Raman Enhancement Research Articles

Quantifying the ultimate limit of plasmonic near-field enhancement

Quantitatively probing the ultimate limit of near-field enhancement around plasmonic nanostructures remains elusive, despite more than five decades since the discovery of surface-enhanced Raman scattering. Theoretical calculations have predicted an ultimate near-field enhancement exceeding 1000 using the best plasmonic material silver, but experimental estimations disperse by orders of magnitude. Here, we design a high-quality silver plasmonic nanocavity with atomic precision and precisely quantify the upper limit of near-field enhancement in ~1 nm junctions. A hot-spot averaged Raman enhancement of 4.27 × 1010 is recorded with a small fluctuation, corresponding to an averaged electric field enhancement larger than 1000 times. This result quantitatively delineates the ultimate limit of plasmonic field enhancement around plasmonic nanostructures, establishing a foundation for diverse plasmon-enhanced processes and strong light-matter interactions at the atomic scale.

Temperature dependence of gold nanostar particles morphology and its SERS application

ABSTRACT Gold nano-star particles (GNS) have broad application prospects in Raman enhancement, photovoltaic, and catalysis fields because of the hot spot effect of their tip structure. However, metal nanoparticles will accumulate heat during applications of high-power laser-focused irradiation, which may lead to the morphological degradation of the nanoparticles. In this paper, we have studied the effect of annealing temperature on the surface tip structure of GNS. Firstly, GNS with the multi-tip structure were synthesised by the two-step method, and GNS thin films were prepared by self-assembly technique without auxiliaries. By means of SEM characterisation, the film is found to be compact and uniform. Secondly, we systematically studied the morphology degradation of GNS at 100°C, 150°C, 200°C and 250°C. The results show that the tip of GNS does not change obviously until the temperature reaches 200°C. Then the four kinds of GNS films were used as surface-enhanced Raman scattering (SERS) substrates, and their Raman enhancement properties have been studied with adenine as the analyte, and stronger Raman enhancement effect can be found for the tip of nanoparticles. For a SERS substrate corresponding to an annealing temperature of 100°C, we have obtained the limit sensitivity of adenine molecule of 10−9 M. Finally, the surface electric field distribution and local resonance spectrum curves of four kinds of gold nanoparticles with different tip sizes were simulated theoretically by using the finite element method, and the results are consistent with the experimental data.

Experimental and Theoretical Comparison and Analysis of Surface-Enhanced Raman Scattering Substrates with Different Morphologies

The following research paper concerns the analysis and characterisation of commercially available surface-enhanced Raman scattering (SERS) substrates. SERS has long been a potentially very powerful method with a great deal of interest around it; however, there are still many obstacles which do not allow SERS to be easily applied to real-world detection and analysis problems. As such, research around the various types of substrates is ongoing, in the hope of streamlining and improving the Raman enhancement mechanism. Scanning electron microscope images were obtained for each of the three substrates, and their features and scales were described. Enhanced Raman spectra for Rhodamine B were obtained for a range of concentrations using each of the three substrates, and, in addition, surface enhancement maps are presented. Enhancement factors were calculated for the 1358 cm−1 peak of Rhodamine B. Complementing the experimental work, theoretical FEM modelling in COMSOL Multiphysics was performed, with the resulting calculations yielding an enhancement prediction adequately accurate to the real substrates.

