Efficient Surface Enhanced Raman Spectroscopy Research Articles

Optical response of Au films for reproducible Si nano-structuring and its application for efficient micro-drop SERS with portable Raman system

Si nanostructuring by metal assisted chemical etching is highly sensitive to morphology of thin metal film, here we demonstrate use of plasmon driven optical or dielectric response of Au films for predicting nanopore or nanowire Si prior to etching, ensuring the process reproducibility. By controlling growth temperature, it is shown that same mass thickness of Au films can produce either nanopore, nanowire or hybrid (mix of the two) Si nanostructures, useful for various applications. Ag nanoparticles coated nanostructure Si is shown to be efficient surface enhanced Raman spectroscopy (SERS) substrate for dry state measurements with micro-Raman system. In contrast, by exploiting super-hydrophilicity and strong light coupling of nanostructure Si, a novel micro-drop SERS using portable Raman spectrometer is demonstrated as low-cost, reliable and easy field-deployable technique. With very low sample volume about 50 μL of as prepared Au nanoparticles and analyte, it is capable of producing SERS signal in samples containing 120 pg thiram, 240 pg Rh6G, 455 pg malachite green and 48 pg methylene blue. With advantages of micro-drop SERS, mainly high intensity signal with 3D dynamic hot-spots at high laser power, longer shelf-life colloidal gold, reusable substrates with no prior sample preparation, this method is envisaged to be an inexpensive technique for on-site trace detection applications and importantly quick generation of large experimental SERS data-set for machine learning (ML) driven studies. This is demonstrated by principal component analysis with ML classifier for 100% accurate prediction of trace dyes, pesticide and their binary mixtures.

Identification of Poly(ethylene terephthalate) Nanoplastics in Commercially Bottled Drinking Water Using Surface-Enhanced Raman Spectroscopy.

Micro/nanoplastics have emerged as global contaminants of serious concern to human and ecosystem health. However, identification and visualization of microplastics and particularly nanoplastics have remained elusive due to the lack of feasible and reliable analytical approaches, particularly for trace nanoplastics. Here, an efficient surface-enhanced Raman spectroscopy (SERS)-active substrate with triangular cavity arrays is reported. The fabricated substrate exhibited high SERS performance for standard polystyrene (PS) nanoplastic detection with size down to 50 nm and a detection limit of 0.001% (1.5 × 1011 particles/mL). Poly(ethylene terephthalate) (PET) nanoplastics collected from commercially bottled drinking water were detected with an average mean size of ∼88.2 nm. Furthermore, the concentration of the collected sample was estimated to be about 108 particles/mL by nanoparticle tracking analysis (NTA), and the annual nanoplastic consumption of human beings through bottled drinking water was also estimated to be about 1014 particles, assuming water consumption of 2 L/day for adults. The facile and highly sensitive SERS substrate provides more possibilities for detecting trace nanoplastics in an aquatic environment with high sensitivity and reliability.

Plasmonic gold dogbone nanorattles sniff out trace molecules through surface enhanced Raman scattering.

In this study, a highly sensitive and efficient surface-enhanced Raman spectroscopy (SERS) substrate was developed using Au dogbone nanorattles (Au-DBNRTs) deposited on a 3D wrinkled polymeric heat shrink film. The plasmonic structures of Au-DBNRTs, which possess a solid gold dogbone-shaped core and a thin, porous gold shell, and Au nanorod nanorattles (Au-NRNRTs), which have a rod-shaped core, were synthesized and their SERS performance was evaluated. Au-DBNRTs exhibited better Raman signal enhancement. The substrate was used to detect the pesticide thiabendazole with a limit of detection of up to 10-8 M. The unique optical properties and geometry of the Au-DBNRT nanoparticles, which have portruding corners in the vicinity of the metal shell, along with the shrinkage of the film after heat treatment, led to the creation of a 3D surface morphology, resulting in the generation of plasmonic electromagnetic hot spots. The fabricated substrate achieved an enhancement factor of 2.77 × 1010 for BDT, and the detection limit was 10-13 M. The current work offers a simple, cost-effective, and sensitive SERS substrate design that has great potential for sensing and detecting trace analytes.

