Surface-enhanced Raman Scattering Detection Research Articles

Fast and straightforward in-situ synthesis of gold nanoparticles on a thread-based microfluidic device for application in surface-enhanced Raman scattering detection

Cotton threads forming a microfluidic device were used for the first time to conduct a fast and straightforward Turkevich synthesis of gold nanoparticles (AuNPs) using minute amounts of reagents. Spherical AuNPs were obtained with sizes that varied from 20 to 40 nm, according to the synthesis conditions. The cotton thread also acted as physical support for the synthesized AuNPs during surface-enhanced Raman scattering (SERS) detection of crystal violet and nicotine. A calibration curve for nicotine with acceptable linearity (R2 = 0.9844) in the concentration range of 2–6 mg L−1 was obtained. The limit of detection for nicotine was 0.18 mg L−1. The proposed substrate was considered cheap, fast, and easy to be fabricated and applied in SERS detection.

Surface-Enhanced Raman Scattering Detection Based on an Interconnected Network of Vertically Oriented Semiconducting Few-Layer MoS2 Nanosheets

As an alternative to costly metals (Au and Ag), semiconducting metal dichalcogenide nanostructures can be used as active surface-enhanced Raman spectroscopy (SERS) substrates for the detection of o...

Deposition of Ag Films on Liquid Substrates via Thermal Evaporation for Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) substrates were prepared by depositing Ag atoms on liquid surfaces via thermal evaporation at room temperature. These free-sustained substrates result in the formation of uniform Ag films, in which ramified Ag aggregates consist of substantial Ag nanoclusters with narrow gaps of several nanometers in between. SERS spectra of rhodamine 6G were investigated for this substrate to evaluate the SERS performance of this characteristic film morphology, and the results indicated that the SERS intensity from the closely-packed Ag nanostructures and small intervals were significantly enhanced. The dependence of SERS enhancement on the film thickness, nanoparticle size, and gap width was studied. An analytical model was proposed to simulate the electric field distribution during SERS detection, and the results validated the experimental observations.

In Situ Integration of SERS Sensors for On‐Chip Catalytic Reactions

AbstractThe rapid progress of microfluidics has contributed to modern analytical methodology. However, in situ integration of chemical/biological sensors for on‐chip reaction monitoring remains a big challenge. Herein, reported is the fabrication of an integrated surface‐enhanced Raman scattering (SERS) sensor and graphene‐based catalytic chip by laser scribing of graphene oxide (GO) and Ag nanoparticles (AgNPs) composite (AgNPs@GO). The surface plasmonic effect of AgNPs can promote the photoreduction of GO, inducing a high porous nanostructure. By combining the AgNPs@RGO nanocomposite patterns with polydimethylsiloxane microfluidic channels, a bi‐functional microfluidic chip capable of on‐chip catalysis and SERS detection is fabricated. As a proof‐of‐concept demonstration, on‐chip AgNPs‐catalyzed 4‐nitrophenol (4‐NP) reduction has been implemented, in which the reaction process can be well monitored using the in situ SERS sensor. The integration of SERS sensors with functional microfluidic devices may hold great promise for developing advanced Lab‐on‐a‐Chip systems.

An integrated approach for trace detection of pollutants in water using polyelectrolyte functionalized magneto-plasmonic nanosorbents

