High Surface-enhanced Raman Scattering Sensitivity Research Articles

One-step synthesized multisize AuAg alloy nanoparticles with high SERS sensitivity in directly detecting SARS-CoV-2 spike protein

The coronavirus disease 2019 (COVID-19) caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has resulted in widespread disease transmission, challenging the stability of global healthcare systems. Surface-enhanced Raman scattering (SERS) as an easy operation, fast, and low-cost technology illustrates a good potential in detecting SARS-CoV-2. In the study, one-step fabrication of gold-silver alloy nanoparticles (AuAgNPs) with adjustable metal proportions and diameters is employed as SERS substrates. The angiotensin-converting enzyme 2 (ACE2) functionalized AuAgNPs are applied as sensor surfaces to detect SARS-CoV-2 S protein. By optimizing the SERS substrates, ACE2/Au35Ag65NPs illustrate higher performance in detecting the SARS-CoV-2 S protein with a limit of detection (LOD) of 10 fg/mL in both phosphate-buffered saline (PBS) and pharyngeal swabs solution (PSS). It also provides excellent reproducibility with a relative standard deviation (RSD) of 7.7 % and 7.9 %, respectively. This easily preparable and highly reproducible SERS substrate has good potential in the practical application of detecting SARS-CoV-2.

Construction of the Au Nanoparticle/Graphene Oxide/Au Nanotube (AuNP/GO/AuNT) Sandwich Membrane for Surface-Enhanced Raman Scattering Sensing.

Au nanotube-based composite membrane served as surface-enhanced Raman scattering (SERS) substrate with an ultralarge aspect ratio possesses an excellent flexibility and widely tunable surface plasmon resonance, and by introducing graphene oxide (GO) as a spacer layer, the SERS enhancement of the composite membrane is obviously better than those from the individual blocks of the Au nanotubes (AuNTS) membrane and the Au nanoparticle/graphene oxide (AuNP/GO) membrane. Such a "sandwich" (AuNP/GO/AuNT) structured membrane has a high SERS sensitivity and a wide tunability by controlling the size of Au nanoparticles and the thickness of graphene oxide, and the detection limits of the AuNP/GO/AuNT substrate for R6G and NBA are as low as 10-12 and 10-7 M, respectively; the large enhancement is attributed to the adsorption and chemical mechanism of graphene oxide and the physical mechanism of the Au nanoparticles and nanotubes (the electromagnetic field coupling between them).

Arrays of Triangular Au Nanoparticles with Self-Cleaning Capacity for High-Sensitivity Surface-Enhanced Raman Scattering

Arrays of Triangular Au Nanoparticles with Self-Cleaning Capacity for High-Sensitivity Surface-Enhanced Raman Scattering

A dual-mode strategy for diacetyl detection based on colorimetry and surface-enhanced Raman scattering

Diacetyl is an important food additive with rich creamy flavor whose excessive intake may cause various diseases. Herein, for the first time, we designed a dual-mode method for diacetyl detection based on colorimetry and surface-enhanced Raman scattering (SERS) technology. Diacetyl exhibited excellent oxidase-like catalytic activity under light-mediated condition, facilitating the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue ox-TMB for colorimetric detection. Notably, diacetyl could control the oxidation process of TMB by simply adjusting light irradiation, unlike traditional enzymatic reactions that required terminators to stop the reaction. Interestingly, ox-TMB was an ideal Raman marker for SERS analysis. Then, a three-dimensional flower-like zinc oxide/silver (ZnO/Ag) for sensitive SERS detection was prepared, which exhibited outstanding SERS effect with a high enhancement factor of 1.89 × 108 due to effective charge transfer and synergistic effect between ZnO and Ag. Based on these, SERS method was constructed to indirectly detect diacetyl, which has not been reported due to low Raman activity of diacetyl. The linear ranges of colorimetry and SERS were 0.5–60 μM and 10−9-10−5 M respectively, with detection limits of 0.41 μM and 0.73 nM. Obviously, the dual-mode strategy combined the simplicity and practicality of colorimetry and the high sensitivity of SERS, offering great potential applications in practical samples.

