Surface Enhanced Raman Spectroscopy Substrates Research Articles

Versatile flexible SERS substrate for in situ detection of contaminants in water and fruits based on Ag NPs decorated wrinkled PDMS film.

Flexible surface-enhanced Raman spectroscopy (SERS) substrate has attracted great attention due to its convenient sampling and on-site monitoring capability. However, it is still challenging to fabricate a versatile flexible SERS substrate, which can be used for in situ detection of analytes either in water or on irregular solid surfaces. Here, we report a flexible and transparent SERS substrate based on a wrinkled polydimethylsiloxane (PDMS) film obtained by transferring corrugated structures on the aluminium/polystyrene bilayer film, onto which silver nanoparticles (Ag NPs) are deposited by thermal evaporation. The as-fabricated SERS substrate exhibits a high enhancement factor (∼1.19×105), good signal uniformity (RSD of 6.27%), and excellent batch-to-batch reproducibility (RSD of 7.3%) for rhodamine 6 G. In addition, the Ag NPs@W-PDMS film can maintain high detection sensitivity even after mechanical deformations of bending or torsion for 100 cycles. More importantly, being flexible, transparent, and light, the Ag NPs@W-PDMS film can both float on the water surface and conformally contact with the curved surface for in situ detection. The malachite green in aqueous environment and on apple peel can be easily detected down to 10-6 M with a portable Raman spectrometer. Therefore, it is expected that such a versatile flexible SERS substrate has great potential in on-site, in situ contaminant monitoring for realistic applications.

A SERS Composite Hydrogel Device for Point-of-Care Analysis of Neurotransmitter in Whole Blood

Point-of-care analysis of neurotransmitters in body fluids plays a significant role in healthcare improvement. Conventional approaches are limited by time-consuming procedures and usually require laboratory instruments for sample preparation. Herein, we developed a surface enhanced Raman spectroscopy (SERS) composite hydrogel device for the rapid analysis of neurotransmitters in whole blood samples. The PEGDA/SA composite hydrogel enabled fast separation of small molecules from the complex blood matrix, while the plasmonic SERS substrate allowed for the sensitive detection of target molecules. 3D printing was employed to integrate the hydrogel membrane and the SERS substrate into a systematic device. The sensor achieved highly sensitive detection of dopamine in whole blood samples with a limit of detection down to 1 nM. The whole detection process from sample preparation to SERS readout can be finished within 5 min. Due to the simple operation and rapid response, the device shows great potential in point-of-care diagnosis and the monitoring of neurological and cardiovascular diseases and disorders.

Ultra-small gold particles via Citrus × sinensis: Theoretical and experimental SERS study

In this study, we have addressed the green synthesis of sub-nanostructured gold species using Citrus × sinensis. Absorption bands in the ultraviolet region (338 nm) were observed. Analysis by atomic resolution microscopy revealed the identification of sub-nanostructured Au species with particle sizes of about 0.9 nm. With favorable results, these systems were tested as substrates for surface-enhanced Raman spectroscopy (SERS) using pyridine. The chemical enhancement mechanism was studied as the source of the SERS effect. Complementarily, the interaction between gold clusters (Au2n, with n = 1–5) and pyridine was modeled using Density Functional at the Becke-3-parameter-Lee-Yang-Parr level of approximation in combination with the LANL2DZ basis set. A correlation between the adsorption energy and the SERS enhancement factor was analyzed as a function of the Au-N interaction distance.

ReS2 Nanoflowers-Assisted Confined Growth of Gold Nanoparticles for Ultrasensitive and Reliable SERS Sensing.