Resistance of pathogenic micro-organisms to conventional antibiotics is an essential issue for public health. The presence of such pharmaceuticals in aquatic ecosystems has been of major concern for which remediation and ultra-sensitive monitoring methods have been proposed. A less explored strategy involves the application of multifunctional nanosorbents for the uptake and subsequent detection of vestigial contaminants. In this study, colloidal nanoparticles (NPs) of iron oxide and gold were encapsulated in multi-layers of a charged polyelectrolyte (PEI: polyethyleneimine), envisaging the effective capture of tetracycline (TC) and its subsequent detection by Surface Enhanced Raman Scattering (SERS). Adsorption studies were performed by varying operational parameters, such as the solution pH and contact time, in order to evaluate the performance of the nanosorbents for the uptake of TC from water. While the magnetic nanosorbents with an external PEI layer (Fe3O4@PEI and Fe3O4@PEI-Au@PEI particles) have shown better uptake efficiency for TC, these materials showed less SERS sensitivity than the Fe3O4@PEI- Au nanosorbents, whose SERS sensitivity for TC in water has reached the limit of detection of 10 nM. Thus, this study highlights the potential of such magneto-plasmonic nanosorbents as multi-functional platforms for targeting specific contaminants in water, by taking into consideration both functionalities investigated: the removal by adsorption and the SERS detection across the nanosorbents’ surfaces.

Using a Graphene-Polyelectrolyte Complex Reducing Agent To Promote Cracking in Single-Crystalline Gold Nanoplates.

It is a challenge to produce single-crystalline gold nanoparticles having regular size definition designed for controlled light absorbance and internal structural inhomogeneities to enhance electro-magnetic fields. Here, we report a synthetic strategy to generate large single-crystalline triangular or hexagonal gold nanoplates with multiple cracks within the plates using a graphene-polyelectrolyte complex as both a surface adsorbent and bulk reducing agent. Large-scale gold nanoplates can be synthesized within 48 h. First-principles calculations indicate that the nanoplates have a kinetically limited morphology resulting from prior growth of {111} facets confined by the graphene-polyelectrolyte multilayer. The nanocracks result from the inability of the bulk reducing agent to enter narrow defect spaces during growth that remained permanently. The nanoplates had extraordinary physical-chemical detection sensitivity when used for surface-enhanced Raman scattering (SERS) and surface-enhanced infrared absorption (SEIRA). The limit of rhodamine 6G (Rh6G) SERS detection is as low as 5 × 10-13 M. The gold nanoplates also showed a remarkable light-to-heat conversion efficiency (68.5%). The approach described may be applicable to other metals so that tunable nanostructures can be generated by the graphene-polyelectrolyte multilayer strategy.

All-fiber SERS sensing with a depressed double cladding fiber probe embedded in a microfluidic chip.

A fiber surface-enhanced Raman scattering (SERS) probe based on the depressed double cladding fiber (DDCF) is demonstrated. Due to the depressed cladding, the optical field distribution of the DDCF is more approachable to the outer surface than that of a no core fiber without depressed cladding, improving the excitation efficiency for generating Raman scattered light. The cladding diameter of the DDCF is only 80 µm, which is smaller than the core diameter (105 µm) of the input multimode fiber (MMF). This small cladding diameter ensures a well collection coupling from the DDCF to the MMF. The impact of the DDCF length on the performance of the probe is investigated. Raman spectra of Rhodamine 6G (R6G) are measured using the DDCF-based SERS probe, which is embedded in a microfluidic chip. The all-fiber optical path configuration realizes an all-fiber Raman detection system that is stable, portable, and convenient to operate. Such results confirm the applicability of the DDCF-based fiber probe in the all-fiber SERS detection area and indicate that the proposed SERS probe renders a new scheme for optimal design of the fiber SERS probe structure.

Manipulating "Hot Spots" from Nanometer to Angstrom: Toward Understanding Integrated Contributions of Molecule Number and Gap Size for Ultrasensitive Surface-Enhanced Raman Scattering Detection.