Quantum mechanical effects in plasmonic sub-nanometer cavities formed by a tip and substrate structure

Enhancing local field intensity through light field compression is one of the core issues in surface plasmon-enhanced spectroscopy. The theoretical framework for the nanostructure composed of a tip and a substrate has predominantly relied on classical electromagnetic models, ignoring the electron tunneling effect. In this paper, we investigate the plasmonic near-field characteristics in the sub-nanometer cavity formed by the tip and the substrate using a quantum-corrected model. Additionally, we analyze the local electric field and Raman enhancement when hexagonal boron nitride (h-BN) monolayer is used as a decoupling layer for the nanocavity. The results indicate that classical electromagnetic theory fails to accurately describe the plasmonic electric field in smaller sub-nanometer gaps. When the gap is reduced to 0.32 nm, the quantum-corrected model shows that the local electric field in the sub-nanometer cavity is significantly reduced due to the tunneling current, aligning more closely with experimental results. Moreover, adding a high-barrier h-BN layer effectively prevents the occurrence of tunneling current, allowing for a strong local electric field even when the gap is less than 0.32 nm. The calculated maximum Raman enhancement reaches up to 15 orders of magnitude. Our research results provide a deep understanding of quantum mechanical effects in tip-enhanced spectroscopy systems, enabling the potential applications based on quantum plasmons in nanocavity.

Ultrasensitive Analysis of Escherichia coli O157:H7 Based on Immunomagnetic Separation and Labeled Surface-Enhanced Raman Scattering with Minimized False Positive Identifications.

It is a big challenge to monitor pathogens in food with high selectivity. In this study, we reported an ultrasensitive method for Escherichia coli O157:H7 detection based on immunomagnetic separation and labeled surface-enhanced Raman scattering (SERS). The bacterium was identified by heterogeneous recognition elements, monoclonal antibody (mAb), and aptamer. E. coli O157:H7 was separated and enriched by magnetic nanoparticles modified by mAb, and then a plasmonic nanostructure functionalized by aptamers with embedded Raman tags and interior gaps was utilized for further discrimination and detection. The selectivity was enhanced by two binding sites. The higher Raman enhancement was obtained by strong local electromagnetic field oscillation in the gap and the firm embedment of 4-mercaptopyridine (4-Mpy). Optimum experiments created that SERS signals of 4-Mpy at 1010 cm-1 had a good linearity with E. coli O157:H7 at a large range of 10 to 107 CFU/mL with a limit of detection of 2 CFU/mL. This method has great potential for on-site food pathogenic bacterial detection.

Multivalent Weak Protections Ultimately Enable Customizable DNA Grafting on Pristine Ag Colloids for Nanoplasmonics

Silver nanoparticles (AgNPs) have superior plasmonic properties surpassing other metals. However, a long‐standing difficulty in valence/density‐tunable DNA grafting of AgNPs disfavors their use in DNA‐directed nanoplasmonics. Herein a close‐to‐ideal surface protection of pristine AgNPs against various notorious stability issues of Ag is achieved based on multidentate weak nucleobase bindings of non‐programming FSDNA (fish sperm DNA). This further allows grafting of thiolated DNA with tunable valence/density on AgNPs. The end‐on format of the thiolated DNA grafts and the very thin FSDNA layer benefit DNA hybridization and plasmon coupling, respectively. Significantly promoted optical coupling and Raman enhancing are achieved. The compatibility of FSDNA‐capped AgNPs with Au enables DNA‐bonded symmetry‐broken Au‐Ag heterodimers with strong near‐field coupling and an easily seen Fano‐induced feature. Our work provides a treasured freedom of using AgNPs in DNA‐programmed, better‐behaving plasmonic devices.

Parallel Plate Capacitor Model at the Nanoscale for Stable and Gigantic SERS Activity of the 4-MBA@R-AuNP-4-MBA@R-AuNP System.