ReS2, as a new member of transition metal dichalcogenides (TMDCs), has emerged as a promising substrate for semiconductor surface-enhanced Raman spectroscopy (SERS) due to its unique optoelectronic properties. Nevertheless, the sensitivity of the ReS2 SERS substrate poses a significant challenge to its widespread application in trace detection. In this work, we present a reliable approach for constructing a novel ReS2/AuNPs SERS composite substrate, enabling ultrasensitive detection of trace amounts of organic pesticides. We demonstrate that the porous structures of ReS2 nanoflowers can effectively confine the growth of AuNPs. By precisely controlling the size and distribution of AuNPs, numerous efficient and densely packed "hot spots" were created on the surface of ReS2 nanoflowers. As a result of the synergistic enhancement of the chemical and electromagnetic mechanisms, the ReS2/AuNPs SERS substrate demonstrates high sensitivity, good reproducibility, and superior stability in detecting typical organic dyes such as rhodamine 6G and crystalline violet. The ReS2/AuNPs SERS substrate shows an ultralow detection limit of 10-10 M and a linear detection of organic pesticide molecules within 10-6-10-10 M, which is significantly lower than the EU Environmental Protection Agency regulation standards. The strategy of constructing ReS2/AuNPs composites would contribute to the development of highly sensitive and reliable SERS sensing platforms for food safety monitoring.

Low-Variance Surface-Enhanced Raman Spectroscopy Using Confined Gold Nanoparticles over Silicon Nanocones.

Surface-enhanced Raman spectroscopy (SERS) substrates are of utmost interest in the analyte detection of biological and chemical diagnostics. This is primarily due to the ability of SERS to sensitively measure analytes present in localized hot spots of the SERS nanostructures. In this work, we present the formation of 67 ± 6 nm diameter gold nanoparticles supported by vertically aligned shell-insulated silicon nanocones for ultralow variance SERS. The nanoparticles are obtained through discrete rotation glancing angle deposition of gold in an e-beam evaporating system. The morphology is assessed through focused ion beam tomography, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. The optical properties are discussed and evaluated through reflectance measurements and finite-difference time-domain simulations. Lastly, the SERS activity is measured by benzenethiol functionalization and subsequent Raman spectroscopy in the surface scanning mode. We report a homogeneous analytical enhancement factor of 2.2 ± 0.1 × 107 (99% confidence interval for N = 400 grid spots) and made a comparison to other lithographically derived assemblies used in SERS. The strikingly low variance (4%) of our substrates facilitates its use for many potential SERS applications.

Electric field enhancement in Au and Ag nanodisks-based photonic crystals: Relevant design insights for efficient SERS substrates

In recent years, noble metal nanoparticle-based periodic nanoarrays (photonic crystals) have received special attention due to their gross potential to achieve exceptionally high Electric-Near Field Enhancement (ENFE) factors for visible light and their prospects as candidates for the fabrication of ultra-sensitive Surface-Enhanced Raman Spectroscopy (SERS) substrates. In this work, we report a simple but exhaustive theoretical analysis of the ENFE in Au and Ag nanodisks-based photonic crystals by Finite-Difference Time-Domain (FDTD) method. Nanostructures with arrays periodicities from 200 to 1000 [nm], nanodisks diameters from 100 to 500 [nm] and thicknesses from 20 to 200 [nm] were studied. Results show that the ENFE is strongly dependent on each one of these geometrical parameters, observing |E/E0|2 factors that can reach up to 1200 for the visible light spectrum. The effects of nanodisks surface curvature-based defects on the ENFE were also analyzed. This kind of defects seem to be also relevant to maximize the ENFE effects, observing that higher surface curvatures tend to considerably attenuate the electric field amplification. Our research provides relevant insights on the design optimization of this kind of photonic crystals to maximize the ENFE effects, which is a critical issue to assess the future fabrication conditions of efficient SERS substrates.

Highly sensitive technique for detection of adulterants in centella herbal samples using surface enhanced Raman spectroscopy (SERS)

The trace level detection of adulterants in food, nutritional supplements and medicinal herbs is highly challenging in the field of food processing and herbal industries. In addition, laborious sample processing procedures and well trained personnel are required to analyse the samples using conventional analytical equipments. In this study, a highly sensitive technique with minimal sampling processes and human intervention is proposed for the trace amount detection of pesticidal residues in centella powder. Herein, graphene oxide gold (GO-Au) nanocomposite coated parafilm is developed as substrate by simple dropcasting technique to facilitate dual surface enhanced Raman signal. The dual SERS enhancement involving chemical enhancement from graphene and electromagnetic signal enhancement from gold nanoparticles is utilized for detection of chlorpyrifos in the ppm level concentration. The flexible polymeric surfaces could be the better choice for SERS substrates due to their inherent properties such as flexibility, transparency, roughness and hydrophobicity. Among the various types of flexible substrates explored, GO-Au nanocomposites coated parafilm substrates showed better Raman signal enhancement. Parafilm coated with GO-Au nanocomposites is successful in achieving detection limits down to 0.1 ppm of chlorpyrifos in centella herbal powder sample. Thus, the fabricated parafilm based GO-Au SERS substrates could be used as a screening tool at quality control of herbal product manufacturing sectors for trace level detection of adulterants in herbal samples from their unique chemical and structural information.

