrays can be formed through sputtering of a thin Au film. Typical surface Raman enhancement effect can be observed by using p‐toluenethiol as the probe molecule. Interestingly, it was found that the Raman signal of probe molecules could be enhanced 2.7 times by pre‐illumination of visible light for a short time within 2 min, while the Raman signal decreased significantly about five times with further long‐term irradiation of more than 60 min. The electromagnetic enhancement effect of Au NP array on semiconductor materials with various extinction coefficients was studied by FDTD simulations. Furthermore, a charge transfer enhancement mechanism was proposed based on band structure of g‐C3N4/Au NP hybrid substrate and molecular orbitals. Our experimental and simulation results demonstrated an approach to construct a visible light‐activated SERS substrate with enhancement and degradation properties based on porous organic semiconductors.

High-sensitivity biosensor based on SERS integrated with dendrimer-assisted boronic acid-functionalized magnetic nanoparticles for IL-6 detection in human serum

High-sensitivity quantitative analysis of sepsis disease markers in circulating blood is essential for sepsis early diagnosis, rapid stratification, and interventional treatment. Herein, a high-sensitivity biosensor combining surface-enhanced Raman spectroscopy (SERS) and functionalized magnetic materials was developed to quantitatively detect interleukin-6 (IL-6), a glycoprotein disease marker closely related to sepsis. First, boronic acid-functionalized magnetic nanomaterials with high adsorption performance were synthesized by utilizing the branched polyethyleneimine to provide many binding sites for boronic acid. Under antibody-free conditions, dendrimer-assisted boronic acid-functionalized magnetic nanomaterials selectively capture glycoproteins in complex biological samples as bio-capture element. Then, a core–shell bimetallic material with plenty of ‘hot spots’ was designed and synthesized as the enhancement substrate. The 4-Mercaptobenzonitrile (4-MP) with a characteristic peak at 2224 cm−1 (Raman-silent region) was embedded as the Raman reporter to form a SERS immune probe with highly efficient electromagnetic enhancement effect, achieving specific recognition and high-sensitivity detection of IL-6 on bio-capture elements. Using this strategy for quantitative analysis of IL-6, a wide detection range (0.5–5000 pg ml−1) and a low detection limit (0.453 pg ml−1) were obtained. Moreover, this method exhibited excellent detection performance for IL-6 in human serum samples, demonstrating its potential promise in screening clinically relevant diseases. The biosensor presented here not only provides a novel and universally applicable sensing strategy for the enrichment and detection of trace glycoprotein disease markers, but also the application of a portable Raman spectrometer provides a more reliable experimental basis for the diagnosis and treatment of major diseases in the clinic or remote and deprived areas.

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.

Coaxially electrospun TiO2@Au core-shell nanofibers for ultrasensitive and reusable SERS detection of furazolidone

We report the core/shell synthesis of TiO2 nanofibers covered with Au nanograins (Au NGs@TiO2 NFs) by the direct coaxial electrospinning method without the need of pre-preparation of Au NGs for the rapid and sensitive SERS detection of furazolidone (FZD). The characterization of the as-synthesized Au NGs@ TiO2 NFs hybrid nanostructure was meticulously examined by diverse microscopic and spectroscopic techniques. The SERS performance of Au NGs@TiO2 NFs for the detection of FZD is verified with the high enhancement factor of 5.96 × 1012 and the limit of detection as low as 3.94 × 10−13 M, which are superior to those reported so far in the literatures. The excellent SERS performance can be attributed to the synergistic effect of electromagnetic enhancement and charge transfer induced in the Au NGs@TiO2 NFs hybrid nanostructure. Besides, the Au NGs@TiO2 NFs display good uniformity and high reproducibility for the FZD detection. In the practical application, the Au NGs@TiO2 NFs based SERS substrate is successfully utilized to detect FZD in food and environmental samples with excellent recovery. The reusability measurement shows that 92.73 % of the original Raman peak intensity is retained after five photocatalytic degradation cycles, which confirms the cost effectiveness of Au NGs@TiO2 NFs in the SERS application. The proposed high-performance SERS substrate has great potential to pave a new avenue in food safety applications, such as detecting antibiotics in real samples.