Application of Nanohybrid Substrates with Layer-by-Layer Self-Assembling Properties to High-Sensitivity Surface-Enhanced Raman Scattering Detection.

The present study was conducted to prepare and investigate large-area, high-sensitivity surface-enhanced Raman scattering (SERS) substrates. Organic/inorganic nanohybrid dispersants consisting of an amphiphilic triblock copolymer (hereafter referred to simply as "copolymer") and graphene oxide (GO) were used to stabilize the growth and size of gold nanoparticles (AuNPs). Ion-dipole forces were present between the AuNPs and copolymer dispersants, while the hydrogen bonds between GO and the copolymer prevented the aggregation of GO, thereby stabilizing the AuNP/GO nanohybrids. Transmission electron microscopy (TEM) revealed that the AuNPs had particle sizes of 25-35 nm and a relatively uniform size distribution. The AuNP/GO nanohybrids were deposited onto the glass substrate by using the solution drop-casting method and employed for SERS detection. The self-assembling properties of two-dimensional sheet-like GO led to a regular lamellar arrangement of AuNP/GO nanohybrids, which could be used for the preparation of large-area SERS substrates. Following removal of the copolymer by annealing at 300 °C for 2 h, measurements were obtained under scanning electron microscopy. The results confirmed that 2D GO nanosheets were capable of stabilizing AuNPs, with the final size reaching approximately 40 nm. These AuNPs were adsorbed on both sides of the GO nanosheets. Because the GO nanosheets were merely 5 nm-thick, a good three-dimensional hot-junction effect was generated along the z-axis of the AuNPs. Lastly, the prepared material was used for the SERS detection of rhodamine 6G (R6G), a commonly used highly fluorescent dye. An enhancement factor (EF) of up to 3.5 × 106 was achieved, and the limit of detection was approximately 10-10 M. Detection limits of 10-10 M and < 10-10 M were also observed with the detection of Direct Blue 200 and the biological molecule adenine. It is therefore evident that AuNP/copolymer/GO nanohybrids are large-area flexible SERS substrates that hold great potential in environmental monitoring and biological system detection applications.

Ag Nanoparticles Decorated CuO@RF Core-Shell Nanowires for High-Performance Surface-Enhanced Raman Spectroscopy Application

Vertical-aligned CuO nanowires have been directly fabricated on Cu foil through a facile thermal oxidation process by a hotplate at 550 °C for 6 h under ambient conditions. The intermediate layer of resorcinol-formaldehyde (RF) and silver (Ag) nanoparticles can be sequentially deposited on Cu nanowires to form CuO@RF@Ag core-shell nanowires by a two-step wet chemical approach. The appropriate resorcinol weight and silver nitrate concentration can be favorable to grow the CuO@RF@Ag nanowires with higher surface-enhanced Raman scattering (SERS) enhancement for detecting rhodamine 6G (R6G) molecules. Compared with CuO@Ag nanowires grown by ion sputtering, CuO@RF@Ag nanowires exhibited a higher SERS enhancement factor of 5.33 × 108 and a lower detection limit (10-12 M) for detecting R6G molecules. This result is ascribed to the CuO@RF@Ag nanowires with higher-density hot spots and surface-active sites for enhanced high SERS enhancement, good reproducibility, and uniformity. Furthermore, the CuO@RF@Ag nanowires can also reveal a high-sensitivity SERS-active substrate for detecting amoxicillin (10-10 M) and 5-fluorouracil (10-7 M). CuO@RF@Ag nanowires exhibit a simple fabrication process, high SERS sensitivity, high reproducibility, high uniformity, and low detection limit, which are helpful for the practical application of SERS in different fields.

Quantitative Detection of Mastitis Factor IL-6 in Dairy Cow Using the SERS Improved Immunofiltration Assay.