A Simple Method for the Fabrication of Silicon Inverted Pyramid Substrates for Surface-Enhanced Raman Spectroscopy.

Silicon inverted pyramids have been shown to exhibit superior SERS properties compared to ortho-pyramids, yet low-cost, simple preparation processes are lacking at present. This study demonstrates a simple method, silver-assisted chemical etching combined with PVP, to construct silicon inverted pyramids with a uniform size distribution. Two types of Si substrates for surface-enhanced Raman spectroscopy (SERS) were prepared via silver nanoparticles deposited on the silicon inverted pyramids by electroless deposition and radiofrequency sputtering, respectively. The experiments were conducted using rhodamine 6G (R6G), methylene blue (MB) and amoxicillin (AMX) molecules to test the SERS properties of the Si substrates with inverted pyramids. The results indicate that the SERS substrates show high sensitivity to detect the above molecules. In particular, the sensitivity and reproducibility of the SERS substrates with a denser silver nanoparticle distribution, prepared by radiofrequency sputtering, are significantly higher than those of the electroless deposited substrates to detect R6G molecules. This study sheds light on a potential low-cost and stable method for preparing silicon inverted pyramids, which is expected to replace the costly commercial Klarite SERS substrates.

Gold vs. Silver Colloidal Nanoparticle Films for Optimized SERS Detection of Propranolol and Electrochemical-SERS Analyses.

The increasing pollution of surface and groundwater bodies by pharmaceuticals is a general environmental problem requiring routine monitoring. Conventional analytical techniques used to quantify traces of pharmaceuticals are relatively expensive and generally demand long analysis times, associated with difficulties in performing field analyses. Propranolol, a widely used β-blocker, is representative of an emerging class of pharmaceutical pollutants with a noticeable presence in the aquatic environment. In this context, we focused on developing an innovative, highly accessible analytical platform based on self-assembled metal colloidal nanoparticle films for the fast and sensitive detection of propranolol based on Surface Enhanced Raman Spectroscopy (SERS). The ideal nature of the metal used as the active SERS substrate was investigated by comparing silver and gold self-assembled colloidal nanoparticle films, and the improved enhancement observed on the gold substrate was discussed and supported by Density Functional Theory calculations, optical spectra analyses, and Finite-Difference Time-Domain simulations. Next, direct detection of propranolol at low concentrations was demonstrated, reaching the ppb regime. Finally, we showed that the self-assembled gold nanoparticle films could be successfully used as working electrodes in electrochemical-SERS analyses, opening the possibility of implementing them in a wide array of analytical applications and fundamental studies. This study reports for the first time a direct comparison between gold and silver nanoparticle films and, thus, contributes to a more rational design of nanoparticle-based SERS substrates for sensing applications.

SERS performance of GaN/Ag substrates fabricated by Ag coating of GaN platforms.

The results of comparative studies on the fabrication and characterization of GaN/Ag substrates using pulsed laser deposition (PLD) and magnetron sputtering (MS) and their evaluation as potential substrates for surface-enhanced Raman spectroscopy (SERS) are reported. Ag layers of comparable thicknesses were deposited using PLD and MS on nanostructured GaN platforms. All fabricated SERS substrates were examined regarding their optical properties using UV-vis spectroscopy and regarding their morphology using scanning electron microscopy. SERS properties of the fabricated GaN/Ag substrates were evaluated by measuring SERS spectra of 4-mercaptobenzoic acid molecules adsorbed on them. For all PLD-made GaN/Ag substrates, the estimated enhancement factors were higher than for MS-made substrates with a comparable thickness of the Ag layer. In the best case, the PLD-made GaN/Ag substrate exhibited an approximately 4.4 times higher enhancement factor than the best MS-made substrate.

