Surface Enhanced Raman Spectroscopy Detection Research Articles

Ag Nanoparticles Modified Sea Urchin-like W18O49 Microstructures for Sensitive Surface Enhanced Raman Spectroscopy Detection

Surface-enhanced Raman scattering (SERS) has gained significant attention in various fields, including biomedical diagnostics, environmental monitoring, and food safety. This technique offers many advantages such as label-free detection and the ability to detect analytes at low concentrations. In this study, we present a variety of tungsten oxide (W18O49) microstructures as solid SERS substrates using various solvents realized by a simple hydrothermal approach. Among them, the well-defined sea urchin-like W18O49 microstructures support greater light scattering and confinement to enhance the SERS signal when compared to other W18O49 structures. The surface of well-defined sea urchin-like W18O49 microstructures was then modified with uniformly distributed silver nanoparticles (Ag NPs). The combination of the unique morphology of the Ag and sea urchin-like W18O49 microstructures (W18O49@Ag) led to improved detection capabilities for analytes such as rhodamine 6G (R6G) and thiram molecules. The SERS enhancement factor (EF) of sea urchin-like W18O49@Ag microstructures was estimated to be as high as 1.53×106 with the lowest detectable concentrations of 1nM and 1μM for R6G and thiram, respectively. Thus, the well-defined sea urchin-like W18O49@Ag microstructures are excellent choice to replace the pure noble metal SERS substrates in the fields of rapid detection and trace analysis due to their high sensitivity, repeatability, and long-term stability.

Rapid Sample Pretreatment Facilitating SERS Detection of Trace Weak Organic Acids/Bases in Complex Matrices.

Fast and efficient sample pretreatment is the prerequisite for realizing surface-enhanced Raman spectroscopy (SERS) detection of trace targets in complex matrices, which is still a big issue for the practical application of SERS. Recently, we have proposed a highly performed liquid-liquid extraction (LLE)-back extraction (BE) for weak acids/bases extraction in drinking water and beverage samples. However, the performance efficiency decreased drastically on facing matrices like food and biological blood. Based on the total interaction energies among target, interferent, and extractant molecules, solid-phase extraction (SPE) with a higher selectivity was introduced in advance of LLE-BE, which enabled the sensitive (μg L-1 level) and rapid (within 10 min) SERS detection of both koumine (a weak base) and celastrol (a weak acid) in different food and biological samples. Further, the high SERS sensitivity was determined unmanned by Vis-CAD (a machine learning algorithm), instead of the highly demanded expert recognition. The generality of SPE-LLE-BE for various weak acids/bases (2 < pKa < 12), accompanied by the high efficiency, easy operation, and low cost, offers SERS as a powerful on-site and efficient inspection tool in food safety and forensics.

Surface-Enhanced Raman Spectroscopy Detection for Fenthion Pesticides Based on Gold Molecularly Imprinted Polymer Solid-State Substrates.

Current label-free surface-enhanced Raman spectroscopy (SERS) assay for the detection and analysis of organophosphorus pesticides has achieved initial success, but the application still faces constraints of substrate portability and specificity. To this end, this paper demonstrates a method for portable, rapid, and specific detection of low concentrations of fenthion pesticides based on a solid substrate of gold nanoparticle monolayers combined with molecularly imprinted polymers (MIPs). The nano-monolayers were transferred to the surface of mercapto-silicon wafers by interfacial self-assembly technique to form a stable connection with S-Au bonds and, at the same time, prevent nanoparticles from dropping off during the surfactant removal process. Then, the fenthion MIPs were directly generated on the surface of the monolayer film by spin-coating with a pre-polymerization solution and ultraviolet-induced polymerization. Tests showed that the molecular imprint was able to accurately bind to fenthion, but not other molecules, in a mixture of structural analogs, achieving a low concentration detection of 10-8 mol/L. The composite substrate maintained a signal uniformity of a relative standard deviation (RSD) = 7.05% and a batch-to-batch reproducibility of RSD = 10.40%, making it a potential pathway for the extended application of SERS technology.

