Raman Enhancement Research Articles

Charge-transfer-driven ultrasensitive SERS sensing in a two-dimensional titanium carbonitride MXene.

Two-dimensional (2D) MXenes stand out as promising platforms for surface-enhanced Raman scattering (SERS) sensing owing to their metallic feature, various compositions, high surface area, compatibility with functionalization, and ease of fabrication. In this work, we report a high-performance 2D titanium carbonitride (Ti3CN) MXene SERS substrate. We reveal that the abundant electronic density of states near the Fermi level of Ti3CN MXene boosts the efficiency of photo-induced charge transfer at the interface of Ti3CN/molecule, resulting in significant Raman enhancement. The SERS sensitivity of Ti3CN MXene is further promoted through a 2D morphology regulation and molecular enrichment strategies. Moreover, prohibited drugs are detectable on this substrate, presenting the potential of trace-amount analysis on Ti3CN MXene. This work provides a deep insight of the SERS mechanisms of Ti3CN MXene and broadens the practical application of transition metal carbonitride MXene SERS substrates.

Polymer composite membranes as SERS substrate materials: Recyclable and highly stable

Surface-enhanced Raman spectroscopy (SERS), as an emerging molecular-level detection technology, has attracted considerable research attention, especially in the context of substrate materials exhibiting Raman enhancement effects. Membrane materials, owing to their commendable uniformity, stability, and ease of modification, hold a pivotal position in the landscape of SERS substrate materials. However, existing SERS substrates based on membrane materials have limited adaptability to a spectrum of extreme environments, including but not limited to high or low pH, elevated salinity, and corrosive solutions. Additionally, SERS substrate materials are synonymous with “waste” and “high investment” because of their inherent disposable nature. This study introduces a pioneering approach, presenting a polymer composite membrane founded on epoxy resin, cellulose paper, and nanometal particles as a novel SERS substrate material. Given the outstanding stability of epoxy resin, the substrate material exhibits normal functionality in environments ranging from −80 ℃ to 100 ℃, with pH levels spanning 1 to 13, and in highly acidic solutions (concentration ≤3 %) and highly alkaline solutions (concentration ≤0.1 M). Moreover, the cleanability inherent in the polymer composite membrane renders the substrate material recyclable. Experimental findings reveal that even after six repeated uses, the substrate material sustains a stable Raman signal enhancement effect. The integration of recyclability and heightened stability makes this SERS substrate material a promising candidate for real-time monitoring and batch testing in chemical production processes or other complex environments.

Thiol-functionalized mesoporous silica-embedded AuNPs with highly sensitive substrates for surface-enhanced Raman scattering detection

Surface-enhanced Raman spectroscopy (SERS) provides a fast, simple, and label-free approach that can directly detect various analytes attached to SERS substrates and provide qualitative and quantitative information based on the SERS spectra of the analyte. The signal enhancement provided by noble metal particles allows us to achieve high sensitivity and good stability even at low concentrations in water quality testing. Over the past decade, SERS has become increasingly popular in the detection field, highlighting its significant application potential. However, the signal enhancement of single AuNPs is inferior to that of AgNPs, but we can achieve an overall enhancement by uniformly arranging multiple AuNPs. The hot-spot effect, which is crucial for Raman signal enhancement, occurs only when NMNPs are within a specific distance. However, when noble metal particles come into contact with each other, the enhancement effect of the hot spot disappears. Therefore, in this study, AuNPs@MPS-SH substrates with surface-enhanced Raman scattering (SERS) activity were successfully synthesized by immobilizing AuNPs on thiol-functionalized mesoporous silica (MPS-SH). MPS nanospheres with tailored pore size and surface-bound -SH groups were synthesized for the controlled embedding of Au nanoparticles (AuNPs). By adjusting the ratio of reactants, uniform AuNP dispersion and strong MPS-AuNP interactions were achieved. This optimized structure creates localized surface plasmon resonance (LSPR) hotspots, significantly enhancing the surface-enhanced Raman scattering (SERS) effect for ultrasensitive analyte detection. Transmission electron microscopy (TEM) revealed that the average diameter of MPS nanoparticles is 260 nm, with a pore size of 8 nm. Optimal Raman enhancement was achieved at an AuNPs concentration of 2.6 × 1018 particles/mL. The lowest detection limit concentration for Rhodamine 6G was below 10−6 M, while for uremic toxin (urea) it was below 10−3 M. The ability to directly detect low concentrations by mixing with the analyte demonstrates the ultra-high sensitivity and label-free detection potential of this study in the fields of water quality and disease detection.