Innovative Surface-Enhanced Raman Spectroscopy Method as a Fast Tool to Assess the Oxidation of Lipids in Ground Pork

A novel method for the determination of lipid oxidation using Raman microscopy was developed. A home-made surface-enhanced Raman spectroscopy (SERS) substrate based on silver nanoparticles deposited on a glass Petri dish was used. The degradation of ground pork stored at 5 °C was monitored for 16 days. Two packages were considered: an active packaging containing an oregano extract with antioxidant properties and a conventional one consisting of a low-density polyethylene (LDPE) film. The lipid fraction of the ground pork was extracted with a mixture of diethyl ether/n-hexane (1:1). A remarkable maximum signal enhancement factor of 1.64 × 107 at 1439 cm−1 shift (and up to 8.58 × 106 at 1655 cm−1, chosen for fat oxidation assessment) was obtained with SERS compared to conventional Raman. In addition, SERS provided better discrimination among samples than the results obtained by the thiobarbituric acid reactive substances (TBARS) method. The experimental conditions for SERS were optimized and discussed.

3D Multilayered Metamaterials with High Plasmonic Hotspot Density for Surface—Enhanced Raman Spectroscopy

Three-dimensional (3D) plasmonic metamaterials have become a trend in the application of nanophotonic devices. In this paper, a convenient and inexpensive method for the design of 3D multilayer plasmonic metamaterials is constructed using a one-step self-shielded reactive-ion-etching process (OSRP) and a thermal evaporation system, which provides an efficient and low-cost method for the preparation of surface-enhanced Raman spectroscopy (SERS) substrates. The near-field enhancement of the 3D plasmonic metamaterials provides highly efficient electromagnetic resonance, and highly sensitive and uniform SERS sensing capabilities. The SERS detection results of rhodamine B (Rh. B) and rhodamine 6G (R6G) on this substrate show that the detection limit could reach 10–13 mol/L, and the signal could give expression to excellent uniform stability. The results show that high sensitivity and high robustness SERS substrates can be prepared with high efficiency and low cost.

A facile method for in-situ detection of thiabendazole residues in fruit and vegetable peels using Surface-Enhanced Raman Spectroscopy

A flexible Surface-Enhanced Raman Spectroscopy (SERS) substrate based on silver nanoparticles encapsulated in an agar gel has been probed to detect the fungicide thiabendazole (TBZ) reaching a limit of detection (LOD) of 30 ng/cm2. In addition, a simple and sensitive strategy was employed for in-situ detection of TBZ on fruit and vegetable peels. For that purpose, peels of different fruits and vegetables were intentionally contaminated with different amount of TBZ, and the analyte was subsequently extracted within few seconds by gently rubbing the surface with the SERS substrate. The lowest value of TBZ detected on eggplant and green pepper peels was 50 ng/cm2. The values achieved for apple and pear peels were 0.20 μg/cm2 and 40 ng/cm2, respectively. On the other hand, for tomato and strawberry peels the lowest value achieved was 0.50 μg/cm2. The variation in sensitivity can be attributed to differences in the surface properties of the different peels. The above results show that this flexible SERS substrate can be further employed for the detection of contaminants in practical applications for food safety inspection.

Au nanogap SERS substrate for the carbaryl pesticide determination in juice and milk using chemomterics