Light-Initiated Imprinted Membrane-Based Biomimetic SERS Sensor toward Selective Detection of Trace MC-LR.

Microcystin-LR (MC-LR) is a severe threat to human and animal health; thus, monitoring it in the environment is essential, especially in water quality protections. Herein, in this work, we synthesize PVDF/CNT/Ag molecular imprinted membranes (PCA-MIMs) via an innovative combination of surface-enhanced Raman spectroscopy (SERS) detection, membrane separation, and molecular-imprinted technique toward the analysis of MC-LR in water. In particular, a light-initiated imprint is employed to protect the chemical structure of the MC-LR molecules. Furthermore, in order to ensure the detection sensitivity, the SERS substrates are combined with the membrane via the assistance of magnetism. The effect of synthesis conditions on the SERS sensitivity was investigated in detail. It is demonstrated from the characteristic results that the PCA-MIMs present high sensitivity to the MC-LR molecules with excellent selectivity against the interfere molecules. Results clearly show that the as-prepared PCA-MIMs hold great potential applications to detect trace MC-LR for the protection of water quality.

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.

Quantitative detecting low concentration polystyrene nanoplastics in aquatic environments via an Ag/Nb2CTx (MXene) SERS substrate

In this study, the plasmonic Ag nanoparticles (Ag NPs) were uniformly anchored on the high conductivity Nb2CTx (MXene) nanosheets to construct an Ag/Nb2CTx substrate for surface-enhanced Raman spectroscopy (SERS) detection of polystyrene (PS) nanoplastics. The KI addition (0.15 mol/L), the volume ratio between substrate colloid and nanoplastic suspension (2:1), and the mass ratio of Nb2CTx in substrate (14%) on SERS performance were optimized. The EM hot spots of Ag/Nb2CTx are significantly enlarged and enhanced, elucidated by FDFD simulation. Then, the linear relationship between the PS nanoplastics concentration with three different sizes (50, 300, and 500 nm) and the SERS intensity was obtained (R2 > 0.976), wherein, the detection limit was as low as 10−4 mg/mL for PS nanoplastic. Owing to the fingerprint feature, the Ag/Nb2CTx-14% substrate successfully discerns the mixtures from two-component nanoplastics. Meanwhile, it exhibits excellent stability of PS nanoplastics on different detection sites. The recovery rates of PS nanoplastics with different sizes in lake water ranged from 94.74% to 107.29%, with the relative standard deviation (RSD) ranging from 2.88% to 8.30%. Based on this method, the expanded polystyrene (EPS) decomposition behavior was evaluated, and the PS concentrations in four water environments were analyzed. This work will pave the way for the accurate quantitative detection of low concentration of nanoplastics in aquatic environments.

Effective enrichment of trace exosomes for the label-free SERS detection via low-cost thermophoretic profiling

Exosome-based liquid biopsies possess great potential in monitoring cancer development However, current exosome detection biosensors require large exosome volumes, showing the weak detection sensitivity. Besides, these methods pay little attention to in situ analysis of exosomes, hence limiting the provision of more accurate clinically-relevant information. Herein, we develop an innovative label-free biosensor combining the low-cost thermophoretic enrichment method with the surface-enhanced Raman spectroscopy (SERS) detection. Based on the thermophoretic enrichment strategy, exosomes and gold nanoparticles can be enriched together into a small area with a scale of 500 μm within 10 min. The Raman signals of various exosomes derived from normal, cancerous cell lines and human serum are dynamically monitored in situ, with the limit of detection of 102–103 particles per microliter, presenting higher sensitivity compared with the similar label-free SERS detection. The spectral data set of different exosomes is applied to train for multivariate classification of cell types and to estimate how the normal exosome data resemble cancer cell exosome. The reliable classification and identification of different exosomes can be realized. The current biosensor is convenient, low-cost and requires small exosome volumes (∼3 μL), and if validated in larger cohorts may contribute to the tumor prediction and diagnosis.