Narrower gaps between metal nanoparticles (so-called "hot spots") in surface-enhanced Raman scattering (SERS) substrates contribute to stronger electromagnetic (EM) enhancement; however, the accompanying steric effect hinders analyte molecules entering hot spots to access the benefit. To comprehensively understand integrated contributions of the gap size and molecule number accommodated in hot spots and then optimize design of SERS substrates, the thermal shrinking method was employed to manipulate hot spots and the "hottest zone" was defined to evaluate the integrated contributions to SERS intensity of the two factors. In the conventional shrink-adsorption mode, the contributions of the molecule number and gap size are competitive when the gap width is comparable with the target molecule size, which leads to oscillating behavior of SERS intensity versus gap size, and it is analyte molecule size dependent. This result suggests that engineering hot spots should be target molecule directed to achieve ultrasensitive detection. In the proposed adsorption-shrink mode, the contributions of the molecule number and gap size are synergistic, which makes the detection ability of the adsorption-shrink mode attains a single-molecule (SM) level. Excellent performance of the adsorption-shrink SERS strategy benefits detection of trace level pollutants in complex environments. Detection ranges for contaminants with different metal affinity, such as thiram, malachite green (MG), and formaldehyde, are as low as parts per billion, even down to parts per trillion.

Citrate-assisted galvanic replacement for fabrication of homogeneous Ag nanosheets as high-performance SERS substrate

An effective and simple method for the fabrication of Ag nanosheets (NSs) was developed via citrate-assisted galvanic replacement at room temperature. The effects of reaction time, concentration of AgNO3 and citrate on the morphology and surface-enhanced Raman scattering (SERS) performance of Ag NSs were investigated systematically. The results indicated that citrate played a vital role on preparing uniform Ag NSs, because it could retard the reaction rate and control the direction of Ag growth. Furthermore, citrate was bound weakly toward Ag NSs and easily replaced by probe molecules, which opened a new avenue for the fabrication of clean SERS substrates. In addition, the Ag NSs substrate exhibited a high sensitivity in SERS detection and the analytical enhancement factor was up to 7.93 × 105 with the minimum detected concentration of R6G as low as 10−8 M. Moreover, the color mapping was relatively uniform and the relative standard deviation was below 15%, revealing that the SERS performance of Ag NSs substrate was highly reproducible. Consequently, we believe this citrate-directed galvanic replacement could regulate the morphology and produce clean and highly active SERS substrates, which would be potentially useful for its practical application.

Enhanced Surface-Enhanced Raman Scattering (SERS) Sensitivity by the Self-Assembly of Silver Nanoparticles (Ag NPs) Laminated on Polydimethylsiloxane (PDMS)

Herein, a transparent and reproducible substrate, fabricated using polydimethylsiloxane (PDMS) laminated with self-assembled Ag nanoparticles (Ag NPs), was employed as a universal surface-enhanced Raman scattering (SERS) substrate for the detection of targets with various matrices. The Ag NPs were assembled in a two-dimensional manner via a self-assembly technique. Due to the electrostatic interaction between the Ag NPs, the reproducibility of the assembly was ensured by the fixed density of the assembled Ag NPs at saturated assembly states. The assembled pattern and plasmon resonance of the Ag NPs were well preserved during the molding and curing of PDMS. As a result, the Ag NP laminated PDMS film exhibited a SERS effect to the adsorbed p-aminothiophenol comparable to that of the assembled Ag NPs on a glass slide. Extra SERS enhancement was achieved by construction of a Ag (PDMS)/molecule/Ag (glass) configuration due to the electromagnetic coupling between the Ag NPs. The Raman scattering of 4-mercaptobenzoic acid and benzotriazole modified on the surfaces of a smooth Au electrode and copper foil, respectively, was detected with the aid of the Ag NP-laminated PDMS film. Furthermore, malachite green dispersed in a KBr solid matrix was quantitatively determined with a detection limit of 0.5 μg/g. It is suggested that the SERS enhancement and consequential SERS detection sensitivity of the target molecules may be further maximized by adjusting the distance between the target molecules and the Ag NPs laminated on the PDMS film.

Plasmonic Gold Nanohole Array for Surface-Enhanced Raman Scattering Detection of DNA Methylation.