Cyano-Hydrol green derivatives: Expanding the 9-cyanopyronin-based resonance Raman vibrational palette

9-cyanopyronin is a promising scaffold that exploits resonance Raman enhancement to enable sensitive, highly multiplexed biological imaging. Here, we developed cyano-Hydrol Green (CN-HG) derivatives as resonance Raman scaffolds to expand the color palette of 9-cyanopyronins. CN-HG derivatives exhibit sufficiently long wavelength absorption to produce strong resonance Raman enhancement for near-infrared (NIR) excitation, and their nitrile peaks are shifted to a lower frequency than those of 9-cyanopyronins. The fluorescence of CN-HG derivatives is strongly quenched due to the lack of the 10th atom, unlike pyronin derivatives, and this enabled us to detect spontaneous Raman spectra with high signal-to-noise ratios. CN-HG derivatives are powerful candidates for high performance vibrational imaging.

Characteristic substance analysis and rapid detection of bacteria spores in cooked meat products by surface enhanced Raman scattering based on Ag@AuNP array substrate

BackgroundBacterial spores are the main potential hazard in medium- and high-temperature sterilized meat products, and their germination and subsequent reproduction and metabolism can lead to food spoilage. Moreover, the spores of some species pose a health and safety threat to consumers. The rapid detection, prevention, and control of bacterial spores has always been a scientific problem and a major challenge for the medium and high-temperature meat industry. Early and sensitive identification of spores in meat products is a decisive factor in contributing to consumer health and safety. ResultsIn this study, we developed a novel and stable Ag@AuNP array substrate by using a two-step synthesis approach and a liquid-interface self-assembly method that can directly detect bacterial spores in actual meat product samples without the need for additional in vitro bacterial culture. The results indicate that the Ag@AuNP array substrate exhibits high reproducibility and Raman enhancement effects (1.35 × 105). The differentiation in the Surface enhanced Raman scattering (SERS) spectra of five bacterial spores primarily arises from proteins in the spore coat and inner membrane, peptidoglycan of cortex, and Ca2⁺-DPA within the spore core. The correct recognition rate of linear discriminant analysis for spores in the meat product matrix can reach 100 %. The average recovery accuracy of the SERS quantitative model was at around 101.77 %, and the limit of detection can reach below 10 CFU/mL. SignificanceIt provides a promising technological strategy for the characteristic substance analysis and timely monitoring of spores in meat products.

Functionalized Single Crystal Perovskite Materials for SERS and Their Potential Detection Applications.

Recent advances in detection and diagnostic tools have improved understanding and identification of plant physiological and biochemical processes. Effective and safe Surface Enhanced Raman Spectroscopy (SERS) can find objects quickly and accurately. Raman enhancement amplifies the signal by 1014-1015 to accurately quantify plant metabolites at the molecular level. This paper shows how to use functionalized perovskite substrates for SERS. These perovskite substrates have lots of surface area, intense Raman scattering, and high sensitivity and specificity. These properties eliminate sample matrix component interference. This study identified research gaps on perovskite substrates' effectiveness, precision, and efficiency in biological metabolite detection compared to conventional substrates. This article details the synthesis and use of functionalized perovskites for plant metabolites measurement. It analyzes their pros and cons in this context. The manuscript analyzes perovskite-based SERS substrates, including single-crystalline perovskites with enhanced optoelectronic properties. This manuscript aims to identify this study gap by comprehensively reviewing the literature and using it to investigate plant metabolite detection in future studies.