Conventional spectroscopic methods like IR, and Raman are not very effective at detecting low levels of pesticides or harmful chemicals in food matrices. A quick, highly accurate approach that can identify pesticides present in different food products at lower levels must be developed in order to address this problem and ensure food safety. In this study, a highly sensitive and uniform wafer-scale Au nanogap surface-enhanced Raman spectroscopy (SERS) substrate was used for the quantitative analysis of carbaryl pesticide levels in standard solution, mango juice, and milk samples using chemometrics. Carbaryl was detected up to 3 ppb concentration levels for all three group of samples. However, due to the higher sensitivity, uniformity, and enhancement factors of the SERS substrate used in this investigation, the limit of detection (LOD) values for the standard solution, mango juice, and milk were 0.37 ppb, 0.57 ppb, and 0.15 ppb at 1380 cm−1, 1380 cm−1, and 1364 cm−1 wavenumber ranges. In order to predict different carbaryl concentrations (1, 2, 3, 4, and 5 ppb), the variable importance in projection (VIP) method combined with partial least squares regression (PLSR) and attained the coefficient of determination (R2) values of 0.994, 0.989, and 0.978 along with minimum root mean square error (RMSE) values of 0.112, 0.190, and 0.278 ppb for the prediction datasets. Furthermore, PLS-DA was able to distinguish between pure and adulterated samples with the highest classification accuracy of 100 % for a standard solution, and mango juice and 94.4 % for milk samples. Considering this, we can conclude that the SERS Au Nanogap substrate can rapidly and effectively detect carbaryl pesticides quantitatively and qualitatively in mango juice and milk.

Three Generations of Surface Nanocomposites Based on Hexagonally Ordered Gold Nanoparticle Layers and Their Application for Surface-Enhanced Raman Spectroscopy

The fabrication technology of surface nanocomposites based on hexagonally ordered gold nanoparticle (AuNP) layers (quasi-arrays) and their possible application as surface-enhanced Raman spectroscopy (SERS) substrates are presented in this paper. The nanoparticle layers are prepared using a nanotextured template formed by porous anodic alumina (PAA) and combined with gold thin-film deposition and subsequent solid-state dewetting. Three types of hexagonal arrangements were prepared with different D/D0 values (where D is the interparticle gap, and D0 is the diameter of the ellipsoidal particles) on a large surface area (~cm2 range), namely, 0.65 ± 0.12, 0.33 ± 0.10 and 0.21 ± 0.09. The transfer of the particle arrangements to transparent substrates was optimized through three generations, and the advantages and disadvantages of each transfer technology are discussed in detail. Such densely packed nanoparticle arrangements with high hot-spot density and tunable interparticle gaps are very beneficial for SERS applications, as demonstrated with two practical examples. The substrate-based enhancement factor of the nanocomposites was determined experimentally using a DNA monolayer and was found to be between 4 × 104 and 2 × 106 for the different particle arrangements. We also determined the sensing characteristics of a small dye molecule, rhodamine 6G (R6G). By optimizing the experimental conditions (e.g., optimizing the laser power and the refractive index of the measurement medium with an ethylene-glycol/water mixture), concentrations as low as 10−16 M could be detected at 633 nm excitation.

Clinical detection of total homocysteine in human serum using surface-enhanced Raman spectroscopy

Cardiovascular diseases cause enormous morbidity and mortality worldwide. Excessive blood total homocysteine (tHcy) is an independent risk factor for cardiovascular diseases. Therefore, it is imperative to measure the content of tHcy in human blood. However, the currently available analytical methods have the disadvantages such as being time-consuming and expensive. Herein, we propose a rapid clinical quantification of tHcy in human serum using high-performance Ag Nanopolyhedra (Ag NPOLY) as surface-enhanced Raman spectroscopy (SERS) substrates. Generally, 80% of homocysteine (Hcy) in serum is oxidized, and only 20% of Hcy is free. To understand this behavior, we explored the reduction effect of tris(2-carboxyethyl) phosphine (TCEP) on serum Hcy at different pH. The results confirmed that our method can detect 2 µM of Hcy in human serum. As a proof-of-concept, the developed method was applied to the actual clinical detection of human serum tHcy, and the serum of 5 hyperhomocysteinemia (HHcy) patients was verified. Moreover, the obtained, results were consistent with high-performance liquid chromatography (HPLC) results. The linear correlation coefficient of the two methods was 0.9766. Importantly, our analysis can be completed within 15 min, while HCLP requires more than 1 h. Overall, we have successfully developed a rapid SERS-based quantitative method for human serum tHcy, which can provide a new solution for the clinical diagnosis of cardiovascular diseases in the future.

Morphology Effect of Photoconverted Silver Nanoparticles on the Performance of Surface-Enhanced Raman Spectroscopy Substrates.