Interleukin-6 (IL-6) is generally used as a biomarker for the evaluation of inflammatory infection in humans and animals. However, there is no approach for the on-site and rapid detection of IL-6 for the monitoring of mastitis in dairy farm scenarios. A rapid and highly sensitive surface enhanced Raman scattering (SERS) immunofiltration assay (IFA) for IL-6 detection was developed in the present study. In this assay, a high sensitivity gold core silver shell SERS nanotag with Raman molecule 4-mercaptobenzoic acid (4-MBA) embedded into the gap was fabricated for labelling. Through the immuno-specific combination of the antigen and antibody, antibody conjugated SERS nanotags were captured on the test zone, which facilitated the SERS measurement. The quantitation of IL-6 was performed by the readout Raman signal in the test region. The results showed that the detection limit (LOD) of IL-6 in milk was 0.35 pg mL−1, which was far below the threshold value of 254.32 pg mL−1. The recovery of the spiking experiment was 87.0–102.7%, with coefficients of variation below 9.0% demonstrating high assay accuracy and precision. We believe the immunosensor developed in the current study could be a promising tool for the rapid assessment of mastitis by detecting milk IL-6 in dairy cows. Moreover, this versatile immunosensor could also be applied for the detection of a wide range of analytes in dairy cow healthy monitoring.

Highly sensitive near-infrared SERS nanoprobes for in vivo imaging using gold-assembled silica nanoparticles with controllable nanogaps

BackgroundTo take advantages, such as multiplex capacity, non-photobleaching property, and high sensitivity, of surface-enhanced Raman scattering (SERS)-based in vivo imaging, development of highly enhanced SERS nanoprobes in near-infrared (NIR) region is needed. A well-controlled morphology and biocompatibility are essential features of NIR SERS nanoprobes. Gold (Au)-assembled nanostructures with controllable nanogaps with highly enhanced SERS signals within multiple hotspots could be a breakthrough.ResultsAu-assembled silica (SiO2) nanoparticles (NPs) (SiO2@Au@Au NPs) as NIR SERS nanoprobes are synthesized using the seed-mediated growth method. SiO2@Au@Au NPs using six different sizes of Au NPs (SiO2@Au@Au50–SiO2@Au@Au500) were prepared by controlling the concentration of Au precursor in the growth step. The nanogaps between Au NPs on the SiO2 surface could be controlled from 4.16 to 0.98 nm by adjusting the concentration of Au precursor (hence increasing Au NP sizes), which resulted in the formation of effective SERS hotspots. SiO2@Au@Au500 NPs with a 0.98-nm gap showed a high SERS enhancement factor of approximately 3.8 × 106 under 785-nm photoexcitation. SiO2@Au@Au500 nanoprobes showed detectable in vivo SERS signals at a concentration of 16 μg/mL in animal tissue specimen at a depth of 7 mm. SiO2@Au@Au500 NPs with 14 different Raman label compounds exhibited distinct SERS signals upon subcutaneous injection into nude mice.ConclusionsSiO2@Au@Au NPs showed high potential for in vivo applications as multiplex nanoprobes with high SERS sensitivity in the NIR region.Graphical

Highly sensitive SERS substrates with multi-hot spots for on-site detection of pesticide residues

Pesticide residues will be a huge threat to food security and ecological environment; therefore, there is an urgent need to achieve rapid and on-site detection of pesticide residues. Herein, a plasmonic substrate with multiple “hot spots” was fabricated by transferring three-dimensional (3D) Au nanoparticles (NPs) onto the polydimethylsiloxane (PDMS) membrane for highly sensitive surface-enhanced Raman scattering (SERS) detection of pesticide residues. In combination with 3D-FDTD simulations, high SERS enhancement (EF = 1.2 × 108) and high detection sensitivity (LOD = 6.3 × 10-10 M) were achieved, mainly due to the enhanced electromagnetic fields around the “hot spots”. Additionally, the PDMS-based SERS substrate held good transparency and flexibility, enabling conformal contact with non-planar surfaces and allowing the laser to penetrate the back of the analytes. Combined with a portable Raman spectrometer, the substrates holds great potential for rapid, high-sensitive, and on-site detection of contaminants in food, especially for the analyte on the nonplanar surfaces.