Immunoassays: Analytical and Clinical Performance, Challenges, and Perspectives of SERS Detection in Comparison with Fluorescent Spectroscopic Detection.

Immunoassays (IAs) with fluorescence-based detection are already well-established commercialized biosensing methods, such as enzyme-linked immunosorbent assay (ELISA) and lateral flow immunoassay (LFIA). Immunoassays with surface-enhanced Raman spectroscopy (SERS) detection have received significant attention from the research community for at least two decades, but so far they still lack a wide clinical commercial application. This review, unlike any other review that we have seen, performs a three-dimensional performance comparison of SERS IAs vs. fluorescence IAs. First, we compared the limit of detection (LOD) as a key performance parameter for 30 fluorescence and 30 SERS-based immunoassays reported in the literature. We also compared the clinical performances of a smaller number of available reports for SERS vs. fluorescence immunoassays (FIAs). We found that the median and geometric average LODs are about 1.5-2 orders of magnitude lower for SERS-based immunoassays in comparison to fluorescence-based immunoassays. For instance, the median LOD for SERS IA is 4.3 × 10-13 M, whereas for FIA, it is 1.5 × 10-11 M. However, there is no significant difference in average relative standard deviation (RSD)-both are about 5-6%. The analysis of sensitivity, selectivity, and accuracy reported for a limited number of the published clinical studies with SERS IA and FIA demonstrates an advantage of SERS IA over FIA, at least in terms of the median value for all three of those parameters. We discussed common and specific challenges to the performances of both SERS IA and FIA, while proposing some solutions to mitigate those challenges for both techniques. These challenges include non-specific protein binding, non-specific interactions in the immunoassays, sometimes insufficient reproducibility, relatively long assay times, photobleaching, etc. Overall, this review may be useful for a large number of researchers who would like to use immunoassays, but particularly for those who would like to make improvements and move forward in both SERS-based IAs and fluorescence-based IAs.

SERS detection of surface-adsorbent toxic substances of microplastics based on gold nanoparticles and surface acoustic waves.

Microplastics adsorb toxic substances and act as a transport medium. When microplastics adsorbed with toxic substances accumulate in the body, the microplastics and the adsorbed toxic substances can cause serious diseases, such as cancer. This work aimed to develop a surface-enhanced Raman spectroscopy (SERS) detection method for surface-adsorbent toxic substances by forming gold nanogaps on microplastics using surface acoustic waves (SAWs). Polystyrene microparticles (PSMPs; 1 μm) and polycyclic aromatic hydrocarbons (PAHs), including pyrene, anthracene, and fluorene, were selected as microplastics and toxic substances, respectively. Gold nanoparticles (AuNPs; 50 nm) were used as a SERS agent. The Raman characteristic peaks of the PAHs adsorbed on the surface of PSMPs were detected, and the SERS intensity and logarithm of the concentrations of pyrene, anthracene, and fluorene showed a linear relationship (R2 = 0.98), and the limits of detection were 95, 168, and 195 nM, respectively. Each PAH was detected on the surface of PSMPs, which were adsorbed with toxic substances in a mixture of three PAHs, indicating that the technique can be used to elucidate mixtures of toxic substances. The proposed SERS detection method based on SAWs could sense toxic substances that were surface-adsorbed on microplastics and can be utilized to monitor or track pollutants in aquatic environments.

Constructing graphene oxide/Au nanoparticle cellulose membranes for SERS detection of mixed pesticide residues in edible chrysanthemum.