Dramatically enhanced SERS and photocatalytic performances over a portable Ag nanoparticles anchored flower-like metal-organic frameworks induced by TiO2/Zn sheet

Aimed at obtaining a new type of bi-functional materials for highly efficient surface enhanced Raman spectroscopy (SERS) detection and photocatalytic degradation of organic pollutants, a low content of Ag nanoparticles (0.5 wt. % Ag) anchored flower-like 2-methylimidazole zinc metal organic frameworks (ZIF-8) induced by TiO2/Zn sheet was facilely constructed without adding any reductants or UV-light reduction. With p-aminothiophenol (PATP, a typical pesticide) as an analyte, SERS and photocatalytic degradation performances of the resulting Zn/TiO2/ZIF-8/Ag (Zn-TZA) sheet were evaluated. The cost-effective Zn-TZA sheet exhibited high SERS activity and excellent stability towards PATP detection, and its detection limit can reach 1 × 10-11 M. In addition, the Zn-TZA sheet showed high and stable photocatalytic performance for PATP degradation. In particularly, by means of the plug and play Zn-TZA, the detection and degradation of PATP in real samples can also be effectively achieved. The strong coupling and electron transfer among Ag NPs, TiO2/Zn, and ZIF-8 in the Zn-TZA sheet were very advantageous to enhancing the bi-functionality. Additionally, the increased enrichment of PATP on the special sheet was also an important factor for the enhanced bi-functionality. It will provide new ideas for designing competitive bi-functional materials that are used to detect and degrade organic poisons in waste water.

Core-shell Au@MIL-100 (Fe) as an enhanced substrate for flunixin meglumine ultra-sensitive detection

This study aimed to develop and validate a simple and efficient surface-enhanced Raman spectroscopy (SERS) method to determine flunixin meglumine (FM) residues in animal tissues through using core-shell Au@MIL-100 (Fe) as enhanced substrate. Au@MIL-100 (Fe) composite material was synthesized by coating metal-organic framework materials (MOFs) on the surface of gold nanoparticles using the solvothermal method. Transmission electron microscopy (TEM), UV–vis spectrum, SERS spectrum, X-ray diffraction (XRD), Infrared spectrum (FT-IR), and EDX elemental mapping results revealed that the structural composition of the compound has good properties with localized surface plasmon resonance (LSPR) properties, high adsorption capacity, excellent SERS sensitivity and stability. When it was used as SERS substrate, the results of quantitative analysis of FM in pork showed a linear range of 0.10–50 mg·L−1 with a correlation coefficient (R2) of 0.9819, the limit of detection (LOD) of 0.15 mg·g−1, the recovery rate of 88.94%∼104.77%, the intra- and inter- batch relative standard deviation (RSD) of 3.57%∼14.22% and 0.18%∼3.44% respectively. Further verification results of the existing standard methods showed no significant difference between the SERS and UV methods (P < 0.05), as well as demonstrating that the SERS method has optimal precision, accuracy, and practicality. These results exposed that Au@MIL-100 (Fe) as a SERS substrate has great potential in rapid and on-site detection analysis.

Silver nanoparticle-coated polydopamine-copper hybrid nanoflowers as ultrasensitive surface-enhanced Raman spectroscopy probes for detecting thiol-containing molecules

In this study, silver nanoparticle-coated polydopamine-copper phosphate hybrid nanoflowers (Ag-PDA-Cu3(PO4)2 NFs) were synthesized and demonstrated to serve as efficient surface-enhanced Raman spectroscopy (SERS) probes for detecting thiol-containing molecules such as benzenethiol and thiocholine. Ag-PDA-Cu3(PO4)2 NFs were fabricated by forming PDA-Cu3(PO4)2 NFs through the nucleation of Cu3(PO4)2 on the PDA surface via interaction between Cu2+ and the free amine groups of dopamine, followed by the anisotropic growth of Cu3(PO4)2 crystals into flower-like microparticles. The NFs were then incubated with silver nitrate for in situ reduction to form Ag nanoparticles (NPs) on the surface of the NFs. The resulting hybrid NFs were demonstrated to act as SERS probes, sensitively detecting thiol-containing molecules, based on the successful interaction between Ag NPs and the thiol group (S-H) of the target molecules. The SERS intensities of benzenethiol and thiocholine at various concentrations were analyzed and found to yield superior limits of detection of 800 and 60 pM, respectively. Therefore, Ag-PDA-Cu3(PO4)2 NFs could be excellent SERS probes for detecting various thiol-containing molecules, particularly to determine the status of patients exposed to thiol-containing pesticides.