Fabrication of stable substoichiometric WOx films with high SERS sensitivity by thermal treatment

Generally, annealing-induced surface oxygen vacancy defects in oxides are easily healed by air. Here, stable Magnéli phase WOx films were fabricated by thermal treatment of WO3 films in vacuum at 500 °C for 4 h. Aboundant electronic levels, derived from W5+-singly charged oxygen vacancy (Vo+) defect complexes, were detected at the surface of the WOx films, which indicates the formation of stable oxygen-defect phases (Magnéli phases). The concentration of surface oxygen vacancy depends on both annealing energy and the oxygen concentration gradient between the surface and the bulk of films. The reduced WO2.88 films exhibited greatly enhanced surface-enhanced Raman scattering (SERS) performance which was even comparable to noble metals without “hot spots”. The detection limit of Rhodamine 6G was decreased from 10−1 to 10−7 M. The outstanding SERS performance was mainly attributed to defect-related levels providing additional and efficient exciton and charge-transfer resonances in the system of molecule and oxide. Combining experimental results with theoretical study, this work demonstrates that the substoichiometric WOx induced by vacuum annealing shows good stability and it is indeed a potential candidate for SERS detection.

Ag-coated 3D Cu(OH)2 nanowires on the woven copper mesh as a cost-effective surface-enhanced Raman scattering substrate

The commercial development of surface-enhanced Raman scattering (SERS) technique is extremely limited to the high-cost and complex fabrication of desired SERS substrate with high SERS sensitivity and good signal reproducibility. Herein, Ag-coated three-dimensional (3D) Cu(OH)2 nanowire arrays on the woven copper mesh were fabricated by a simply in-situ chemical engraving and sputtering deposition as the promising SERS substrate. Importantly, ascribed to the large surface area, the 3D hierarchical micro-nanostructures containing dense needle-like Cu(OH)2 nanowires offer an excellent platform to load the Ag nanoparticles and enrich target molecules, which is favorable for enhancing the Raman signals of adsorbates. As a result, a limit concentration of probe molecule Rhodamine 6G (R6G) down to 0.1 pM was identified, corresponding to an average enhancement factor of 7 orders. The relative signal deviation was tested to be 17.5% for a single sample and 19.3% among 10 samples. Furthermore, thiram fungicide (a sort of pesticide) residue was also analyzed, showing a linear detection range between 0.1 mM and 50 nM. This simple, large-scale and low-cost fabrication approach offers a promising candidate of SERS chips to the practical detection of pesticide residues, food safety inspection and organic pollutants in the environment.

A Sensitive Surface-Enhanced Raman Spectroscopy Method for Detecting Tetracycline in Milk.

Tetracycline, an animal antibiotic, may remain in milk to cause harm to human health. For economic reasons, the abuse of antibiotics is becoming more and more common. Therefore, the abuse of tetracycline has alarmed the dairy industry and many countries such as New Zealand, China, and the USA have proposed strict standards. Surface-enhanced Raman scattering (SERS) is an emerging detection method which has been applied in food detection with the advantages of no complex pretreatment, fast detection, and weak water environment interference. Considering the abuse of antibiotics in dairy industry, we used polydimethylsiloxane (PDMS) plasma cavity as SERS substrate to detect tetracycline in milk. We found that the enhancement ability of PDMS substrate is affected by addition of 4-amino-1-butanol and complex interplay in the milk--tetracycline system. The modified PDMS plasma cavity has high SERS sensitivity that allows us to achieve low detection limit of 0.28 μg/L. The correlation coefficient was 0.987. The detection of tetracycline in milk using PDMS substrate is quick (within 10 min) and it provides a possible method for in-site detection of tetracycline.