Nowadays, surface-enhanced Raman spectroscopy (SERS) substrates are of great interest for many researchers, aiming to fabricate substrates with high sensitivity and low fabrication costs. In this study, we photoconverted Ag nanoparticles by using a simple and affordable red-green-blue light-emitting diode photoreactor. The obtained dispersions were transformed into a paste of nanoparticles and used to fabricate SERS substrates by a simple drop-casting process under controlled humidity conditions. The performance of these substrates was tested using p-aminothiophenol as a Raman probe. The results indicate that the particle shape has an influence on the Raman intensities and substrate sensitivity, showing a significant enhancement as the number of faces and vertices in the particle increases.

Surface-enhanced Raman scattering of As2S3 and Se thin films formed on Au nano-structures

The effect of plasmonic nanostructures (NSs) on the Raman spectra and underlying structural changes in thin chalcogenide films is investigated. Several tens of nanometers thick As 2 S 3 and Se films were deposited by thermal sputtering on glass and surface-enhanced Raman spectroscopy (SERS) substrates based on gold nanostructures for comparison. The films on glass were practically not detectable by the Raman spectroscopy. Using gold NSs as the substrates enabled reliable registration of the Raman spectra of both the As 2 S 3 and Se films. The registered Raman spectra contained all the features usually present in the films with the thicknesses ~1 μm or more. Based on our analysis of the spectra obtained at different excitation wavelengths, we may conclude that the SERS chemical mechanism makes the main contribution to the enhancement of the Raman signal from chalcogenide films. Adjustment of the parameters of SERS substrates to tune their plasmon band position in resonance with the excitation laser radiation enables increasing the plasmonic enhancement contribution. Besides the effect of enhancement, localized plasmon resonance in the gold NSs causes local heating of the chalcogenide film around them leading to local structural transformations, which can be controlled using the Raman spectra.

Two-Dimensional Printed AgNPs@Paper Swab for SERS Screening of Pesticide Residues on Apples and Pears.

In recent years, growing food safety and quality concerns have emerged and created an urgent need for the development of rapid and reliable food control technologies. This study proposes a novel surface-enhanced Raman spectroscopy (SERS) substrate printing technology that utilizes commercial filter paper functionalized by silver nanoparticles. We modified the Automatic TLC Sampler using a two-dimensional (2D) printer. The modification allows for various sampling modes which can be applied to 2D printing. The shape and size of nano silver on the substrate were determined, and the substrate sensitivity, uniformity, and stability were evaluated. As demonstrated by the experimental outcomes, the proposed technology is highly sensitive and reproducible, that is, the limit of quantitation was 10-5 mg/kg, and the spot-to-spot and block-to-block Raman intensity variations were below 4.2%. We also successfully applied the technology to pears and apples for thiram recognition, yielding outstanding detectability down to 2.5 × 10-6 and 3.9 × 10-7 mg/mL (equal to 2.5 × 10-3 and 3.9 × 10-4 mg/kg), respectively. These were well below the maximum residue limit (7 mg/kg). More importantly, the linear relationships between thiram levels and the SERS intensity allow for sensitive monitoring of minute variations in agricultural insecticide residues. This proposed detection method can realize in situ detection with a strong signal fingerprint.

Hot Spot Engineering in Hierarchical Plasmonic Nanostructures

The controllable nanogap structures offer an effective way to obtain strong and tunable localized surface plasmon resonance (LSPR). A novel hierarchical plasmonic nanostructure (HPN) is created by incorporating a rotating coordinate system into colloidal lithography. In this nanostructure, the hot spot density is increased drastically by the long-range ordered morphology with discrete metal islands filled in the structural units. Based on the Volmer-Weber growth theory, the precise HPN growth model is established, which guides the hot spot engineering for improved LSPR tunability and strong field enhancement. The hot spot engineering strategy is examined by the application of HPNs as the surface-enhanced Raman spectroscopy (SERS) substrate. It is universally suitable for various SERS characterization excited at different wavelengths. Based on the HPN and hot spot engineering strategy, single-molecule level detection and long-range mapping can be realized simultaneously. In that sense, it offers a great platform and guides the future design for various LSPR applications like surface-enhanced spectra, biosensing, and photocatalysis.