Surface-enhanced Raman spectroscopy (SERS) is an emerging and promising technique for the chemical analysis of food. The use of metallic nanosubstrates improves the sensitivity and capacity of conventional Raman spectroscopy greatly. This paper comprehensively reviews the development and applications of SERS in the chemical analysis of food, mainly focusing on food additives and chemical contaminants. The progress of SERS development and their applications in chemical analysis of food, from detection and characterization of target analytes in simple solvents to complex food matrices, is summarized. The advantages and limitations of different SERS substrates and methodologies are discussed. As most of the current SERS research on chemical analysis of food is still in an early stage, there are still several hurdles for further advancing SERS techniques into real-world applications for complex food products. This review includes our perspectives on the future trends of the SERS technique in the field of food analysis.

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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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Silver nanoparticles (AgNPs) are the most commonly used nanoparticles in consumer products. Concerns over human exposure to and risk from these particles have resulted in increased interest in novel strategies to detect AgNPs. This study investigated the feasibility of surface-enhanced Raman spectroscopy (SERS) as a method for the detection and quantification of AgNPs in antimicrobial products. By using ferbam (ferric dimethyl-dithiocarbamate) as an indicator molecule that binds strongly onto the nanoparticles, AgNPs detection and discrimination were achieved based on the signature SERS response of AgNPs-ferbam complexes. SERS response with ferbam was distinct for silver ions, silver chloride, silver bulk particles, and AgNPs. Two types of AgNPs with different coatings, citrate and polyvinylpirrolidone (PVP), both showed strong interactions with ferbam and induced strong SERS signals. SERS was effectively applicable for detecting Ag particles ranging from 20 to 200 nm, with the highest signal intensity in the 60-100 nm range. A linear relationship (R(2) = 0.9804) between Raman intensity and citrate-AgNPs concentrations (60 nm; 0-20 mg/L) indicates the potential for particle quantification. We also evaluated SERS detection of AgNPs in four commercially available antimicrobial products. Combined with ICP-MS and TEM data, the results indicated that the SERS response is primarily dependent on size, but also affected by AgNPs concentration. The findings demonstrate that SERS is a promising analytical platform for studying environmentally relevant levels of AgNPs in consumer products and related matrices.

Herein we developed a rapid and simple method which used surface-enhanced Raman spectroscopy (SERS) coupled with antibody-modified silver dendrites to detect ovalbumin (OVA), the egg white protein, introduced into whole milk. OVA was first captured out of milk by use of antibody-modified silver dendrites and then directly measured on the silver dendrites by Raman spectroscopy. Results show that this method is capable of detecting OVA at 0.1 μg/mL in phosphate buffered saline (PBS) and 5 μg/mL in milk within 30 min based on the principal component analysis. This method has the potential for wide use in areas such as allergenic protein detection and bioterrorism agent detection in complex matrixes.

Removal of pesticide residues from fresh produce is important to reduce pesticide exposure to humans. This study investigated the effectiveness of commercial and homemade washing agents in the removal of surface and internalized pesticide residues from apples. Surface-enhanced Raman scattering (SERS) mapping and liquid chromatography tandem mass spectrometry (LC-MS/MS) methods were used to determine the effectiveness of different washing agents in removing pesticide residues. Surface pesticide residues were most effectively removed by sodium bicarbonate (baking soda, NaHCO) solution when compared to either tap water or Clorox bleach. Using a 10 mg/mL NaHCO washing solution, it took 12 and 15 min to completely remove thiabendazole or phosmet surface residues, respectively, following a 24 h exposure to these pesticides, which were applied at a concentration of 125 ng/cm. LC-MS/MS results showed, however, that 20% of applied thiabendazole and 4.4% of applied phosmet had penetrated into the apples following the 24 h exposure. Thiabendazole, a systemic pesticide, penetrated 4-fold deeper into the apple peel than did phosmet, a non-systemic pesticide, which led to more thiabendazole residues inside the apples, which could not be washed away using the NaHCO washing solution. This study gives us the information that the standard postharvest washing method using Clorox bleach solution for 2 min is not an effective means to completely remove pesticide residues on the surface of apples. The NaHCO method is more effective in removing surface pesticide residues on apples. In the presence of NaHCO, thiabendazole and phosmet can degrade, which assists the physical removal force of washing. However, the NaHCO method was not completely effective in removing residues that have penetrated into the apple peel. The overall effectiveness of the method to remove all pesticide residues diminished as pesticides penetrated deeper into the fruit. In practical application, washing apples with NaHCO solution can reduce pesticides mostly from the surface. Peeling is more effective to remove the penetrated pesticides; however, bioactive compounds in the peels will become lost too.

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.