Facile fabrication of ultrathin freestanding nanoporous Cu and Cu-Ag films with high SERS sensitivity by dealloying Mg-Cu(Ag)-Gd metallic glasses

Nanoporous metals prepared by dealloying have attracted increasing attention due to their interesting size-dependent physical, chemical, and biological properties. However, facile fabrication of metallic ultrathin freestanding nanoporous films (UF-NPFs) by dealloying is still challenging. Herein, we report a novel strategy of facile preparation of flexible Cu, Cu3Ag, and CuAg UF-NPFs by dealloying thick Mg-Cu(Ag)-Gd metallic glass ribbons. During dealloying, the local reaction latent heat-induced glass transition of the precursor ribbons leads to the formation of a solid/liquid interface between the initially dealloyed nanoporous layer and the underlying supercooled liquid layer. Due to the bulging effect of in situ generated H2 on the solid/liquid interface, Cu, Cu3Ag, and CuAg UF-NPFs with thicknesses of ∼200 nm can self-peel off from the outer surface of the dealloying ribbons. Moreover, it was found that the surface-enhanced Raman scattering (SERS) detection limit of Rhodamine 6G (R6G) on the Cu and CuAg UF-NPF substrates are 10−6 M and 10−11 M, respectively, which are lower than most of the Cu and Cu-Ag substrates prepared by other methods. This work presents a reliable simple strategy to synthesize a variety of cost effective and flexible metallic UF-NPFs for functional applications.

Monolayer ZnS@Ag Nanospheres SERS Substrate for Highly Sensitive Dye Molecules Detection

Surface-enhanced Raman scattering (SERS) substrates with low cost, high sensitivity and good reproducibility are still challenging in practical application. Herein, we propose a facile method to prepare monolayer ZnS@Ag nanospheres (NSs) by sputtering Ag nanoparticles (NPs) on the surfaces of the monolayer ZnS NSs produced by self-assembly. The monolayer ZnS@Ag NSs have rough surface and nanoscale gaps, which can produce large SERS effect. The dye molecules, Rhodamine 6G (R6G) and Rhodamine B (RhB), were used as probe to evaluate the SERS performance on the monolayer ZnS@Ag NSs. It was found that the monolayer ZnS@Ag NSs showed the high SERS sensitivity in the detection of R6G and RhB, the limit of detection (LOD) down to 9.12×10−13 M and 8.55×10−11 M, respectively. The corresponding enhancement factors (EF) are 3.01×108 and 8.2×106, respectively. Furthermore, the ordered structure makes the monolayer ZnS@Ag NSs substrate with high signal reproducibility and stability, and the relative standard deviation (RSD) values are less than 15%. Therefore, the monolayer ZnS@Ag NSs is a candidate for detecting organic dyes in the environment.

Label-Free Detection of Multiplexed Metabolites at Single-Cell Level via a SERS-Microfluidic Droplet Platform

Single-cell metabolomics could be used to discover the chemical strategies of cells for coping with chemical or environmental stress because metabolomics provides a more immediate and dynamic picture of cell functionality. However, these small-molecule metabolites are the most difficult to measure because they characterize rapid metabolic dynamics, structural diversity, and incapacity to achieve signal amplification or labeling. In order to solve above problems, we presented a surface-enhanced Raman scattering (SERS)-microfluidic droplet platform to realize the label-free simultaneous analysis of multiplexed metabolites at the single-cell level via a versatile magnetic SERS substrate composed by silver nanoparticles (AgNPs, 30 nm)-decorated 400 nm Fe3O4 magnetic microspheres. This metal-magnetic composite substrate is beneficial to efficient adsorption of single cell metabolites, fast separation from complex matrixes, and high SERS sensitivity. Also, the endocytosis effect can be fully prohibited due to its relatively large size. This work achieves label-free, nondestructive, simultaneous determination of three single-cell metabolites, pyruvate, adenosine triphosphate (ATP), and lactate, owing to their intrinsic SERS fingerprints. The "hotspots" effect induced by the magnetic aggregation of Fe3O4@AgNPsallows highly sensitive SERS detection. Encapsulating metabolites in such a limited and isolated droplet accelerates the process of diffusion and adsorption equilibriums. Activation with saponin for metabolites was assessed on different cell lines. The SERS-microdroplet platform is a powerful tool for exploring single-cell heterogeneity at the metabolic level.

