Flexible and adhesive tape decorated with silver nanorods for in-situ analysis of pesticides residues and colorants.

A flexible adhesive tape decorated with SERS-active silver nanorods (AgNRs) in the form of an array nanostructure is described. The tape was constructed by transferring the AgNRs nanostructures from silicon to the transparent tape by a "paste & peel off" procedure. The transparent, sticky, and flexible properties of commercial tapes allow almost any SERS-inactive irregular surface to be detected in-situ by pasting the SERS tape onto the position to be analyzed. Three examples for an analytical application are presented, viz. determination of (a) tetramethylthiuram disulfide and thiabendazole (two pesticides), (b) colorants in the gel of a writing pen, and (c) the fluorophore Rhodamine B. The tetramethylthiuram disulfide on apple surface was rapidly detected with a LOD of 28.8 ng·cm-2. The AgNRs effectively quenched the fluorescence of the matrix and fluorophores, this enabling the colorants and Rhodamine B to be identified. The results demonstrated that the SERS tape can be used for versatile in-situ detection. Conceivably, it may find applications in food analysis, non-invasive identification, environmental monitoring, and in other areas of daily life. Graphic abstract A flexible and adhesive SERS active tape decorated with silver nanorods (AgNRs) arrays was constructed through a "paste & peel off" method. It can be used as a versatile in situ analysis platform for various applications.

Ag Nanorods-Based Surface-Enhanced Raman Scattering: Synthesis, Quantitative Analysis Strategies, and Applications.

Surface-Enhanced Raman Scattering (SERS) is a powerful technology that provides abundant chemical fingerprint information with advantages of high sensitivity and time-saving. Advancements in SERS substrates fabrication allow Ag nanorods (AgNRs) possess superior sensitivity, high uniformity, and excellent reproducibility. To further promote AgNRs as a promising SERS substrate candidate to a broader application scope, oxides are integrated with AgNRs by virtue of their unique properties which endow the AgNRs-oxide hybrid with high stability and recyclability. Aside from SERS substrates fabrication, significant developments in quantitative analysis strategies offer enormous approaches to minimize influences resulted from variations of measuring conditions and to provide the reasonable data analysis. In this review, we discuss various fabrication approaches for AgNRs and AgNRs-oxide hybrids to achieve efficient SERS platforms. Then, we introduce three types of strategies which are commonly employed in chemical quantitative analysis to reach a reliable result. Further, we highlight SERS applications including food safety, environment safety, biosensing, and vapor sensing, demonstrating the potential of SERS as a powerful and promising technique. Finally, we conclude with the current challenges and future prospects toward efficient SERS manipulations for broader real-world applications.

Slanted Ag-Al alloy nanorods arrays for highly active and stable surface-enhanced Raman scattering substrates.

Aluminum has been established as an earth-abundant and low-cost alternative to gold and silver for plasmonic applications. Particularly, aluminum largely tends to combines with oxygen compared with silver. Here, a simple glancing angle deposition technique is presented to prepare Ag-Al alloy nanorods (NRs) with a small amount of aluminum. The effect of aluminum is to combine oxygen or corroded substances under certain conditions, such as in the air and in etchants. Beside this, owing to the large diffusion coefficient of aluminum in a Si wafer, the aluminum diffuses easily into a Si wafer, so the bonding force between the Ag-Al alloy NRs and Si wafer can be improved accordingly. In this work, 3.5 at% Al alloy NRs are optimal to exhibit high surface-enhanced Raman scattering (SERS) sensitivity, long-time stability as well as strong bonding force with a Si wafer. Ag-Al alloy NRs make a metal-metal alloy a promising material platform to develop pretty sensitive as well as stable SERS substrates.

Standing wave type localized surface plasmon resonance of multifold Ag nanorods.

Multifold Ag nanorods (AgNRs) have demonstrated great potentials in applications such as surface-enhanced Raman scattering technique due to their specially organized nanostructures. However, there is so far no systematic understanding of their localized surface plasmon resonance (LSPR) behaviors. This work comprehensively studied the plasmonic behaviors of AgNRs with 1, 2 and 3 folded arms. LSPR modes with charge oscillations resembling standing waves were excited in all nanostructures. As arm length increases, there were linear relationships between resonance wavelength and arm length, which applied to all LSPR modes studied. In addition, directly proportional relationships between the slopes of the linear functions and arm number were found for same order LSPR modes of AgNRs. For different modes of a specific AgNR, inversely proportional relationships between the slope and the resonance order N were discovered. These findings evidenced AgNR's standing wave type LSPR characteristics.