Selective use of ingredients out of a specific natural product (e.g., fruit, leaf, flower, or honey extract) or their mixture (e.g., bacteria, viruses, fungi, plants, etc.) by smart manipulation of precursors and reaction conditions to synthesize nanoparticles can provide us a low-cost, environmentally friendly route for their industrial-scale production. The presence of more than one active ligand (sourced natural product extract) on the surface not only makes them the most stable (electrostatically) and monodispersed (controlled kinetics) but also devoid of any external ligand-assisted aggregation. This empowered us to modify the surface of the nanoparticles in a monolayered fashion or to couple between nanoparticles through a ligand-assisted chemical coupling pathway to avoid their aggregation and hence to keep their nanoscale property intact. A metal-to-ligand charge transfer (MLCT) trajectory combined with electromagnetic field-induced coherent capacitive coupling between two nanoparticles was introduced to explain the gigantic Raman enhancement observed from these nanoparticles. As a model system, we have synthesized the nanoparticles from rose extract as the active ligand ingredient source for 2-phenyl ethanol, linalool, citronellol, nerol, geraniol, pyrogallol (C6H3(OH)3), and quercetin (3,3',4',5,7-pentahydroxyflavone) and the surface of the synthesized nanoparticles has been modified by 4-mercaptobenzoic acid (4-MBA) acting as a Raman tag. The obtained structural and spectroscopic data correlate well between our numerical and density functional theory (DFT)-based calculations to justify their gigantic SERS activity, which may lead us to propose an unexplored coherent capacitive coupling-based Raman enhancement mechanism.

Femtosecond laser-induced black silicon: a dual application in photodetection and surface-enhanced Raman scattering

A multifunctional structured silicon with enhanced optical and photoelectric properties has been processed by femtosecond (fs) laser in ambient air. The structured surface decorated with Au nanoparticles (NPs) exhibits excellent infrared absorption properties related to localized surface plasmon resonance (LSPR) coupled to microstructures. Over 75% absorption is achieved at 1550 nm, which is three orders of magnitude higher than that of unprocessed Si. The absorption enhancement results in increased photocurrent response in n + -n junction diodes, exhibiting a responsivity of 125 mA/W and an external quantum efficiency (EQE) of 10% at 1550 nm, for a bias voltage of 10 V. Moreover, the structured Si is also tested as a surface-enhanced Raman spectroscopy (SERS) substrate showing a strong signal under 638 nm excitation with Raman enhancement factors (EFs) as high as 108. In particular, the capability of detecting Raman analyte down to 10−11 M for RhB and 10−10 M for 4-MBA is demonstrated, simultaneously assessing the enhanced near-field due to the LSPR originating from the processed surface roughness leading to the valuable performances achieved by the n + -n junction diodes. These results offer a new path toward the elaboration of high-efficiency applications of Si structured surfaces in the fields of photoelectric sensing and detection.

Dual LSPR and CT synergy: 3D urchin-like Au@W18O49 enables highly sensitive in-situ SERS detection of dissolved furfural in insulating oils

Assessing the levels of furfural in insulating oils is a crucial technical method for evaluating the degree of aging and mechanical deterioration of oil-paper insulation. The surface-enhanced Raman spectroscopy (SERS) technique provides an effective method for enhancing the sensitivity of in-situ detection of furfural. In this study, a homogeneous three-dimensional (3D) urchin-like Au@W18O49 heterostructure was synthesized as a SERS substrate using a straightforward hydrothermal method. The origin of the superior Raman enhancement properties of the 3D urchin-like heterostructures formed by the noble metal Au and the plasmonic semiconductor W18O49, which is rich in oxygen vacancies, is analyzed experimentally in conjunction with density-functional theory (DFT) calculations. The Raman enhancement is further amplified by the remarkable dual localized surface plasmon resonance (LSPR) effect, which generates a strong local electric field and creates numerous "hot spots," in addition to the interfacial charge transport (CT). The synergistic effect of these factors results in the 3D urchin-like Au@W18O49 heterostructure exhibiting exceptionally high SERS activity. Testing the rhodamine 6G (R6G) probe resulted in a Raman enhancement factor of 3.41 × 10−8, and the substrate demonstrated excellent homogeneity and stability. Furthermore, the substrate was effectively utilized to achieve highly sensitive in-situ surface-enhanced Raman scattering (SERS) detection of dissolved furfural in complex plant insulating oils. The development of the 3D urchin-like Au@W18O49 heterostructure and the exploration of its enhancement mechanism provide theoretical insights for the advancement of high-performance SERS substrates.