Cotton fiber-biotemplated synthesis of Ag fibers: Catalytic reduction for 4-nitrophenol and SERS application

In this work, a facile and environment-friendly process is developed for synthesis of Ag fibers (AFs) by using natural cotton as the template. The as-prepared AFs are characterized using Thermal gravimetric analysis (TGA), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), energy disperse X-ray (EDX), Transmission Electron Microscopy (TEM) and UV-Visible spectroscopy. The results show that AFs are built by Ag particles initially formed on the surface of cotton. The AFs maintain the cotton-like fibrous structure after the removing of cotton. The as-prepared AFs can effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. Moreover, the AFs can be served as highly sensitive surface-enhanced Raman scattering (SERS) platforms for the detection of dye molecules, showing significantly high SERS activity toward methylene blue (MB). The superior SERS and catalytic activities of this material are useful in future for potential applications in catalysis and environmental determination based on SERS.

One-step fabrication of dopamine-inspired Au for SERS sensing of Cd2+ and polycyclic aromatic hydrocarbons

We report the development of a versatile surface-enhanced Raman scattering (SERS) sensor based on the use of multifunctional polymer-coated Au colloids. Our results demonstrated that dopamine (DA) serves as a reducing agent for the facile one-pot synthesis of Au nanoparticles (NPs). Under Au reductive conditions, DA was subsequently oxidized to dopamine quinone (DQ), 5,6-dihydroxyindole (DHI), and polydopamine (PDA) via classical Raper–Mason mechanism. HPLC-MS, FTIR, and SERS analysis verified the effect of initial DA concentration on its oxidation products. The universal adhesion of DA, DQ, DHI, and PDA on Au surface allows for customized synthesis of multi-sized and multifunctional Au NPs containing different mussel polymer shells. The PDA on Au exhibited a reactive scaffold to exclusively lock PAHs into the hotspots for SERS sensing. More interestingly, the two-dimensional correlation spectroscopy showed that DQ modified Au exhibited a strong binding ability towards Cd2+, yielding SERS vibrational profiles that allowed the qualitative determination of Cd2+ with a detection limit of 10−8 mol L−1. The systematic investigation reported herein fills significant gaps in the understanding of the DA-mediated Au reduction mechanism, and provides a reliable working basis that allows for the formation of melanin-like polymer coatings on the Au surface. Remarkably, this simple method provides high SERS sensitivity and selectivity in a high-throughput fashion without the requirement for complex pretreatment methods and complicated instruments.

Monodisperse Au@Ag core-shell nanoprobes with ultrasensitive SERS-activity for rapid identification and Raman imaging of living cancer cells

The rapid identification of living cancer cells is highly crucial for cancer diagnosis, prognosis, and treatment monitoring. However, it is a great challenge to develop an effective way for rapid identification and imaging of cancer cells in a living state. Moreover, synthesis of monodisperse nanoparticles (NPs) with high sensitive surface-enhanced Raman scattering (SERS) activity is also a tough work. Herein, we creatively reported a convenient method to synthesize the novel NPs as the substrate of SERS sensors, which possessed a gold nanobipyramid core and silver nanorod shell. These gold nanobipyramid core and silver nanorod shell NPs (Au NBP@Ag NRs) were further modified with 4-mercaptobenzoicacid (4-MBA, Raman reporter molecule) and then conjugated with reduced bovine serum albumin (rBSA) and folic acid (FA) on their surfaces, to finally acquire Au NBP@Ag NR-MBA-rBSA-FA nanoprobes. In this system, With the enhancement factor (EF) of Au NBP@Ag NRs was about 4 × 107, it could significantly enhance Raman signal for Raman reporter molecules, and 4-MBA molecules performed high SERS signals based on their structures; the nanoprobes have favorable specificity and biocompatibility owing to the modification of rBSA which effectively avoided the nonspecific attachment of non-targeted cells. Moreover, the obtained SERS nanoprobes have excellent sensitivity for gastric cancer cells (MGC-803 cells) due to the conjugation of folic acid. Thus, the finally obtained Au NBP@Ag NR-MBA-rBSA-FA nanoprobes possess excellent detection efficiency for living MGC-803 cells. Therefore, our synthesized nanoprobes exhibit ultrasensitive SERS-activity, excellent specificity and superior cancer cells targeting ability, which could be applied for rapid identification and Raman imaging of living cancer cells via the SERS signal detection of the nanoprobes.