Label-free and ultrasensitive SERS detection of pesticide residues using 3D hot-junction of a Raman enhancing montmorillonite/silver nanoparticles nanocomposite.

Montmorillonite (MMT) coated with roughened noble metal nanoparticles are novel hybrid nanocomposite with a wide range of applications including agriculture, materials science and biomedical engineering. Herein, we developed a hybrid nanocomposite (MMT/AgNPs) based on MMT coated with silver nanoparticles (AgNPs), which can be used as a cost-effective and efficient surface-enhanced Raman spectroscopy (SERS) substrate for the detection of pesticides in fruits and vegetables. MMT itself is negatively charged and can be assembled with positively charged AgNPs through electrostatic interactions. Moreover, MMT has a layered 2D structure that possesses a large surface area, which can load a large number of AgNPs to form more SERS hotspots for the ultrasensitive measurement. SERS performance of the MMT/AgNPs nanocomposite was tested by 5,5'-dithiobis-(2-nitrobenzoic acid) (DTNB) and the substrate can obtain the strongest SERS enhancement effect with the volume ratio of MMT/AgNPs of 1 : 10. These substrates were applied in the measurement of thiram in apples and spinach samples by SERS. Detection limits of pesticide molecules of 5.0 × 10-8 M and 1.0 × 10-7 M in apples and spinach, respectively, were obtained. Most importantly, MMT nanosheets are a robust platform that allowed AgNPs to be evenly and thoroughly distributed and stabilized over the substrate, improving the repeatability and stability of SERS detection. These results reveal that the MMT/AgNPs nanocomposites are suitable substrates for the real-world SERS analysis of pesticide and other contaminants in complex food matrices.

Fabrication of flexible, cost-effective, and scalable silver substrates for efficient surface enhanced Raman spectroscopy based trace detection

The fabrication and optimization of cost-effective, eco-friendly, uniform and flexible SERS platforms by facile synthesis routes has recently attracted great attention for trace detection of various analytes. Herein, we report the fabrication of interconnected Ag nanostructures on the unmodified filter paper-based flexible substrates by a facile recipe, which involves evaporation of Ag precursor solution on the filter paper followed by its reduction with a strong reducing agent, NaBH4. The fabrication process is time-efficient, reproducible, and has the potential of being scaled up. The presence of inter-connected nanostructures results in high concentration of uniformly distributed hotspots on the substrate, which in turn provide excellent and reproducible SERS sensitivity. The finite element simulation results showed that fabricated nanostructures are much more effective for field enhancement as compared to the agglomerated spherical nanoparticles. Crystal violet (CV) concentration of 10−8 M was easily detected with these substrates both via solution drying and swabbing. Similarly, AgFPS have proven effective for swab-based detection of urea nitrate (UN), a well-known constituent of homemade explosives. The C-N and NO3- symmetric stretching modes of UN are detectable down to 1 µM and 100 µM concentrations, respectively. Moreover, these substrates showed SERS signal uniformity both from different spots of a single substrate, and substrates from different batches, with spot-to-spot relative standard deviation (RSD) of 15% and sample-to-sample RSD of 15–19%. This makes them excellent for reliable and quick quantitative detection. The simple synthesis strategy, flexibility, cost-effectiveness, and quantitative detection makes these substrates ideal for SERS based trace detection, especially for on-site analysis, and various sensing applications.