Edible chrysanthemum is widely cultivated and used as an important ingredient of medicine, tea and multifunctional food. During the planting of chrysanthemum, pesticides are extensively used for preventing plant diseases and insect pests. To ensure the food safety of edible chrysanthemum, rapid detection methods are urgently needed for on-site inspection. In this study, a graphene oxide/Au nanoparticle (GO/Au NP) cellulose substrate was prepared through layer-by-layer assembly of GO and Au NPs on a mixed cellulose ester membrane. Surface-enhanced Raman spectroscopy (SERS) detection of four types of organophosphorus and organosulfur pesticides was achieved by filtering the extracting solution through the substrate and analysing SERS spectra. Qualitative and semi-quantitative detection of fenthion, phoxim, isocarbophos and thiram was accomplished with the detection limits of 38.01, 8.13, 48.97 and 8.74 ng mL-1, respectively. A spiking experiment further demonstrated the feasibility of this method for rapid and on-site detection of mixed pesticides in chrysanthemum. This study provides a new approach for rapid detection of multiple hazardous substances in flowering and herbal plants.

A novel dual-mode aptasensor based on a multiple amplification system for ultrasensitive detection of lead ions using fluorescence and surface-enhanced Raman spectroscopy.

In this work, we develop a dual recycling amplification aptasensor for sensitive and rapid detection of lead ions (Pb2+) using fluorescence and surface-enhanced Raman scattering (FL-SERS). The aptasensor allows targeted cleavage of substrates through specifically binding with the Pb2+-dependent aptamer (M-PS2.M). Ultrasensitive detection of trace Pb2+ has been achieved using an enzyme-free nonlinear hybridization chain reaction (HCR) and the FL-SERS technique. The lower limit of detection (LOD = 3σ/k) is 0.115 pM in FL mode and 1.261 fM in SERS mode. The aptasensor is characterized by high reliability and specificity, among other things, to distinguish Pb2+ from other metal ions. In addition, the aptasensor can detect Pb2+ in actual water with good recovery. Compared with the single-mode aptasensor, the dual-mode aptasensor is characterized by high reliability, an extensive detection range, and high specificity.

Aggregation of Ag nanoparticle based on surface acoustic wave for surface-enhanced Raman spectroscopy detection of dopamine

BackgroundDopamine (DA), a vital neurotransmitter, plays a critical role in the human brain and relates to neuropsychiatric disorders such as Parkinson's disease and schizophrenia. Numerous studies have explored detection of such biomarkers through surface-enhanced Raman spectroscopy (SERS). However, most of the studies focused on SERS detection face significant challenges with plasmonic nanostructure development. Such challenges often include time-consuming processes, complex fabrication, specialized chemical labeling, poor reproducibility, and random hotspot generation. Therefore, the need for simple and rapid nanostructure development is evident in SERS. ResultsWe propose an innovative SERS-active sensing technique for 50 nm silver nanoparticle (AgNP) clustering based on surface acoustic wave (SAW). When a 1 μL droplet of AgNP colloid is dispensed onto the SAW-propagation zone, the AgNP cluster is deposited after the droplet completely evaporates, developing plasmonic nanogaps for SERS hotspot caused by spherical AgNP aggregation. By optimizing the SAW system through the hydrophobic treatment and modulation of the operational power, the SAW-induced AgNP clustering showed densely packed AgNP within a dot-like configuration (∼2200 AgNP μm−2), effectively preventing particle welding. The characterization of 4-mercaptobenzoic acid as a probe analyte revealed that concentrations as low as 1.14 pM was detected using our SAW-SERS system under 785 nm laser excitation. Moreover, DA was detected up to 4.28 nM with a determination of 0.99 (R2). SignificanceThis technique for AgNP clustering induced by SAW provides a rapid, in situ, label-free SERS sensing method with outstanding sensitivity and linearity. A mere act of dropping can create extensive plasmonic hotspots featuring nanogap of ∼1.5 nm. The SAW-induced AgNP clustering can serve as an ultrasensitive SERS-active substrate for diverse molecular detections, including neurotransmitter detection.

