The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

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Present and Future of Surface-Enhanced Raman Scattering

In the era of climate change, global agricultural systems are facing numerous, unprecedented challenges. In order to achieve food security, advanced nano-engineering is a handy tool for boosting crop production and assuring sustainability. Nanotechnology helps to improve agricultural production by increasing the efficiency of inputs and minimizing relevant losses. Nanomaterials offer a wider specific surface area to fertilizers and pesticides. In addition, nanomaterials as unique carriers of agrochemicals facilitate the site-targeted controlled delivery of nutrients with increased crop protection. Due to their direct and intended applications in the precise management and control of inputs (fertilizers, pesticides, herbicides), nanotools, such as nanobiosensors, support the development of high-tech agricultural farms. The integration of biology and nanotechnology into nonosensors has greatly increased their potential to sense and identify the environmental conditions or impairments. In this review, we summarize recent attempts at innovative uses of nanotechnologies in agriculture that may help to meet the rising demand for food and environmental sustainability.

https://www.mdpi.com/1420-3049/24/14/2558/pdf

Applications of Nanotechnology in Plant Growth and Crop Protection: A Review

A Review on Surface-Enhanced Raman Scattering.

The SERS effect was initially discovered in the 1970s. Early research focused on understanding the phenomenon and increasing enhancement to achieve single molecule detection. From the mid-1980s to early 1990s, research started to move away from obtaining a fundamental understanding of the phenomenon to the exploration of analytical applications. At the same time, significant developments occurred in the field of photonics that led to the advent of inexpensive, robust, compact, field-deployable Raman systems. The 1990s also saw rapid development in nanoscience. This convergence of technologies (photonics and nanoscience) has led to accelerated development of SERS substrates to detect a wide range of chemical and biological analytes. It would be a monumental task to discuss all the different kinds of SERS substrates that have been explored. Likewise, it would be impossible to discuss the use of SERS for both chemical and biological detection. Instead, a review of the most common metallic (Ag, Cu, and Au) SERS substrates for chemical detection only is discussed, as well as SERS substrates that are commercially available. Other issues with SERS for chemical detection have been selectivity, reversibility, and reusability of the substrates. How these issues have been addressed is also discussed in this review.

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Review of SERS Substrates for Chemical Sensing.

Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

Metal-Organic Frameworks for Food Safety.

Pesticides are essential in modern agricultural practices. Detection of pesticides is an essential step in regulating and monitoring the levels of pesticides in the environment. Even though GC/LC-MS is often the gold standard method for pesticide detection, recent technological advancements has promoted the creation of alternative techniques, such as Surface Enhanced Raman Spectroscopy (SERS), that provide added advantages such as ultrasensitive detection, faster turnover, simpler protocols, in situ sampling, on-site capability and reduced cost. In this review, a comprehensive report of recent advances in SERS detection of synthetic chemical pesticides is given. The development and applications of the SERS technique for pesticide detection in both simple and complex matrices are discussed. The main advantages of using SERS for pesticide detection are highlighted, together with its limitations. Lastly, promising future trends and applications of SERS for pesticides detection are also discussed.

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Review of surface enhanced Raman spectroscopic (SERS) detection of synthetic chemical pesticides

The objective of this study was to develop a simple and rapid method that could detect and discriminate four specific pesticides (isocarbophos, omethoate, phorate, and profenofos) using a single aptamer-based capture procedure followed by Surface Enhanced Raman Spectroscopy (SERS). The aptamer is a single stranded DNA sequence that is specific to capture these four pesticides. The thiolated aptamer was conjugated onto silver (Ag) dendrites, a nanostructure that can enhance the Raman fingerprint of pesticides, through Ag–thiol bonds. It was then backfilled with 6-mercaptohexanol (MH) to prevent nonspecific binding. The modified SERS platform [Ag–(Ap + MH)] was then mixed with each pesticide solution (P) for 20 min. After capturing the pesticides, the Ag–(Ap + MH)–P complex was analyzed under a DXR Raman microscope and TQ Analyst software. The results show that the four pesticides can be captured and detected using principal component analysis based on their distinct fingerprint Raman peaks. The limits of detection (LODs) of isocarbophos, omethoate, phorate, and profenofos were 3.4 μM (1 ppm), 24 μM (5 ppm), 0.4 μM (0.1 ppm), and 14 μM (5 ppm) respectively. This method was also validated successfully in apple juice. These results demonstrated the super capacity of aptamer-based SERS in rapid detection and discrimination of multi-pesticides. This technique can be extended to detect a wide range of pesticides using specific aptamers.