Cerebrospinal fluid-induced stable and reproducible SERS sensing for various meningitis discrimination assisted with machine learning

Cerebrospinal fluid (CSF)-based pathogen or biochemical testing is the standard approach for clinical diagnosis of various meningitis. However, misdiagnosis and missed diagnosis always occur due to the shortages of unusual clinical manifestations and time-consuming shortcomings, low sensitivity, and poor specificity. Here, for the first time, we propose a simple and reliable CSF-induced SERS platform assisted with machine learning (ML) for the diagnosis and identification of various meningitis. Stable and reproducible SERS spectra are obtained within 30 s by simply mixing the colloidal silver nanoparticles (Ag NPs) with CSF sample, and the relative standard deviation of signal intensity is achieved as low as 2.1%. In contrast to conventional salt agglomeration agent-induced irreversible aggregation for achieving Raman enhancement, a homogeneous and dispersed colloidal solution is observed within 1 h for the mixture of Ag NPs/CSF (containing 110–140 mM chloride), contributing to excellent SERS stability and reproducibility. In addition, the interaction processes and potential enhancement mechanisms of different Ag colloids-based SERS detection induced by CSF sample or conventional NaCl agglomeration agents are studied in detail through in-situ UV–vis absorption spectra, SERS analysis, SEM and optical imaging. Finally, an ML-assisted meningitis classification model is established based on the spectral feature fusion of characteristic peaks and baseline. By using an optimized KNN algorithm, the classification accuracy of autoimmune encephalitis, novel cryptococcal meningitis, viral meningitis, or tuberculous meningitis could be reached 99%, while an accuracy value of 68.74% is achieved for baseline-corrected spectral data. The CSF-induced SERS detection has the potential to provide a new type of liquid biopsy approach in the fields of diagnosis and early detection of various cerebral ailments.

Two-Orders-of-Magnitude Enhancement of SERS Activity via a Simple Surface Engineering of Quasi-Metal Single-Crystal Frameworks.

Beyond noble metals and semiconductors, quasi-metals have recently been shown to be noteworthy substrates for surface enhanced Raman spectroscopy, and their excellent quasi-metal surface-enhanced Raman spectroscopy (SERS) sensing has demonstrated a wider range of application scenarios. However, the underlying mechanism behind the enhanced Raman activity is still unclear. Here, we demonstrate that surface hydroxyls play a crucial role in the enhancement of the SERS activity of quasi-metal nanostructures. As a demonstration material, quasi-metallic MoO2 single-crystal frameworks rich in surface hydroxyls have been shown to have 100 times higher SERS activity than MoO2 single-crystal frameworks without hydroxyl functionalization, with a Raman enhancement factor of up to 7.6 × 107. Experimental and first-principles density-functional theory calculation results show that the enhanced Raman activity can be attributed to an effective interfacial charge transfer within the MoO2/OH/molecule system.

Metallo-Supramolecular Helicates as Surface-Enhanced Raman Scattering (SERS) Substrates with High Tailorability.

The exploration of novel functionalized supramolecular coordination complexes (SCCs) can enable new applications in domains that include purification and sensing. In this study, employing a coordination-driven self-assembly strategy, we designed and prepared a series of benzochalcogenodiazole-based metallohelicates as high-efficiency charge transfer surface-enhanced Raman scattering (SERS) substrates, expanding the range of applications for these metallohelicates. Through structural modifications, including the substitution of single heteroatoms on ligands, replacement of coordinating metals, and alteration of ligand framework linkages, the Raman performance of these metallohelicates as substrates were systematically optimized. Notably, the SERS enhancement factors (EFs) of the metallohelicate-based SERS substrates were significantly enhanced to levels as high as 1.03 × 107, which rivals the EFs of noble metals devoid of "hot spots". Additionally, the underlying Raman enhancement mechanisms of these metallohelicates have been investigated through a combination of control experiments and theoretical calculations. This study not only demonstrates the utility of metallohelicates as SERS substrates but also offers insights and materials for the development of high-efficiency new charge transfer SERS substrates.