ZnO nanorods decorated with Ag nanoflowers as a recyclable SERS substrate for rapid detection of pesticide residue in multiple-scenes

Pesticide residues threaten the ecological environment and human health. Therefore, developing high performance SERS substrate to achieve highly sensitive detection of pesticide residues is meaningful. In this study, based on the strategy of combining “hot spots” engineering and material hybridization, we construct a novel hybrid SERS substrate by depositing Ag nanoflowers (NFs) on ZnO nanorods (NRs). Benefiting from the synergistic effect of electromagnetic enhancement and charge transfer effect, the Ag NFs@ZnO NRs substrate exhibits a low detection limit (10−13 M) for crystal violet molecules. This SERS substrate has good uniformity with a relative standard deviation of 7.463 %. Besides, owning to the photocatalytic property of ZnO NRs, the hybrid substrate can degrade probe molecules after SERS detection and realize recyclability. As a demonstration, we employed our SERS substrate for the trace detection of pesticide residues on apple surface and in river water. This study provides a new idea for improving the SERS performance of hybrid substrates.

A molecularly-imprinted SERS sensor based on a TiO2@Ag substrate for the selective capture and sensitive detection of tryptamine in foods

Herein, a molecularly imprinted surface-enhanced Raman spectroscopy (SERS) sensor was developed for the selective capture and sensitive detection of tryptamine in foods. The SERS sensor exploited silver nanoparticle-decorated TiO2 (TiO2@Ag) substrates for Raman signal enhancement via synergistic effect of electromagnetic enhancement and photoinduced charge-transfer, whilst surface functionalization with the molecularly imprinted polymer ensured selective tryptamine capture. The SERS spectrum of tryptamine on the sensor closely matched that predicted by density functional simulations. The SERS intensity for tryptamine on the developed TiO2@Ag@MIP sensor increased linearly with the logarithm of the tryptamine concentration over the range of 10−6–10−2 mol L−1, with a LOD of 4.85 × 10−7 mol L−1. Tryptamine was detected in a spiked white vinegar sample, and its recoveries were in the range of 92.00%–111.40%. The SERS sensor could be used for the detection of tryptamine in actual samples.

Polarization-Resolved Electrochemiluminescence Sensor Based on the Surface Plasmon Coupling Effect of a Au Nanotriangle-Patterned Structure

This work focused on the construction of a nanomaterial-patterned structure for high-resolved ECL signal modulation. Due to the surface coupling effect, the different shapes and distribution states of surface plasmonic nanomaterials not only affect the luminescence intensity enhancement but also decide the electrochemiluminescence (ECL) polarization characteristics. Herein, tin disulfide quantum dots were synthesized via a solvothermal method as ECL emitters. Compared with other nanostructures, Au nanotriangle (Au NT) displayed both the localized surface plasmon resonance electromagnetic enhancement effect and the tip amplification effect, which had significant hot spot regions at three sharp tips. Therefore, self-assembled Au NT-based patterned structures with high density and uniform hot spots were constructed as ideal surface plasmonic materials. More importantly, the distribution states of the hot spots affect the polarization characteristics of ECL, resulting in directional ECL emission at different angles. As a result, a polarization-resolved ECL biosensor was designed to detect miRNA 221. Moreover, this polarization-resolved biosensor achieved good quantitative detection in the linear range of 1 fM to 1 nM and showed satisfactory results in the analysis of the triple-negative breast cancer patients' serum.

Strong Visible Light Absorption and Abundant Hotspots in Au-Decorated WO3 Nanobricks for Efficient SERS and Photocatalysis.

Metal/semiconductor hybrids show potential application in fields of surface-enhanced Raman spectroscopy (SERS) and photocatalysis due to their excellent light absorption, electric field, and charge-transfer properties. Herein, a WO3-Au metal/semiconductor hybrid, which was a WO3 nanobrick decorated with Au nanoparticles, was prepared via a facile hydrothermal method. The WO3-Au hybrids show excellent visible light absorption, strong plasmon coupling, high-performance SERS, and good photocatalytic activity. In particular, on sensing rhodamine B (RhB) under 532 nm excitation, bare WO3 nanobricks have a Raman enhancement factor of 2.0 × 106 and a limit of detection of 10–8 M due to the charger-transfer property and abundant oxygen vacancies. WO3-Au metal/semiconductor hybrids display a largely improved Raman enhancement factor compared to pure Au and WO3 components owing to the synergistic effect of electromagnetic enhancement and charge transfer. The Raman enhancement factor and limit of detection are further improved, reaching 5.3 × 108 and 10–12 M, respectively, on increasing the content of Au to 2.1 wt %, owing to the strong plasmon coupling between the Au nanoparticles. Additionally, the WO3-Au hybrids also exhibit excellent photocatalytic activity toward degradation of RhB under visible light irradiation. WO3-Au (2.1 wt %) possesses the fastest photocatalytic rate, which is 6.1 and 2.0 times that of pure WO3 nanobricks and commercial P25, respectively. The enhanced photocatalytic activity is attributed to the strong plasmon coupling and the efficient charge transfer between Au and WO3 nanobricks. The as-prepared materials show great potential in detecting and degrading pollutants in environmental treatment.