Fabrication and simulation of V-shaped Ag nanorods as high-performance SERS substrates.

Bending straight Ag nanorods (AgNRs) into V-shaped structures can generate a higher surface-enhanced Raman scattering (SERS) performance. Numerical simulations showed that V-shaped AgNRs with a total length between 300 nm and 800 nm were more sensitive than equal-length straight AgNRs under a 785 nm laser in most cases. It was found that at a laser wavelength between 500 nm and 1000 nm, the Raman enhancement factor (EF) of a V-shaped AgNR's 3rd plasmon mode was not only optimal among the other major plasmon modes, but also outperformed the plasmon modes of straight AgNRs. Besides, a linear relationship between the resonance wavelength of the V-shaped AgNR's 3rd mode and its length was observed both numerically and experimentally, which was beneficial for the optimization of SERS substrates. Under 785 nm laser excitation, V-shaped AgNR substrates with a single arm length between 330 nm and 340 nm possessed the highest SERS efficiency. This work took AgNR array substrates one step closer to practical applications.

Highly stable and active SERS substrates with Ag-Ti alloy nanorods.

Silver (Ag) nanostructures have been intensively studied as one of the most promising surface-enhanced Raman scattering (SERS) substrates; however, their practical applications have been limited by the chemical instability with regard to oxidation, sulfuration and etching of Ag. Therefore, designing and fabricating highly active Ag nanostructures with high SERS stability has been recognized as an important research area. Herein, Ag-Ti alloy nanorods (Ag-Ti alloy NRs) are designed and fabricated by the oblique angle deposition (OAD) method to protect Ag. Taking advantage of the higher chemical activity of Ti compared with Ag, Ti can be sacrificed against oxidation and corrosion, protecting Ag in harsh environments, further ensuring long-term stability of the SERS substrates. It is demonstrated that a 2% Ti (in atoms) substrate possesses extremely high SERS sensitivity, and is stable both in air for more than 1 month and in 10 mM HNO3 solution for 1 hour. The alloy nanostructure provides a new opportunity to achieve highly sensitive and highly stable SERS substrates.

Quantification of trace chemicals in unknown complex systems by SERS.

The chemical quantitative analysis at trace level has been widely explored by means of various techniques. While it still remains challenging to achieve ultrasensitive but facile, rapid, and inexpensive detection methods. In this paper, the possibility of employing surface-enhanced Raman scattering technique on a portable Raman system for rapid and accurate quantitative analysis of target chemicals in unknown systems was investigated. This detection approach contains 3 steps: (1) adding target chemicals with different amount to the initial unknown solution, leading to new solutions with target molecules of various concentrations; (2) Obtaining different samples' SERS spectra and capturing featured SERS peaks whose intensity grew up with the addition of target chemicals; (3) examining the relationship between featured peak intensity increment after adding target chemicals and its corresponding addition amount, and thus we could perform quantitative analysis of the chemical in an unknown solution and obtain its initial concentration. The validity of this method was systematically demonstrated by estimating the concentrations of 2-Naphthalenethiol (2-NaT) and 4-Mercaptopyridine (4-MPY) both in their single-component solutions and binary solutions, respectively. Predictions are close to their real values. Furthermore, we successfully predicted the concentrations of malachite green (MG) in fish water and benzidine in ground water. This study clearly demonstrates an accurate and facile approach to calculate the concentration of target chemicals in unknown systems, which fully exploit the potential of SERS quantitative analysis.

Surface-Enhanced Raman Scattering Detection of Pesticide Residues Using Transparent Adhesive Tapes and Coated Silver Nanorods.