Surface-enhanced Raman spectroscopy (SERS), which utilizes nanogaps between noble-metal nanostructures as hot spots to yield ultrasensitive SERS signals, is an outstanding label-free and straightforward tool for DNA methylation analysis. Herein, a plasmonic gold nanohole array (PGNA) with well-controlled hot spots and an open surface was designed as a SERS substrate for DNA methylation detection. A finite-difference time-domain (FDTD) simulation was first employed to investigate the electric field distributions of the PGNA as a function of the geometric parameters. The plasmonic response was tuned to 785 cm-1 to match the ring breathing vibrational band of cytosine, the intensity change of which was revealed to be a marker of DNA methylation. Then, guided by the FDTD simulation results, the PGNA was fabricated via the electron beam lithography (EBL) technique. The fabricated PGNA had an open and easily accessible surface topology, a SERS enhancement factor of ∼106, and a relative standard deviation (RSD) of 7.1% for 500 repetitions over an area of 20 × 20 μm2 using 1 μM Rhodamine 6G as the Raman reporter. The fabricated PGNA was further used as a platform for determining DNA methylation. The proposed method exhibited a sensitivity for detecting 1% of methylation changes. Moreover, insight into the dynamic information on methylation events was obtained by combining principal component analysis (PCA) with 2D correlation spectroscopy analysis. Finally, clear discrimination of the different methylation sites, such as 5-methylcytosine and N6-methyladenine, was demonstrated.

Highly sensitive surface-enhanced Raman scattering detection of organic pesticides based on Ag-nanoplate decorated graphene-sheets

Organic pesticides are widely used in the modern agriculture. Their residues in food, water and soil pose a huge threat to human health. Surface-enhanced Raman scattering (SERS) spectroscopy is a powerful tool for detecting trace organic pesticides due to its high sensitivity and rich fingerprinting structure information for molecules. In this work, we construct a highly sensitive SERS substrate based on Ag-nanoplates decorated graphene-sheets for ultra-sensitive SERS detection of organic pesticides. The Ag-nanoplates are holded by the graphene and stay closely to each other, creating “hot spots” for SERS-signal amplification. On the other hand, the graphene sheets can serve as pesticides molecules assemblier because of its strong absorption ability and π − π interaction with pesticides molecules. Therefore, the Ag-nanoplates@graphene hybrids (Ag-NP@GH) substrate shows high sensitivity for detecting trace-level organic pesticides, including thiram and methyl parathion (MP), and their mixtures. The limit of detection for thiram and MP was as low as 40 nM and 600 nM, respectively. In addition, a good linear relationship between the Raman intensity and molecular concentration was obtained, indicating the potential application of the Ag-NP@GH substrate for quantitative SERS detection. Importantly, the Ag-NP@GH substrate shows good SERS-signal reproducibility with a relative signal deviation down to 5.6%. These results show high potential of the Ag-NP@GH as effective SERS substrates for rapid detection of trace-level organic pesticides in environment.

Cysteine-mediated synthesis of silver nanonets and their use for Surface Enhanced Raman Scattering (SERS)

Highly-branched plasmonic nanostructures are interesting substrates to be exploited in Surface-Enhanced Raman Scattering (SERS) detection, as sources of efficient Raman “hot-spots”. In this study, l-cysteine is proposed as reducing/capping agents for the production of Ag nanonets showing different morphologies by varying the synthesis conditions. Substrates are coupled to PDMS membranes and characterized by Raman spectroscopy using 4-MBA to define their SERS performance. Experimental evidences confirm that only the thinnest structures are able to guarantee significant SERS responses.

One-Step Preparation Method of Flexible Metafilms on the Water-Oil Interface: Self-Assembly Surface Plasmon Structures for Surface-Enhanced Raman Scattering Detection.