Size and dimension dependent surface-enhanced Raman scattering properties of well-defined Ag nanocubes

Understanding the role of the morphology and particle–particle interactions on the plasmonic properties is of significant importance for the development of nanomaterials with excellent optical properties. However, the preparation of precisely defined nanomaterials with sizes that span a large range and their controllable self-assembly still remain a great challenge. Here, a multistep seed-mediated method has been established for preparing uniform Ag nanocubes over a broad size range from nanoscale (50nm) to microscale (1400nm) and with different hierarchical nanostructures range from “zero-dimension” (“0D”) to “three-dimension” (“3D”). The influence of the size and the interactions between the Ag nanocubes on their surface-enhanced Raman scattering (SERS) properties have been systematically and quantitatively investigated. It is demonstrated through experiments and finite-difference time-domain (FDTD) calculations that the SERS activity is dependent on the matching of the nanocube size to the excitation wavelength. The optimal combinations are 80, 110 and 130nm nanocubes with respect to 532, 638 and 785nm excitation wavelength, respectively. Furthermore, the Raman enhancement of the Ag nanocube hierarchical nanostructures increases rapidly from “0D” to “3D”, due to the extra increase of the hot spots that is attributed to the out-of-plane plasmonic coupling realized in the “3D” hierarchical nanostructures. This work clearly illustrates the quantitative role of the size and dimension of Ag nanocubes on their SERS properties and provides fundamental information for the design of advanced nanomaterials with higher SERS sensitivity.

Nickel foam–caged Ag-Au bimetallic nanostructure as a highly rugged and durable SERS substrate

A three-dimensional nickel foam (NF) caging Ag-Au bimetallic nanostructure (Ag-Au@NF) has been demonstrated as a highly rugged and sensitive surface-enhanced Raman scattering (SERS) substrate. The main concept employed in designing this substrate was the protection of SERS-active nanostructures by holding them within a sturdy frame. For this purpose, NF was readily chosen as a strong porous frame to secure the internal nanostructures owing to its excellent structural strength and ability to easily incorporate analytes due to its porous structure. The next issue was the construction of stable and SERS-efficient nanostructures within the NF frame. To meet this need, an Ag-Au bimetallic nanostructure was chosen, combining the high SERS efficiency of Ag and the good surface stability of Au. To fabricate the Ag-Au nanostructure, first a Sn-Ag alloy was constructed on the NF frame by means of electrodeposition (producing Sn-Ag@NF) and then Sn was selectively leached from the alloy by means of free corrosion in NaOH solution (producing Ag@NF). This selective leaching was adopted to make the surface rough to enhance the SERS efficiency in the final substrate. Finally, Au was incorporated into the Ag@NF by means of a galvanic replacement reaction (producing Ag-Au@NF). The use of Ag-Au@NF enabled identification of rhodamine 6G at concentrations as low as 0.1 nM. The Ag-Au@NF substrates were rugged, showing small Raman signal drops after 100 cycles of sandpaper abrasion or 30 min of sonication. Also, the signal decrease was only 4.26% upon 3 days of exposure to ambient air without special care. Overall, the Ag-Au@NF developed herein shows practical merits for adoption in routine and field SERS analyses.