The efficient extraction of analytes from complex and severe environments is significant for promoting the surface-enhanced Raman scattering (SERS) technique to actual applications. In this paper, a proof-of-concept strategy is proposed for the rapid detection of pesticide residues by utilizing the flexible, transparent, and adhesive properties of commercial tapes and SERS performance of Al2O3-coated silver nanorod (AgNR@Al2O3) arrays. The function of tapes is to rapidly transfer the analytes from the actual surface to the SERS substrate. The novel "tape-wrapped SERS (T-SERS)" approach was constructed by a simple "paste, peel off, and paste again" procedure. The easily obtained but clearly distinguished SERS signals allow us to quickly determine the constituents of complex surfaces, such as tetramethylthiuram disulfide and thiabendazole pesticides from fruits and vegetables, which may be practically applied to food safety, environmental monitoring, and industrial production process controlling.

Ag Nanorods-Oxide Hybrid Array Substrates: Synthesis, Characterization, and Applications in Surface-Enhanced Raman Scattering.

Over the last few decades, benefitting from the sufficient sensitivity, high specificity, nondestructive, and rapid detection capability of the surface-enhanced Raman scattering (SERS) technique, numerous nanostructures have been elaborately designed and successfully synthesized as high-performance SERS substrates, which have been extensively exploited for the identification of chemical and biological analytes. Among these, Ag nanorods coated with thin metal oxide layers (AgNRs-oxide hybrid array substrates) featuring many outstanding advantages have been proposed as fascinating SERS substrates, and are of particular research interest. The present review provides a systematic overview towards the representative achievements of AgNRs-oxide hybrid array substrates for SERS applications from diverse perspectives, so as to promote the realization of real-world SERS sensors. First, various fabrication approaches of AgNRs-oxide nanostructures are introduced, which are followed by a discussion on the novel merits of AgNRs-oxide arrays, such as superior SERS sensitivity and reproducibility, high thermal stability, long-term activity in air, corrosion resistivity, and intense chemisorption of target molecules. Next, we present recent advances of AgNRs-oxide substrates in terms of practical applications. Intriguingly, the recyclability, qualitative and quantitative analyses, as well as vapor-phase molecule sensing have been achieved on these nanocomposites. We further discuss the major challenges and prospects of AgNRs-oxide substrates for future SERS developments, aiming to expand the versatility of SERS technique.

Semi-quantitative analysis of multiple chemical mixtures in solution at trace level by surface-enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) technology combines with chemometric method of principal component analysis (PCA) was used to calculate the composition of chemical mixtures in solution. We reported here that there exists composition discrepancy between molecules in solution and molecules adsorbed on Ag@Al2O3 nanorods substrates due to difference in adsorption kinetics of each component. We proposed here a way to calculate the adsorption kinetics factor for each component using a standard sample as the reference, with which one could correct the predictions given by PCA. We demonstrate the validity of this approach in estimating the compositions of mixtures with two, three and four components of 1, 4-Benzenedithiol, 2-Naphthalenethiol, 4-Mercaptobenzoic acid, and 4-Mercaptopyridine molecules, with acceptable errors. Furthermore, a general formula applied to more complex mixtures was proposed to calculate compositions in solution.

High-Performance Real-Time SERS Detection with Recyclable Ag Nanorods@HfO2 Substrates.

Ag nanorods coated with an ultrathin HfO2 shell (Ag NRs@HfO2) were prepared for the synthesis of a versatile, robust, and easily recyclable surface-enhanced Raman scattering (SERS) substrate. This substrate maximizes the high melting point of the HfO2 shell and thus ensures the excellent plasmonic efficiency of Ag NRs. Therefore, it possesses extraordinary thermal stability and SERS activity, which could act as a reusable and cost-effective SERS detector. After SERS detection, the regeneration of Ag NRs@HfO2 was achieved by annealing the substrate within several seconds. This procedure led to the thermal release of adsorbed molecules and resulted in a refreshed substrate for subsequent measurements. The composite substrate maintained its SERS efficiency well during multiple "detection-heating" cycles, hence demonstrating the stability and recyclability of Ag NRs@HfO2. Furthermore, in addition to revealing the feasibility of SERS sensing in liquids, Ag NRs@HfO2 also provided continuous real-time monitoring of vapor-phase samples at ultralow concentrations. This work provides a robust and renewable SERS sensor with advantages of high sensitivity, stability, cost effectiveness, and easy operation, which can be implemented for both aqueous and gaseous analyte detection and is thus an intriguing candidate for practical applications in environmental, industrial, and homeland security sensing fields.