Plasmonic cellulose microfilament assisted SERS detection in microfluidics

Limited by the narrow enhanced area of nanoscale on the metal surface, the sensitivity of surface-enhanced Raman spectroscopy (SERS) detection in solution is usually much lower than the detection in a solid substrate, which is dramatic in microfluidics for online detection. In this work, a cellulose microfilament embraced by Ag nanoparticles, called plasmonic cellulose microfilament, is located in a microchannel for SERS detection in microfluidics. Benefiting from the congestion caused by the plasmonic cellulose microfilament in a microchannel, the trace molecule in the solution is much easier to gather in Ag nanoparticles for Raman enhancement. To obtain high sensitivity, the structure of plasmonic cellulose microfilament is optimized. The SERS spectra collected in this novel microfluidics demonstrate that the plasmonic cellulose microfilament presents a high sensitivity at 10−13 M and good reproducibility in SERS detection. In addition, automatic identification of urea presence or absence was achieved based on deep learning (DL) here. The results show excellent diagnostic accuracy (99 %), which suggests that a fast, label-free urea screening tool can be developed. These results point out this SERS microfluidics with plasmonic cellulose microfilament has a great application prospective in online SERS detection with high sensitivity.

Chemical-Chemical Redox Cycle Signal Amplification Strategy Combined with Dual Ratiometric Immunoassay for Surface-Enhanced Raman Spectroscopic Detection of Cardiac Troponin I.

Improving the sensitivity and reproducibility of surface-enhanced Raman spectroscopy (SERS) methods for the detection of bioactive molecules is crucial in biological process research and clinical diagnosis. Herein, we designed a novel SERS platform for cardiac troponin I (cTnI) detection by a chemical-chemical redox cycle signal amplification strategy combined with a dual ratiometric immunoassay. First, ascorbic acid (AA) was generated by enzyme-assisted immunoreaction with a cTnI-anchored sandwich structure. Then, oxidized 4-mercaptophenol (ox4-MP) was reacted with AA to produce 4-mercaptophenol (4-MP). Quantitative analysis of cTnI was realized by a Raman signal switch between ox4-MP and 4-MP. Specifically, AA could be regenerated by reductant (tris(2-carboxyethyl) phosphine, TCEP), which in turn produced more signal indicator 4-MP, causing significant signal amplification for cTnI analysis by SERS immunosensing. Moreover, a dual ratiometric-type SERS method was established with the intensity ratio I1077/I822 and I633/I822, which improved the reproducibility of the cTnI assay. The excellent performance of the chemical-chemical redox cycle strategy and ratio-type SERS assay endows the method with high sensitivity and reproducibility. The linear ranges of cTnI were 0.001 to 50.0 ng mL-1 with detection limits of 0.33 pg mL-1 (upon I1077/I822) and 0.31 pg mL-1 (upon I635/I822), respectively. The amount of cTnI in human serum samples yielded recoveries from 89.0 to 114%. This SERS method has remarkable analytical performance, providing an effective approach for the early diagnosis of cardiovascular diseases, and has great latent capacity in the sensitive detection of bioactive molecules.

Designing of a functional paper-tip substrate for sensitive surface-enhanced Raman spectroscopy (SERS) detection

A simple and flexible fabrication method of paper SERS substrate was developed by nanoparticles (NPs) droplet self-assembly at the paper tip with a temperature gradient (PTTG). We turned the drawback of the coffee ring effect into an effective way of preparing paper SERS substrate. When the NPs droplets were continuously dripped onto the PTTG, NPs were densely and uniformly distributed at the paper-tip front based on the combination of gravity and the coffee ring effect, which could achieve 91.2-fold improvement of SERS performance compared to a flat filter paper. Meanwhile, the analytes could also be enriched at the paper-tip front, which could achieve 9.3-fold signal enhancement compared to the paper-tip tail. Thus, the PTTG realized an excellent signal amplification for SERS detection. The paper-tip SERS substrate combined with a portable Raman spectrometer yielded an excellent analytical enhancement factor of 1.15 × 105 with the detection limit of 10 nM Rhodamine 6G (R6G). The whole fabrication procedure was completed within 2 h, and the paper-tip substrate showed a satisfactory substrate-to-substrate reproducibility with a relative standard deviation (RSD) of 5.13% (n = 10). It was successfully applied for quantitatively detecting real samples of oxytetracycline and malachite green with recoveries of 83.84–105.25% (n = 3). Meanwhile, we further evaluated the SERS performance of the PTTG using a laboratory-based Raman spectrometer, and it could realize the detection as low as 10 pM R6G. The proposed paper-tip substrate would offer a promising potential application for the on-site SERS analysis of food safety and environmental health.