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Development of a single aptamer-based surface enhanced Raman scattering method for rapid detection of multiple pesticides.

Highly sensitive and selective detection of nitrite ions using Fe3O4@SiO2/Au magnetic nanoparticles by surface-enhanced Raman spectroscopy

Acetamiprid is a neonicotinoid pesticide that is commonly used in modern farming. Acetamiprid residue in food commodities can be a potential harm to human and has been implicated in the honey bee hive die off crisis. In this study, we developed rapid, simple, and sensitive methods to detect acetamiprid in apple juice and on apple surfaces using surface-enhanced Raman spectroscopy (SERS). No pretreatment of apple juice sample was performed. A simple surface swab method was used to recover acetamiprid from the apple surface. Samples were incubated with silver dendrites for several minutes and SERS spectra were taken directly from the silver surface. Detection of a set of 5 apple juice samples can be done within 10 min. The swab-SERS method took 15 min for a set of 5 samples. Resulting spectral data were analyzed using principal component analysis. The highest acetamiprid peak at 634 cm(-1) was used to detect and quantify the amount of acetamiprid spiked in 1:1 water-methanol solvent, apple juice, and on apple surface. The SERS method was able to successfully detect acetamiprid at 0.5 μg/mL (0.5 ppm) in solvent, 3 μg/mL (3 ppm) in apple juice, and 0.125 μg/cm(2) on apple surfaces. The SERS methods provide simple, rapid, and sensitive ways to detect acetamiprid in beverages and on the surfaces of thick skinned fruits and vegetables.

Rapid Detection of Acetamiprid in Foods using Surface-Enhanced Raman Spectroscopy (SERS)

Here we presented a simple, rapid and label-free surface-enhanced Raman spectroscopy (SERS) based mapping method for the detection and discrimination of Salmonella enterica and Escherichia coli on silver dendrites. The sample preparation was first optimized to maximize sensitivity. The mapping method was then used to scan through the bacterial cells adsorbed on the surface of silver dendrites. The intrinsic and distinct SERS signals of bacterial cells were used as the basis for label-free detection and discrimination. The results show the developed method is able to detect single bacterial cells adsorbed on the silver dendrites with a limit of detection as low as 104 CFU mL−1, which is two orders of magnitude lower than the traditional SERS method under the same experimental condition. The time needed for collecting a 225 points map was approximately 24 minutes. Moreover, the developed SERS mapping method can realize simultaneous detection and identification of Salmonella enterica subsp. enterica BAA1045 and Escherichia coli BL21 from a mixture sample using principle component analysis. Our results demonstrate the great potential of the label-free SERS mapping method to detect, identify and quantify bacteria and bacterial mixtures simultaneously.

Shintaro Pang

Papers

Review of surface enhanced Raman spectroscopic (SERS) detection of synthetic chemical pesticides

Development of a single aptamer-based surface enhanced Raman scattering method for rapid detection of multiple pesticides.

Highly sensitive and selective detection of nitrite ions using Fe3O4@SiO2/Au magnetic nanoparticles by surface-enhanced Raman spectroscopy

Rapid Detection of Acetamiprid in Foods using Surface-Enhanced Raman Spectroscopy (SERS)

Label-free mapping of single bacterial cells using surface-enhanced Raman spectroscopy