Two-dimensional tellurium nanosheet: A novel sensitive and stable surface-enhanced Raman scattering substrate

Two-dimensional (2D) materials with merits such as low cost, high chemical inertness and tunable electronic structure have become favorable candidates for next generation of surface-enhanced Raman scattering (SERS) platforms. However, the SERS sensitivity of 2D materials still needs to be improved and the large-scale synthesis methods should be developed to meet the requirements of practical applications. In this work, we explored performances of a brand-new SERS substrate made of 2D Te nanosheets (NSs), which exhibited thickness-dependent SERS properties, with thinner nanosheets yielding stronger SERS intensity. Under optimized conditions, the limits of detection (LODs) reached the order of 10−9 M combining with SERS enhancement factors (EFs) as high as 105 for copper phthalocyanine (CuPc) and methylene blue (MB). This impressive SERS performance could be attributed to the strong interaction and photoinduced charge transfer (PICT) processes between 2D Te NSs and molecules. Benefiting from the appropriate positions of valence band (VB) and conduction band (CB), the 2D Te NSs showed significant Raman enhancement for various molecules. Furthermore, the 2D Te NSs exhibited good air-stability for up to ∼2 months. These outstanding performances establish 2D Te NSs as a favorable SERS detection material with enormous potential in practical applications.

Preparation of Flower-like Nanosilver Based on Bioderived Caffeic Acid for Raman Enhancement and Dye Degradation.

In this study, a simple, green, and low-cost room temperature synthesis of broccoli-like silver nanoflowers (AgNF) with a particle size of about 300-500 nm was developed using plant-derived caffeic acid as a reducing agent and polyvinylpyrrolidone as a dispersant under ultrasound assistance. The flower clusters covered by small nanocrystals of 20-50 nm significantly enhance the electromagnetic field signals. AgNF was deposited on the surface of silicon wafers as a surface-enhanced Raman spectroscopy sensor for the detection of probe molecules such as rhodamine 6G (R6G) and malachite green with high sensitivity, homogeneity, and reproducibility. AgNF was deposited on cotton fabrics in the form of composites to catalyze the degradation of dye pollutants such as R6G, MG, and methyl orange in the presence of sodium borohydride. 0.1 g of AgNF/cotton fabric could assist 15 mmol/L NaBH4 to achieve over 90% degradation of various dyes as well as a high concentration of dyes in 12 min with good reusability and recyclability. The AgNF synthesized in this work can not only monitor the type and amounts of pollutants (dyes) in wastewater but also catalyze the rapid degradation of dyes, which is expected to be valuable for industrial applications.

A new strategy for constructing 3D hybrid graphene/Au/rectangular pyramids PMMA on a flexible SERS substrate for trace molecule detection

Surface enhanced Raman spectroscopy (SERS) has attracted interest in the fields of hazardous substance detection and food safety. However, its limited sensitivity and SERS signal consistency inhibit the widespread use of SERS technology. Herein, a novel approach for the fabrication of a graphene/Au NP/rectangular pyramid PMMA hybrid SERS substrate (Gr/Au/RP PMMA) with high uniformity and sensitivity is presented. The Gr/Au/RP PMMA substrate is machined by indentation firstly, then following wet etching of the copper substrate. The Raman enhancement of Gr/Au/RP PMMA is studied in terms of both electromagnetic enhancement and chemical enhancement. The field strength enhancement of the obtained Gr/Au/RP PMMA substrate is more than 4.9 times greater than that of the Gr/Au/flat PMMA substrate, established using a COMSOL simulation. By actively modulating the machining parameters on a Cu-Gr surface, the number of Gr layers, as well as the Gr/Au/RP PMMA topography, can be controlled, which can effectively influence the performance of the SERS substrate. Moreover, compared with other SERS substrates, including Gr/Au/RP PMMA, Gr/Au/flat PMMA, Au/Gr/RP Cu, Gr/RP PMMA, and Au/RP PMMA, the Raman intensities of R6G were strongest on the Gr/Au/RP PMMA. In addition, the minimum detectable concentrations of paraquat (PQ) and 2,4-d used in situ detection were 10−8 M and 10−6 M, respectively, after being covered with the Gr/Au/RP PMMA flexible substrate. To test its practical applicability with actual fruit surfaces, the Gr/Au/RP PMMA flexible substrate was used for the in situ SERS detection of PQ on apples. Clear Raman peaks of 10−7 M PQ were detected on the apple surface.