Metallo‐Supramolecular Helicates as Surface‐Enhanced Raman Scattering (SERS) Substrates with High Tailorability

The exploration of novel functionalized supramolecular coordination complexes (SCCs) can enable new applications in domains that include purification and sensing. In this study, employing a coordination‐driven self‐assembly strategy, we designed and prepared a series of benzochalcogenodiazole‐based metallohelicates as high‐efficiency charge transfer surface‐enhanced Raman scattering (SERS) substrates, expanding the range of applications for these metallohelicates. Through structural modifications, including the substitution of single heteroatoms on ligands, replacement of coordinating metals, and alteration of ligand framework linkages, the Raman performance of these metallohelicates as substrates were systematically optimized. Notably, the SERS enhancement factors (EFs) of the metallohelicate‐based SERS substrates were significantly enhanced to levels as high as 1.03 × 107, which rivals the EFs of noble metals devoid of "hot spots". Additionally, the underlying Raman enhancement mechanisms of these metallohelicates have been investigated through a combination of control experiments and theoretical calculations. This study not only demonstrates the utility of metallohelicates as SERS substrates but also offers insights and materials for the development of high‐efficiency new charge transfer SERS substrates.

SERS activity of silver nanoparticles and silver-modified 2D graphitic carbon nitride towards ciprofloxacin drug

Herein, silver nanoparticles (AgNPs) and silver-loaded graphitic carbon nitride (Ag@g-C3N4) nanocomposites have been synthesized and used as an effective surface-enhanced Raman scattering (SERS) substrates for the detection of low concentrations (10-14 M) of ciprofloxacin (CIP), a commonly bioactive medication used to treat bacterial illnesses. A combined approach of vibrational spectroscopy and density functional theory (DFT) has been developed to understand the possible modes of analyte (CIP) and SERS substrate (AgNPs and Ag@g-C3N4) interactions. Furthermore, it has been noticed that the behavior of drug molecules in terms of SERS response and energetics of interaction changed significantly when interacted with the noble metal AgNPs decorated onto the g-C3N4 framework in comparison to only AgNPs as substrate. The most prominent interaction scenario between AgNPs and CIP is likely to be through the –NH moiety of drug molecule with an interaction energy of −306 kcal/mol. Whereas, the CIP molecules adsorbed onto Ag@g-C3N4 nanocomposite were more flexible with interaction energy of −107 kcal/mol, suggesting a greater association of analyte with the skeletal modes of substrate leading to Raman enhancements in the low wavenumber region i.e. below 600 cm−1. Hence, the Ag@g-C3N4 nanocomposite-based SERS substrates investigated served two distinct spectral ranges, making them complementary of each other in terms of SERS detection of CIP. The characteristics of the computed frontier molecular orbitals indicated a pronounced amount of charge transfer between the drug and the substrate, highlighting the significance of the chemical mechanism of the overall process. These results represent a successful approach to have an extended spectral range that covers lower wavenumber shifts by applying simple and meaningful modifications to the normally utilized noble metal-based nanoparticles, which can lead to more effective and reliable detection of bioactive drugs.

Charge Transfer‐Induced SERS Enhancement of MoS2/Dopants Dependent on their Interaction Difference

Abstract2D transition metal dichalcogenide materials have attracted increasing attention as active surface‐enhanced Raman spectroscopy (SERS) platforms. In this study, the influence of n‐ and p‐type doping of exfoliated MoS2 (exMoS2) hybrids on the SERS performance is investigated, employing Rhodamine 6G (R6G) as a probe molecule. It is demonstrated that n‐doped exMoS2 hybrids (exMoS2 mixed with C60, graphene, and sodium dodecyl sulfate) exhibit enhanced SERS intensities, while p‐doping (exMoS2 mixed with TCNQ) resulted in inhibited SERS enhancement. A key discovery is the linear relationship between Raman enhancement of MoS2/dopant hybrids and the difference in their LUMO energy levels, which dictate the degree and direction of charge transfer. Interestingly, MC60‐4, a C60‐doped hybrid, deviates from the linear relationship, displaying remarkable SERS enhancement owing to its chemical interaction and unique Raman scattering activity. The findings provide critical insights into the SERS enhancement behavior of doped MoS2, facilitating precise tuning of SERS intensities by manipulating the MoS2 doping state.