Monolithic 3D structural-substrate SERS sensing platform for ultrasensitive and highly-specific analysis of trace bisphenol A

Constructing advanced substrates with excellent features is promising for sensitive surface-enhanced Raman spectroscopy (SERS) detection. Here a novel capillary monolithic 3D structural-substrate SERS platform with Au@cDNA@Ag@Cyanine 3-aptamer nanoparticles (Au@cDNA@Ag@Cy3-Apt NPs) was fabricated for rapid, highly specific profiling of ultra-trace Bisphenol A (BPA). The proposed SERS platform combined both in-capillary SERS and aptamer-affinity recognition strategies, in which the superior SERS properties of Au–Ag NPs, aptamer selectivity, and the advantages of capillary monolith were integrated. A 3D hierarchically porous network was constructed in the monolithic column, which was endowed with rich hotspots for SERS, rapid sample permeation, and better analysis efficiency than most plane-shaped SERS modes. By varying the amount of Ag+ precursor, the Ag-shell thickness on SERS was finely tuned to guarantee Cy3 label in proximity to the plasmonic surface. Based on the biorecognition of aptamer, the selective identification of BPA occurred and exhibited a significant change in SERS intensity without obvious interference. As a result, the monolithic SERS platform featured facile operation, excellent specificity, and rapid analysis (10 min, much less than the solution-based or planar substrate SERS modes). Ultra-high sensitivity and robust reproducibility for BPA analysis was achieved with a low limit of detection (LOD) at 9.12 × 10-4 ng/L. The feasibility of this SERS platform for monitoring BPA in water and milk samples was also validated. This work lights a new access to capillary monolithic SERS-sensing platform for ultrasensitive and specific analysis of BPA.

Dark background–surface enhanced Raman spectroscopic detection of nanoplastics: Thermofluidic strategy

This study aims to develop a cost-effective and time-efficient method for detecting nanoplastics, which have recently garnered significant attention due to their potential harmful impact on the water environment (XiaoZhi, 2021; Gigault et al., 2021; Mitrano et al., 2021; Ferreira et al., 2019). Although several techniques are available to accumulate data on microplastics, there is currently no universally accepted analytical technique for detecting nanoplastics (Gigault et al., 2021; Mitrano et al., 2021; Mitrano et al., 2019; Cai et al., 2021a; Allen et al., 2022). In this study, we have developed a substrate that exhibits Surface-enhanced Raman scattering (SERS) (Zhou et al., 2021; Lv et al., 2020; Lê et al., 2021; Hu et al., 2022; Chang et al., 2022; Yang et al., 2022; Xu et al., 2020; Jeon et al., 2021; Lee and Fang, 2022; Vélez-Escamilla and Contreras-Torres, 2022; Liu et al., 2022; Xie et al., 2023) activity over a large area and a dark background in optical (darkfield mode) vision, enabling the detection of sparkling nanoplastics on the substrate. This darkfield-based strategy allows for the point-by-point detection of single nanoplastics, offering cost and time-saving advantages over other resource-intensive analytical techniques. Our findings reveal the presence of PP nanoplastics in commonly used laboratory equipment, individual PE nanoplastics from a hot water-contained commercial paper cup, and the first detection of natural nanoplastics in coastal seawater. We believe that this technique will have a universal application in establishing a global map of nanoplastics and advancing our understanding of the environmental life cycle of plastics.