Construction of composite SERS substrate based on black phosphorus/mesoporous ZIF-67 and its selective monitoring of food additives

Semiconductor-based surface-enhanced Raman scattering (SERS) dependent on chemical mechanism has shown favorable selective enhancement and recognition capabilities. However, the limited Raman enhancement capability of conventional semiconductor-based still remains a great challenge in the effective monitoring of trace molecules in a practical complex environment. In this context, a novel two-dimensional composite semiconductor substrate was developed by in-situ growing reticular ZIF-67 mesoporous film upon black phosphorus (BP) nanosheets. An attractive synergistic chemical enhancement was triggered attributed to the efficient continued charge transfer process in the BP/ZIF-67 system. Particularly, a selective SERS enhancement of food additive molecules with different orbital structures was found owing to the coupling degree of intrinsic molecular resonance and photo-induced charge transfer. A sensitive detection of lycopene in beverage samples with a high recovery rate was finally realized by the BP/ZIF-67 composite substrate, which exhibited great potential in practical molecular selective recognition.

Strong‐Coupling‐Enhanced Raman Spectroscopy (SCERS) in a Cascade Microsphere‐Cavity

AbstractSurface‐enhanced Raman spectroscopy (SERS) is a powerful optical technique with high sensitivity to identify analytes down to a single molecule by fingerprinting vibrational information. The strong coupling in microcavities for supermodes with promoted quality factors demonstrates the capability to boost the interaction between photons and molecules for nonlinear effects. Here a strong‐coupling cascade microsphere‐cavity (MC) achieving spontaneous Raman enhancement is reported, for the first time. The cascade MC is composed of two size‐mismatched microspheres, both of which support optical whispering‐gallery modes (WGMs) with significantly different free‐space ranges. The strong coupling between the supported WGMs in the microspheres can be achieved when the quasi‐vernier effect of resonant modes occurs, by which the energy splitting is up to 4 meV. The fast energy transfer between the size‐mismatched MCs therefore increases the quality factor up to 2.1 × 103 for the upper supermode branch. The strong‐coupling cascade MC structure provides an extra enhancement channel for the Au‐based SERS substrate, demonstrating an enhancement factor of Raman intensity (EFRI) up to 2.6 × 1010 for the limit of detection (LoD) down to 10−12 M of 4‐aminothiophenol (4‐ATP). The strong‐coupling cascade MC substrates also exhibit the versatility for identification of multiple analytes for high‐performance Raman trace‐detection applications.

Nanoscale Kirkendall effect induced void formation in Au–Ag nanostructures and their application as SERS substrate

Triangular-shaped silver nanostructures were synthesized via a seed-mediated two-step method. A galvanic replacement reaction coupled with the Kirkendall effect was employed to transform Ag nanostructures into porous Au–Ag structures having voids at the nanoscale. Compared with previous reports, the medium and the binding agent used in the synthesis of silver nanoparticles employed as templates play a vital role in determining the extent of nanoscale voids formed due to the Kirkendall effect. Raman activity of these porous structures was tested with crystal violet as the probe molecule, and it was found that the Raman enhancement factor varies with cathode concentration.

Tuning the Fermi Level of Graphene by Two-Dimensional Metals for Raman Detection of Molecules.

Graphene-enhanced Raman scattering (GERS) offers great opportunities to achieve optical sensing with a high uniformity and superior molecular selectivity. The GERS mechanism relies on charge transfer between molecules and graphene, which is difficult to manipulate by varying the band alignment between graphene and the molecules. In this work, we synthesized a few atomic layers of metal termed two-dimensional (2D) metal to precisely and deterministically modify the graphene Fermi level. Using copper phthalocyanine (CuPc) as a representative molecule, we demonstrated that tuning the Fermi level can significantly improve the signal enhancement and molecular selectivity of GERS. Specifically, aligning the Fermi level of graphene closer to the highest occupied molecular orbital (HOMO) of CuPc results in a more pronounced Raman enhancement. Density functional theory (DFT) calculations of the charge density distribution reproduce the enhanced charge transfer between CuPc molecules and graphene with a modulated Fermi level. Extending our investigation to other molecules such as rhodamine 6G, rhodamine B, crystal violet, and F16CuPc, we showed that 2D metals enabled Fermi level tuning, thus improving GERS detection for molecules and contributing to an enhanced molecular selectivity. This underscores the potential of utilizing 2D metals for the precise control and optimization of GERS applications, which will benefit the development of highly sensitive, specific, and reliable sensors.