Theoretical study of tip-enhanced photoluminescence of single molecule in nanocavity formed by apex protrusion and substrate

Tip-enhanced photoluminescence techniques, characterized by ultra-high detection sensitivity and spatial resolution, have exhibited unprecedented capabilities in exploring optoelectronic phenomena and unraveling intrinsic physical mechanism at the single-molecule level. To suppress the quenching of molecular luminescence and achieve high-resolution optical imaging, a rational design of the tip-substrate configuration is required. In this paper, we systematically investigate the tip-enhanced photoluminescence characteristics of single molecules located within the plasmonic nanocavity formed by the tip protrusion and the substrate from a theoretical perspective. The impacts of electron tunneling and electron-hole pair creation on localized electric field and quantum yield are discussed using the quantum correction model and nonlocal dielectric theory, respectively. The crucial roles of atomic-scale protrusion at the tip apex and the decoupling layer on the substrate in enhancing vertical and horizontal electric fields as well as quantum yields have been emphasized. The results indicate that in smaller sub-nanometer cavities, electron tunneling and nonlocal dielectric effects greatly weaken the electric field intensity and fluorescence quantum yield. Meanwhile, due to the sharp lightning rod effect, the presence of atomic-level protrusion at the tip apex can provide a strong and highly localized plasmonic field. We find that the added NaCl layer not only blocks charge transfer between molecules and the substrate but also effectively prevents fluorescence quenching. The maximum fluorescence and Raman enhancement factors near the tip apex approach up to 5 and 12 orders of magnitude, respectively, achieving sub-nanometer spatial resolution. Finally, compared to vertical electric field and dipole, sharp protrusion can excite a stronger horizontal electric field and couple with horizontal dipoles to yield a higher quantum yield, resulting in a three orders of magnitude higher in the fluorescence enhancement of horizontal dipole compared to the tip without protrusion. Our theoretical research not only confirms the experimental results of spectral enhancement with the proximity of the tip to the molecule in tip-enhanced photoluminescence, but also provides effective guidance for a deeper understanding of the mechanism of tip-enhanced fluorescence and Raman spectroscopy, as well as optimizing the experimental system.

Raman enhancement via double optical resonances in all-dielectric photonic crystal slabs

All-dielectric photonic structures are an important class of substrates in surface-enhanced Raman spectroscopy (SERS), utilizing optical resonant modes to significantly enhance the electromagnetic field and amplify the Raman signals. In this study, we demonstrate the double-resonance approach to realize significant Raman enhancement using all-dielectric photonic crystal (PhC) slab. The double-resonance condition is satisfied by designing optical resonant modes in photonic bands to match frequencies of both excitation laser and Raman signals. By the fabricated PhC slab, the significant enhancement for the Raman signal of silicon is demonstrated. The enhanced Raman signals exhibit a uniform distribution on the PhC slab. The method of Raman enhancement via double optical resonances can advance the field of all-dielectric SERS and holds potential for future SERS applications.