Selective surface enhanced Raman detection and effective photocatalytic degradation of sulfonamides antibiotic based on a flexible three-dimensional chitosan/carbon nitride/silver substrate

The prevalence of sulfonamide residues in aquatic environments poses serious environmental risks, and the sensitive detection and effective degradation of sulfonamides have attracted widespread attention. Here, the environmentally friendly chitosan (CS)/carbon nitride (CN) with three-dimensional porous structure is fabricated by freeze-drying method, and subsequently a new bifunctional flexible substrate (CS/CN/Ag) is prepared by anchoring of small sized AgNPs (6 ∼ 12 nm) on CS/CN. Importantly, the CS/CN/Ag substrate shows high adsorption capacity (∼ 83.06%) for sulfamethoxazole (SMX) solution within 20 mins and the limit of detection can be as low as 7.46 × 10−9 mol·L−1 with an enhancement factor of 3.3 × 105. Also, the CS/CN/Ag substrate displays highly selective for surface-enhanced Raman spectroscopy (SERS) detection of sulfonamides and also shows excellent SERS response for SMX in hospital wastewater samples. In addition, the photocatalytic degradation efficiency of SMX could reach as high as 99.22% within 20 mins of irradiation and the CS/CN/Ag still maintains outstanding photocatalytic performance after six cycles. Moreover, the Ag content in the CS/CN/Ag substrate is only 2.35%, and also the CS/CN/Ag exhibits good uniformity, repeatability, recyclability and stability. Therefore, this flexible and cost-effectively substrate of CS/CN/Ag shows great potential for the simultaneous SERS detection and photocatalytic degradation of pollutants in actual wastewater samples.

Flexible plasmonic nanoparticle-on-a-mirror metasurface-enabled substrates for high-quality surface-enhanced Raman spectroscopy detection

Surface-enhanced Raman scattering (SERS) technology with the advantages of ultra-high sensitivity, non-destructive analysis, and quick measurement for molecular detection applications is receiving increasing attention. However, traditional rigid SERS substrates face challenges in in-suit conformal detection and weak structure coupling effect for real-life applications. Here we report a flexible polydimethylsiloxane (PDMS) substrate loaded with plasmonic nanoparticle-on-a-mirror (NPOM) metasurface for SERS detection that featured outstanding sensitivity, uniformity, repeatability, and excellent mechanical flexibility. The upper multilayered NPOM metasurface can be fabricated in a single-step process by ion beam sputtering of various targets. This NPOM configuration consists of dense silver nanoparticles over a silver mirror, separated by a SiO2 spacer layer, which can realize near-total power absorption and exhibits superior SERS ability. The bottom PDMS layer for support can provide excellent mechanical properties. In the test, the as-prepared NPOM/PDMS substrates show high SERS performance in detecting crystal violet and chlorpyrifos molecules. This flexible metasurface SERS substrate promises to provide an in-suit and efficient approach for trace substance detection.

Zr-MOF-Induced Smart Accumulation Enables Surface-Enhanced Raman Spectroscopic Detection of Dioxin at ppt Level in Food Samples.

The fast and economical detection of trace polychlorinated dibenzo-p-dioxins (PCDDs) in food samples by current mass spectrum-based methods is hindered by tedious sample preparation and bulky & expensive analytical instruments. Surface-enhanced Raman spectroscopy (SERS) successfully detects many organic pollutants in foods but not dioxins because the employed metal nanoparticles weakly adsorb hydrophobic PCDDs. Herein, we report the detection of PCDDs in milk with SERS for the first time using a bifunctional substrate consisting of Au nanoparticles embedded in a zirconium-based metal-organic framework shell (AuNP/Zr-MOF). 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), as the most toxic PCDD, is detected as low as 1.2 parts per trillion (ppt) in real milk samples with massive interfering substances in 30 min, which is the lowest among all reported methods. The aromatic rings of Zr-MOF promote the smart accumulation of TCDD through π-π interactions, and Au-Cl interactions drive TCDD onto Au surfaces. Zr-MOF shells with pore sizes of 12.7 and 20 Å block the accessibility of larger interfering molecules. A one-step apparatus and protocol are established to be superior to traditional methods in terms of time and cost. This work provides new insight into a rational screening method for the detection of persistent organic pollutants in a real sample matrix.