Highly ordered nanocavity as photonic-plasmonic-polaritonic resonator for single molecule miRNA SERS detection

Strong light-matter coupling between molecules and electromagnetic field lead to the formation of hybrid polaritonic states for surface enhanced Raman scattering (SERS) detection. However, owing to the inefficient interaction between zero-point fluctuations of photons/plasmons and molecular electronic transitions, the Raman enhancement is limited in relative low levels. Here, we propose and fabricate a TiOx/Cu2-xSe/R6G nanocavity based photonic-plasmonic-polaritonic resonator for single molecular SERS detection. Through precisely matching the energy levels of illuminated photon, generated plasmon, and molecular polariton, an extremely high Raman enhancement factor of 2.6 × 109 is implemented. The rationally designed SERS substrate allows sensitive detection of miRNA-21 in single molecular level with a detection limit of 1.58 aM. The hybrid SERS mechanism both from electromagnetic and chemical perspectives in this photonic-plasmonic-polaritonic resonance strategy provides insight into polaritonic semiconductor systems, thus paving the way for new experimental possibilities in light-matter hybrids.

Preparation of Langmuir-Blodgett composite films based on sericin protein and silk fibroin with good surface-enhanced Raman scattering and photovoltaic properties

In this work, the self-assembled films of sericin protein (SP), silk fibroin (SF), and dye molecules were prepared by the Langmuir-Blodgett (LB) technique. Surface-enhanced Raman scattering (SERS) experiments demonstrated that the SP/saffron T (ST)-80 and SF/ST-60 composite LB films exhibited good Raman enhancement characteristics with enhancement factors (EFs) of 5.74×104 and 7.05×104, respectively. The relative standard deviations (RSDs) of Raman intensity were 7.19% and 18.40%, respectively, confirming the uniformity of the composite LB films. Furthermore, photoelectric conversion efficiencies indicate that the electrodes fabricated from SP/ST and SF/ST film electrodes have high carrier rates and good photocurrent generation properties. This study provides novel insights into the fabrication of multifunctional SP/dye and SF/dye composite LB films, demonstrating their potential applications in SERS and photovoltaic conversion.

Observation of single-molecule Raman spectroscopy enabled by synergic electromagnetic and chemical enhancement

There has been a long fundamental pursuit to enhance and levitate the Raman scattering signal intensity of molecule by a huge number of ~ 14–15 orders of magnitude, to the level comparable with the molecule fluorescence intensity and truly entering the regime of single-molecule Raman spectroscopy. In this work we report unambiguous observation of single-molecule Raman spectroscopy via synergic action of electromagnetic and chemical enhancement for rhodamine B (RhB) molecule absorbed within the plasmonic nanogap formed by gold nanoparticle sitting on the two-dimensional (2D) monolayer WS2 and 2 nm SiO2 coated gold thin film. Raman spectroscopy down to an extremely dilute value of 10–18 mol/L can still be clearly visible, and the statistical enhancement factor could reach 16 orders of magnitude compared with the reference detection sample of silicon plate. The electromagnetic enhancement comes from local surface plasmon resonance induced at the nanogap, which could reach ~ 10–11 orders of magnitude, while the chemical enhancement comes from monolayer WS2 2D material, which could reach 4–5 orders of magnitudes. This synergic route of Raman enhancement devices could open up a new frontier of single molecule science, allowing detection, identification, and monitor of single molecules and their spatial–temporal evolution under various internal and external stimuli.

Coherent Electron-Vibron Interactions in Surface-Enhanced Raman Scattering (SERS).

In this Letter we identify coherent electron-vibron interactions between near-resonant and nonresonant electronic levels that contribute beyond standard optomechanical models for off-resonant or resonance surface-enhanced Raman scattering (SERS). By developing an open-system quantum model using first molecular interaction principles, we show how the Raman interference of both resonant and nonresonant contributions can provide several orders of magnitude modifications of the SERS peaks with respect to former optomechanical models and over the fluorescence backgrounds. This cooperative optomechanical mechanism allows for generating an enhancement of nonclassical photon pair correlations between Stokes and anti-Stokes photons, which can be detected by photon-counting measurements. Our results demonstrate Raman enhancements and suppressions of coherent nature that significantly impact the standard estimations of the optomechanical contribution from SERS spectra and their quantum mechanical observable effects.