A nanozyme-based enhanced system for total removal of organic mercury and SERS sensing

Total removal of organic mercury in industrial wastewater is a crucially important task facing environmental pollution in the current world. Herein, we demonstrate the fabrication of Au-NiFe layered double hydroxide (LDH)/rGO nanocomposite as not only an efficient nanozyme with oxidase-like activity but also an efficient surface-enhanced Raman spectroscopy (SERS) substrate to determine organic mercury, with the minimum detection concentration as low as 1 × 10−8 M. According to the binding energy of X-Ray photoelectron spectrometer (XPS) and the free radicals of electron paramagnetic resonance (EPR) spectra, the mechanism of catalytic enhanced degradation is the production of Au-amalgam on Au surface, accelerating the electron transfer and the generation of O2•– radicals from oxygen molecules and •CH3 radicals from the methyl group in MeHg to participate the oxidase-like reaction. Furthermore, the Au-NiFe LDH/rGO nanocomposite is able to degrade and remove 99.9% of organic mercury in two hours without the secondary pollution by Hg2+. In addition, the material can be used for the multiple degradation-regeneration cycles in actual applications, which is significant in terms of the environmental and economic point of view. This work may open a new horizon for both highly sensitive detection and thorough degradation of organic mercury in environmental science and technology.

Ordered gold-coated glass nano-sting array with large density tips as highly SERS-active chips for detection of trace organophosphorous toxicant

A simple and cost-effective route to fabricating gold-coated glass nano-stings’ arrays is presented for highly efficient surface enhanced Raman spectroscopy (SERS) chips via reactive ion etching of the glass slide covered with polystyrene (PS) colloidal monolayer and sputtering deposition of gold on it. The as-fabricated SERS chips consist of the nearly-hemispherical particles with submicron-size, which are hexagonally arranged into the ordered arrays. There are many short and long Au-coated glass nano-stings standing vertically on the hemispherical particles, showing high density tips (up to 7.0 × 103 μm−2). The formation of such gold-coated glass hierarchically structured array is attributed to the geometry of PS colloidal monolayer and the nanoscale roughness of glass slide’s surface. Further, it has been demonstrated that such gold-coated glass array chip is highly SERS-active and can be utilized to detect trace organophosphorous toxicant with the limit below ppt level and good reproducibility in measurements. The intensity of the Raman peak shows the linear relation, in logarithmic scale, with the organophosphorous concentration from ppt to ppm level, exhibiting the possibility of quantitative detection in a large concentration range. This work has demonstrated the cost-effective method to fabricate the high performance SERS chips for trace detection of toxic molecules.

Cu/Ag Sphere Segment Void Array as Efficient Surface Enhanced Raman Spectroscopy Substrate for Detecting Individual Atmospheric Aerosol.

Surface enhanced Raman spectroscopy (SERS) shows great promise in studying individual atmospheric aerosol. However, the lack of efficient, stable, uniform, large-array, and low-cost SERS substrates constitutes a major roadblock. Herein, a new SERS substrate is proposed for detecting individual atmospheric aerosol particles. It is based on the sphere segment void (SSV) structure of copper and silver (Cu/Ag) alloy. The SSV structure is prepared by an electrodeposition method and presents a uniform distribution, over large 2 cm2 arrays and at low cost. The substrate offers a high SERS enhancement factor (due to Ag) combined with lasting stability (due to Cu). The SSV structure of the arrays generates a high density of SERS hotspots (1.3 × 1014/cm2), making it an excellent substrate for atmospheric aerosol detection. For stimulated sulfate aerosols, the Raman signal is greatly enhanced (>50 times), an order of magnitude more than previously reported substrates for the same purpose. For ambient particles, collected and studied on a heavy haze day, the enhanced Raman signal allows ready observation of morphology and identification of chemical components, such as nitrates and sulfates. This work provides an efficient strategy for developing SERS substrate for detecting individual atmospheric aerosol.

Controlling the Nanoscale Gaps on Silver Island Film for Efficient Surface-Enhanced Raman Spectroscopy.

We control the nanoscale gaps on silver island films by different processing methods and investigate the surface-enhanced Raman scattering (SERS) efficiency on the films. We propose a facile technique to control the film morphology by substrate bending while keeping the evaporation rate constant. The films developed by our new method are compared to the films developed by traditional methods at various evaporation rates. The SERS signals generated on the samples prepared by the new method have similar strengths as the traditional methods. Substrate bending allows us to reduce the gap sizes while using a higher evaporation rate, hence the film can be developed in a shorter time. This cost-effective and time-efficient method is suitable for the mass production of large-area SERS sensors with good sensitivity. Scanning electron microscope images are analyzed to quantify the gap densities and widths to elucidate the relationship between the film morphology and the SERS intensity. While the gap size appears to be the major factor influencing the enhancement, the shape of the nano-island also seems to influence the SERS efficiency.