The present study demonstrated a one-step method for the first time to fabricate self-assembled gold nanoparticle (AuNP) metafilms at the water-toluene interface by adding polystyrene-polyisoprene-polystyrene as the support layer. The thiolated polyethylene glycol and ethanol were used to tune the surface charge density on the AuNPs, constructing a balanced situation at the water-toluene interface. The flexible (AuNP) metafilm can be easily obtained after evaporation of the toluene phase and further used as a surface-enhanced Raman scattering (SERS) substrate for trace thiram detection. The SERS sensitivity was tested using standard Raman probes such as crystal violet and malachite green, both with the detect concentration reaching 1 × 10-11 M. Moreover, the excellent reproducibility and elastic properties make the metafilm promising in practical detection. Hence, the trace thiram detection on an orange pericarp was inspected with the detection limit of 0.5 ppm (1 × 10-6 M) as well as a favorable linearity relation with a correlation coefficient of 0.979, exactly matching the realistic application requirements.

Surface-Enhanced Raman Scattering Detection of Fipronil Pesticide Adsorbed on Silver Nanoparticles.

This work presents a surface-enhanced Raman scattering (SERS) and density functional theory (DFT) study of a fipronil adsorbed on colloidal silver nanoparticles (AgNPs). A standard curve was established to quantify fipronil within a range of 0.0001–0.1 ppm (r2 ≥ 0.985), relying on the unique fipronil Raman shift at ~2236 cm−1 adsorbed on AgNPs. DFT calculations suggest that the nitrile moiety (C≡N) binding should be slightly more favorable, by 1.92 kcal/mol, than those of the nitrogen atom of the pyrazole in fipronil and Ag6 atom clusters. The characteristic peaks of the SERS spectrum were identified, and both the calculated vibrational wavenumbers and the Raman intensity pattern were considered. The vibrational spectra of fipronil were obtained from the potential energy distribution (PED) analysis and selective Raman band enhancement.

Graphene oxide coated popcorn-like Ag nanoparticles for reliable sensitive surface-enhanced Raman scattering detection of drug residues

Abstract

Immobilization and 3D Hot-Junction Formation of Gold Nanoparticles on Two-Dimensional Silicate Nanoplatelets as Substrates for High-Efficiency Surface-Enhanced Raman Scattering Detection.

We synthesize a high-efficiency substrate for surface-enhanced Raman scattering (SERS) measurements, which is composed of gold nanoparticles (AuNPs) on two-dimensional silicate nanoplatelets acting as an inorganic stabilizer, via the in-situ reduction of hydrogen tetrachloroaurate (III) by sodium citrate in an aqueous solution. Silicate platelets of ~1-nm thickness and various sizes, viz. laponite (50 nm), sodium montmorillonite (Na+–MMT, 100 nm), and mica (500 nm), are used to stabilize the AuNPs (Au@silicate), which are formed with uniform diameters ranging between 25 and 30 nm as confirmed by transmission electron microscopy (TEM). In particular, the laponite SERS substrate can be used in biological, environmental, and food safety applications to measure small molecules such as DNA (adenine molecule), dye (Direct Blue), and herbicide (paraquat) as it shows high detection sensitivity with a detection limit of 10−9 M for adenine detection. These highly sensitive SERS substrates, with their three-dimensional hot-junctions formed with AuNPs and two-dimensional silicate nanoplatelets, allow the highly efficient detection of organic molecules. Therefore, these Au@silicate nanohybrid substrates have great potential in biosensor technology because of their environmentally-friendly and simple fabrication process, high efficiency, and the possibility of rapid detection.

A microfluidic-SERSplatform for isolation and immuno-phenotyping of antigen specific T-cells