Purines recognition and quantitative analysis by surface-enhanced Raman spectroscopy

The common quantification methods of purines, including high-performance liquid chromatography, micellar electrokinetic chromatography, reverse phase ion pair chromatography, and capillary zone electrophoresis, have been used for the analysis of purines. These conventional techniques are limited by long operation times, large sample volumes, requirements for pretreatment and separation processes, or sophisticated, bulky and expensive equipment. Here, we have developed a simple method to prepare a probe for the quantitative analysis of purines using the surface-enhanced Raman scattering (SERS) method. The SERS probe is a rough Ag wire obtained with simple electrochemical treatment, which is optimized to reach the maximum SERS signal enhancement. The Raman enhancement factor (EF) of Ag wire after roughening can reach ∼106. Under optimized conditions, the rough Ag wire is capable of recognizing four purine bases (namely, guanine, adenine, hypoxanthine, and xanthine) in the range of 10−5 to 10−1 mg/mL with a linear relationship between SERS intensity of signature peak and purine concentration. The recovery rate of each purine base is higher than 80% in the mixture of four purines. The overall method was successfully applied to the monitoring of the level of purines in marketplace beer beverages. The novel wire-based SERS sensor used with portable Raman spectroscopy is prospective in diet safety and personalized point-of-care medical detection.

Single crystal polarization-orientation Raman spectroscopy of zeolite LTA with confined S3− anions - High dielectric constant nanoporous material

We apply polarization-orientation Raman spectroscopy, as an alternative to X-ray diffraction, to LTA single crystals containing S3− in sodalite cages additionally to S8 rings in large cavities. The sample was obtained via sulfur vapor adsorption at ∼550 °C (LTA-S-550). We show that S3− is located in the (110) plane with its 2-fold axis along the LTA 4-fold axis. The anion position suggests strong interaction of its terminal atoms with Na+ localized in LTA 6-membered rings. The anions display optical absorption band at ∼590 nm (2.1 eV) and resonant Raman enhancement. We observe a record-high S3− bond-bending mode frequency ∼274 cm−1 due to a strong bond-angle contraction. This leads to the Fermi resonance of its overtone with the symmetric bond-stretching mode in the frequency range of 544–552 cm−1. An anomalous Raman downshift of the S3− bond-stretching modes with a decrease of temperature is observed and attributed to partial compressive stress relaxation. Luminescence band at ∼845 nm is observed suggesting considering LTA-S-550 as an interesting light-emitting material. We discuss a role of S3− in the high dielectric constant up to ∼160 and a possible contribution of the anion to the ion-exchange selectivity to Sr2+/Cs+ enhancements of LTA with sulfur.

Fabrication of polydopamine functionalized AgNF SERS substrate: Applications for sensitive detection of nivalenol in food samples and cell biocompatibility

Surface-enhanced Raman spectroscopy (SERS) is a robust analytical tool applicable for the quick and accurate determination of mycotoxins. However, there hasn't been any attempt to use SERS for the quantitative detection of nivalenol (NIV) thus far. To improve the Raman signals of NIV, we fabricated a polydopamine-coated silver nanoflower (PDA-AgNFs) SERS substrate with strong “hot-spots”. The PDA-AgNFs substrates showed superior SERS enhancement activities in the target analyte detection and quantification. It produced good substrate uniformity (relative standard deviation of SERS signals, RSD = 4.1% for substrate-to-substrate test, and 3.24% for spot-to-spot test), an enhancement factor of 2.87 × 106 towards rhodamine 6B (R6G), and detection sensitivity as low as 1 femtomolar (10−15 M) against R6G probe molecule. Moreover, the PDA-AgNFs SERS substrates were successfully used, for the first time, to detect NIV in corn, horse beans, and mushroom samples. The calibration curve showed a satisfactory linear fit based on the SERS intensities of different NIV concentrations. The detection limit (LOD) for the suggested approach was 0.22 nM (S/N = 3). Interestingly, the MTT assay experiment demonstrated that PDA-AgNFs had no toxicity against mammalian NIH-3T3 cells. The biocompatible PDA-AgNFs substrates with intense plasmonic effects and binding sites demonstrated impressive Raman enhancement, and could serve as an effective, label-free, and fast SERS-based analysis of NIV in real samples.