Mesoporous plasmonic nanocomposites based on Au/Ag-TiO2 aerogels as SERS substrates.

Au/Ag-TiO2 mesoporous nanocomposite aerogels are special materials that can be applied as efficient surface-enhanced Raman spectroscopy (SERS) substrates, in order to detect low concentration of analytes from aqueous environments. At the same time, they benefit from structural and intrinsic properties of aerogels and TiO2, respectively, and also the plasmonic effects of Au/Ag nanoparticles. Here, several composites of TiO2 aerogel modified with various concentrations of Au, Ag, and a mixture of Au-Ag nanoparticles were prepared by applying two different methods of synthesis. The SERS detection efficiency of the nanocomposites was established by using the dye crystal violate (CV) as the test molecule. The lowest concentration of CV detectable by SERS, which was 10-10 M, was found to depend on the method of synthesis, size, and type of the nanoparticles that were used in the nanocomposite structure. In addition, the morphological and structural characterizations of the nanocomposites were investigated through Brunauer-Emmet-Teller results, field emission scanning electron microscopy (FESEM), and transmission electron microscope images.

Nanostructured films based on branched gold particles

Nanostructured films based on branched gold nanoparticles were obtained by self-assembly method. The possibility of controlling the film thickness in the range of 500 to 800 nm with preservation of their homogeneity and nanoparticle size (DSEM = 55 ± 12 nm) was shown. Position of localized surface plasmon resonance in absorption spectra of the film structures at λlspr = 595 to 600 nm is almost independent on the film thickness. The efficient surface-enhanced Raman spectroscopy substrates based on branched gold nanostructures were developed.

Photothermally Enhanced Plasmon‐Driven Catalysis on Fe5C2@Au Core–Shell Nanostructures

AbstractPlasmon‐driven catalysis has attracted great attention in recent years, but the reaction efficiency remains to be improved. Photothermal Fe5C2@Au core–shell nanostructures are fabricated through a self‐assembly process of Fe5C2 and Au nanoparticles (NPs) with the assistance of hexanethiol, which can be highly efficient surface enhanced Raman spectroscopy (SERS) platforms for the study of plasmon‐driven dimerization of 4‐aminothiophenol (4‐ATP) and 4‐nitrothiophenol (4‐NTP). As compared to bare Au NPs, much accelerated reaction kinetics can be achieved on the Fe5C2@Au core–shell nanostructures by quantitatively determining the Raman intensity of the ν(N=N) band in the generated 4,4′‐dimercaptobenzene (DMAB). The photothermal effect from the Fe5C2 NPs may lower the energy barrier and generate more hot electrons for the plasmon‐driven catalysis. This photothermal route may open up new avenues for enhancing the reaction rate and broadening the research area of the plasmon‐driven catalysis.

Dual-Functionalized Virus-Gold Nanoparticle Clusters for Biosensing.

Metallic nanoscale 3D architectures concentrate electromagnetic energy at precise spatial locations to enable sensing and photocatalysis applications. We have developed solution-based methods to reproducibly fabricate 3D gold nanostructures useful as efficient surface-enhanced Raman spectroscopy (SERS) biosensors. Virus capsids were recruited as templates to assemble gold nanoparticles on their surfaces at well-defined locations to prepare the nanoscale 3D structures. Cowpea mosaic virus (CPMV) and its variants were selected as specific templates due to their high symmetry, scalability, and stability, which have proven useful in materials science applications. While the methods described herein were optimized for the CPMV capsids, they also provide a useful starting point for researchers who are working toward the nanoassembly of metal nanoparticles on other protein scaffolds.

Development of a SERS Probe for Selective Detection of Healthy Prostate and Malignant Prostate Cancer Cells Using ZnII.