T-cells play a major role in host defense mechanisms against many diseases. With the current growth of immunotherapy approaches, there is a strong need for advanced technologies to detect and characterize these immune cells. Herein, we present a simple approach for the isolation of antigen specific T-cells from the complex biological sample based on T-cell receptor (TCR) and peptide major histocompatibility complex (pMHC) interaction. Subsequently, we characterize those antigen specific T-cells by profiling TCR expression heterogeneity. Our approach utilizes an alternating current electrohydrodynamic (ac-EHD) based microfluidic platform for isolation and surface enhanced Raman scattering (SERS) for TCR expression profiling. The use of ac-EHD enables specific isolation of T-cells by generating a nanoscopic shear force at the double layer of the sensing surface which enhances the frequency of pMHC and TCR interactions and consequently shears off the nonspecific targets. TCR expression profiling of the isolated T-cells was performed by encoding them with SERS-labelled pMHCs followed by SERS detection in bulk as well as in single T-Cell. In proof-of-concept experiments, 56.93 ± 7.31% of the total CD4+T-cells were captured from an excess amount of nonspecific cells (e.g., PBMCs) with high specificity and sensitivity (0.005%). Moreover, TCR analysis data using SERS shows the heterogeneity in the T-cell receptor expression which can inform on the activation status of T-cells and the patient’s response to immunotherapy. We believe that this approach may hold potential for numerous applications towards monitoring immune status, understanding therapeutic responses,and effective vaccine development.

Plasmonic 3D Semiconductor-Metal Nanopore Arrays for Reliable Surface-Enhanced Raman Scattering Detection and In-Site Catalytic Reaction Monitoring.

It is urgent to develop a rapid, reliable, and in-site determination method to detect or monitor trace amounts of toxic substances in the field. Here, we report an alternative surface-enhanced Raman scattering (SERS) method coupled with a portable Raman device on a plasmonic three-dimension (3D) hot spot sensing surface. Plasmonic Ag nanoparticles (AgNPs) were uniformly deposited on 3D TiO2 nanopore arrays as a sensitive SERS substrate, and further coated with graphene oxide (GO). We demonstrate the plasmon-induced SERS enhancement (5.8-fold) and the improvement of catalytic activity by incorporation of plasmonic AgNPs into the 3D TiO2 nanopore arrays. The modification of GO on the TiO2-Ag nanopore array further increases by a 6.2-fold Raman enhancement compared to TiO2-Ag while maintaining good uniformity (RSD < 10%). The optimized TiO2-Ag-GO substrate shows powerful quantitative detection potential for drug residues in fish scales via a simple scrubbing method, and the limit of detection (LOD) for crystal violet (CV) was 10-8 M. The SERS substrate also showed detection practicability of pesticide residues in banana peel with an LOD of 10-7 M. In addition, our TiO2-Ag-GO substrate exhibits excellent SERS self-monitoring performance for catalytic reduction of multiple organics in NaBH4 solution, and the substrate shows good recyclability of 6 cycles. Such a 3D TiO2-Ag-GO substrate is a promising SERS substrate with good sensitivity, uniformity, and reusability, and may be utilized for further miniaturization for point of analytical applications.

Three-Dimensional-Stacked Gold Nanoparticles with Sub-5 nm Gaps on Vertically Aligned TiO2 Nanosheets for Surface-Enhanced Raman Scattering Detection Down to 10 fM Scale.

Seeking for ultrasensitive and low-cost substrates is highly demandable for practical applications of surface-enhanced Raman scattering (SERS) technology. In this work, we report an ultrasensitive SERS-active substrate based on wet-chemistry-synthesized vertically aligned large-area TiO2 nanosheets (NSs) decorated by densely packed gold nanoparticles (Au NPs) with sub-5 nm gaps. Via a multistep successive deposition process, three-dimensional-stacked Au NPs sandwiched by a 3 nm SiO2 layer were assembled onto the TiO2 NS, enabling numerous hotspots due to the formation of both ultratiny plasmonic gaps and semiconductor/metal interfaces. Experimental results show that the fabricated substrate displays a detection limit down to 10 fM (10-14 M) without involving any condensation process by using the crystal violet as probe molecules. Control experiments and electromagnetic simulations indicate that the nanogaps defined by the 3 nm spacer are essential for the obtained excellent SERS performance. With its ultrasensitive detection capability, we demonstrate that the fabricated SERS substrate can be used for the trace analysis of melamine in milk.