New screen-printed electrodes for Raman spectroelectrochemistry. Determination of p-aminosalicylic acid

BackgroundThe availability of new surface enhanced Raman scattering (SERS) substrates is essential to develop quantitative analytical methods. Electrochemistry is an easy, fast and reproducible methodology to prepare SERS substrates on screen-printed electrodes (SPEs). ResultsThis work proposes new SPEs based on a three-electrode system all made of silver. Using the same ink for the whole electrode system facilitates the fabrication process, reduces production costs, and leads to excellent analytical performance. The results showed that Raman enhancement depends strongly on the type of silver ink. To demonstrate the capabilities of the new electrodes developed, 4-aminosalicylic acid was determined in complex matrices and in the presence of strong interfering compounds such as salicylic acid and acetylsalicylic acid. The proposed analytical method is based on the electrochemical surface oxidation enhanced Raman scattering (EC-SOERS) strategy. AgCl nanocrystals are generated on the working electrode surface, which amplify the Raman signal of 4-aminosalicylic acid. Good figures of merit were obtained both in the absence and in the presence of the interfering compounds, achieving a correct estimation of a 4-aminosalicylic test sample in complex matrices. SignificanceThe new SPEs have been demonstrated to be very sensitive and reproducible which, together to the high specificity of the Raman signal, makes this methodology very attractive for chemical analysis.

Three dimensional noble metal-metal organic framework composite as SERS substrate for efficient capture and detection of pesticides

Hybrids of noble metal and metal-organic framework (MOF) are promising substrates for molecule sensing by surface enhanced Raman scattering (SERS) technique. However, most of these composite SERS substrates are zero-dimensional (0D) or two-dimensional (2D) structures, limiting their efficiency in adsorption and Raman enhancement. In this work, a new three-dimensional (3D) SERS substrate CC/ZnO-Ag@ZIF-8 composed of carbon cloth (CC) supported ZnO nanorod array decorated with AgNPs and coated with ZIF-8 layer was prepared for sensitive detection of pesticide. Compared with common 0D/2D substrates, the synergy of ZnO, AgNPs and MOF in 3D space achieved the highly efficient utilization of each component’s advantages, greatly enhancing the adsorption capacity to analyte and significantly amplifying the EM enhancement effect. Consequently, the 3D SERS substrate showed high SERS sensitivity to pesticide intermediate 4-ATP with a detection of limit (LOD) as low as 10−10 M, which is 3 orders of magnitude lower than its 2D counterpart CC/Ag@ZIF-8, or 2 orders of magnitude lower than that of CC/ZnO-Ag without MOF coating. Additionally, ZIF-8 coating also improves the stability, anti-interference ability and signal consistency of the substrate. Finally, the 3D CC/ZnO-Ag@ZIF-8 was successfully applied to the quantitative analysis of pesticide thiram in real lake water sample, which achieved a linear range of 10−5 to 10−9 M and a LOD of 1 nM. Such 3D noble metal-MOF hybrid SERS substrate with multiple merits in adsorption, Raman enhancement, stability and reproducibility holds great promise in environmental analysis.

Ag nanoparticle-embedded fish scales as SERS substrates for sensitive detection of forever chemical in real samples

Biological materials with unique surface properties provide a new avenue for fabricating green and sensitive SERS-active substrates. Herein, we present a simple but efficient method to prepare surface-enhanced Raman scattering (SERS) substrates by depositing silver nanoparticles (AgNPs) on fish scale substrates using an evaporation-induced self-assembly method (EISA). Characterization of the formed flexible Ag-impregnated substrate proved outstanding SERS sensitivity, uniformity, and reproducibility properties, with a Raman enhancement factor of 1.3 × 106 and a relative standard deviation of 6.4 %. Using this powerful fish scale substrate, a toxic environmental pollutant perfluorooctane sulfonamide (PFOSA) was indirectly detected in lake water, soil, and human urine samples. Due to its chemical structure, it is difficult to detect low concentrations of PFOSA in real samples. Interestingly, malachite green (MG) was smartly used as the Raman label for PFOSA detection in real samples. One of the main appeals is that the concentration of PFOSA can be correlated with a decrease in the SERS signal of MG in real samples. In conclusion, the strategy employed and reproducible SERS substrates may have diverse applications in clinical and environmental analyses.