Even in the 21st century, prostate cancer remains the second leading cause of cancer-related death for men. Since a normal prostate gland has a high ZnII content and there are huge differences in ZnII content between healthy and malignant prostate cancer cells, mobile zinc can be used as a biomarker for prostate cancer prediction. A highly efficient surface enhanced Raman spectroscopy (SERS) probe using a p-(imidazole)azo)benzenethiol attached gold nanoparticle as a Raman reporter, which has the capability to identify prostate cancer cells based on ZnII sensing, has been designed. A facile synthesis, characterization and evaluation of a ZnII sensing Raman probe are described. Reported data indicate that after binding with ZnII , Raman reporter attached to a gold nanoparticle forms an assembly structure, which allows selective detection of ZnII even at 100 ppt concentration. Theoretical full-wave finite-difference time-domain (FDTD) simulations have been used to understand the enhancement of the SERS signal. The SERS probe is highly promising for in vivo sensing of cancer, where near-IR light can be easily used to avoid tissue autofluorescence and to enhance tissue penetration depth. Reported data show that the SERS probe can distinguish metastatic cancer cells from normal prostate cells very easily with a sensitivity as low as 5 cancer cells mL-1 . The probe can be used as a chemical toolkit for determining mobile ZnII concentrations in biological samples.

Surface-enhanced Raman spectroscopy using linearly arranged gold nanoparticles embedded in nanochannels

A micro/nanofluidic device containing linearly arranged gold nanoparticles embedded in nanochannels was developed for highly sensitive and highly efficient surface-enhanced Raman spectroscopy (SERS). The Si nanochannel array was fabricated using a photolithography-based process. The nanochannel width was controlled from 100 to 400 nm. Synthesized particles of mean diameter 100 nm were arranged linearly in the nanochannels, using a nanotrench-guided self-assembly process. We developed a process for integrating linearly arranged nanoparticles and micro/nanofluidic components. The particle geometry provided significant Raman enhancement. Furthermore, efficient Raman analysis was possible by scanning a laser spot, because the particles were arranged in one direction. The fabricated structures were evaluated for SERS using 4,4′-bipyridine molecules at concentrations of 1 mM and 10 µM. The Raman peaks was obtained from a few hot spots. The Raman spectra showed that the molecule-specific Raman intensities were correlated with the number of hot spots in the nanochannel.

Controllable synthesis of tetrapod gold nanocrystals with precisely tunable near-infrared plasmon resonance towards highly efficient surface enhanced Raman spectroscopy bioimaging.

Tetrapod gold nanocrystals, to be the core of surface-enhanced Raman spectroscopy (SERS) nanoprobes, with tunable localized surface plasmon resonance (LSPR) from 650 nm to 785 nm in the Vis-NIR region have been successfully prepared by a facile seeded growth approach. The local electromagnetic field distribution and the huge extinction cross section of the tetrapod gold nanocrystals were simulated by a finite-difference time-domain method. Both the calculated and experimental results reveal that the LSPR property of the tetrapod gold nanocrystals is closely dependent on the morphology features of their tips, where a strong field enhancement appears. These tetrapod nanocrystals have exhibited a good capability not only for Raman signal enhancement but also when successfully utilized as NIR SERS bioimaging nanoprobes. In vitro SERS imaging of stained breast cancer cells has also been demonstrated. The tetrapod gold nanocrystals developed here with a precisely tunable LSPR offer advantages of enhanced signal quality, good stability and better biocompatibility in SERS imaging, which has great potential for various biomedical applications.

Gravure printed flexible surface enhanced Raman spectroscopy (SERS) substrate for detection of 2,4-dinitrotoluene (DNT) vapor

An efficient surface enhanced Raman spectroscopy (SERS) substrate was successfully fabricated by gravure printing a thin film of silver nanoparticle (Ag NP) ink, with average particle size of 150nm, on flexible polyethylene terephthalate (PET) sheet. The feasibility of the printed SERS substrate for detecting explosive organic compounds such as 2,4-dinitrotoluene (DNT), in vapor phase, was investigated. The SERS based response of the printed substrate demonstrated an enhancement factor of four in the intensity of the Raman signal of DNT vapor when compared to target molecules adsorbed on bare PET. An 85% decrease in the intensity of the Raman spectrum was also observed as the temperature increased from 25°C to 65°C. The results obtained show the efficiency of the gravure printed SERS substrate to be used in applications for the detection of explosive organic compounds.