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Food safety is a critical issue that is closely related to people's health and safety. As a simple, rapid, and sensitive detection technique, surface-enhanced Raman scattering (SERS) technology has significant potential for food safety detection. Recently, researchers have shown a growing interest in utilizing silent region molecules for SERS analysis. These molecules exhibit significant Raman scattering peaks in the cellular Raman silent region between 1800 and 2800 cm -1 avoiding overlapping with the SERS spectrum of biological matrices in the range 600-1800 cm -1 , which could effectively circumvent matrix effects and improve the SERS accuracy. In this review, the application of silent region molecules-based SERS analytical technique for food safety detection is introduced, detection strategies including label-free detection and labeled detection are discussed, and recent applications of SERS analysis technology based on molecules containing alkyne and nitrile groups, as well as Prussian blue (PB) in the detection of pesticides, mycotoxins, metal ions, and foodborne pathogens are highlighted. This review aims to draw the attention to the silent region molecules-based SERS analytical technique and to provide theoretical support for its further applications in food safety detection., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

A competitive sensitive bio-barcode immunoassay based on bimetallic nanozyme (Au@Pt: gold@platinum) catalysis has been designed for the detection of the pesticide parathion. Gold nanoparticles (AuNPs) were modified with single-stranded thiol oligonucleotides (ssDNAs) and monoclonal antibodies (mAbs) to form AuNP probes; magnetic nanoparticles (MNPs) were coated with ovalbumin (OVA)-parathion haptens as MNP probes, and bimetallic nanozyme (Au@Pt) nanoparticles functionalized with the complementary thiolated ssDNA were used as Au@Pt probes. The Au@Pt probes reacted with the AuNP probes through complementary base pairing. Further, parathion competed with MNP probes to bind the mAbs on the AuNP probes. Finally, the complex system was separated by a magnetic field. The released Au@Pt probes catalyzed a chromogenic system consisting of teramethylbenzidine (TMB). The bimetallic nanozyme-based bio-barcode immunoassay was performed on rice, pear, apple, and cabbage samples to verify the feasibility of the method. The immunoassay exhibited a linear response from 0.01 to 40 μg·kg -1 , and the limit of detection (LOD) was 2.13 × 10 -3 μg·kg -1 . The recoveries and relative standard deviations (RSDs) ranged from 73.12 to 116.29% and 5.59 to 10.87%, respectively. The method was found to correlate well with data obtained by liquid chromatography-tandem mass spectrometry (LC-MS/MS). In conclusion, this method exhibits potential as a sensitive alternative method for the detection of a variety of pesticides, ensuring the safety of fruits and vegetables in agriculture.

The biomimetic enzyme-linked immunosorbent assay (BELISA) is widely used for detection of small-molecule compounds as a result of low cost and reagent stability of molecularly imprinted polymers (MIPs). However, enzyme labels used in BELISA still suffer some drawbacks, such as high production cost and limited stability. To overcome the drawbacks, a biomimetic nanozyme-linked immunosorbent assay (BNLISA) based on MIPs and nanozyme labels was first proposed. For nanozyme labels, platinum nanoparticles (PtNPs) acted as peroxidase by catalyzing the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) into an ideal surface-enhanced Raman scattering (SERS) marker. Blue TMB 2+ and bovine serum albumin (BSA)-hapten showed superior selectivity when competing with targets for binding sites on MIPs, named the Pt@BSA-hapten probe. The BNLISA method was employed to detect triazophos with a limit of detection of 1 ng mL -1 via colorimetric and SERS methods. Replacing traditional enzymes with nanozymes for combination with MIPs may bring about a new prospect for other compound analyses.

A novel and highly sensitive enzyme inhibition assay was developed for the rapid detection of the organophosphate pesticide dichlorvos and the carbamate pesticide carbofuran. It achieves signal amplification by the secondary catalysis of platinum nanoparticles. Acetylcholinesterase (AChE) is capable of catalyzing the hydrolysis of acetylthiocholine to form thiocholine. Thiocholine causes the aggregation of citrate-capped platinum nanoparticles which then lose their peroxidase-mimicking properties. After addition of pesticides, the activity of AChE is inhibited, less thiocholine is produced, less aggregation occurs, and the peroxidase-mimetic properties are increasingly retained. In the presence of tetramethylbenzidine and H 2 O 2 , a deep blue coloration with an absorption maximum at 650 nm will be formed. The assay was applied to the determination of dichlorvos and carbofuran, and detection limits of 2.3 μg·L -1 and 1.4 μg·L -1 were obtained, respectively. Recovery experiments with spiked tap water and pears gave satisfactory relative standard deviations. Graphical abstract The blue product formed by platinum nanoparticle-catalyzed oxidation of 3,3'5,5'-tetramethylbenzidine (TMB) by H 2 O 2 is reduced if acetylthiocholine (ATCh) is hydrolyzed by acetylcholinesterase (AChE) to form thiocholine. However, if AChE is inhibited by pesticides, color formation will recover.

Fast immunoassay-based screening methods are unavailable for most small-molecule pesticides because of a lack of immunogenicity and the difficulty in obtaining antibodies by animal immunization. Aptamers are single-stranded DNA molecules selected through an in vitro process, which can bind to any target including nonimmunogenic small molecules with high affinity and specificity. Although various aptamer-based sensing methods have been developed for antibiotics, microorganisms, heavy metal ions, and biotoxins, there are few reports on aptamer-based methods for quick detection of organophosphorous pesticides. The gold (Au) nanoparticle (AuNP) colorimetric assay is a widely utilized rapid detection method because of properties such as easy operation and visualized results. In the present study, organophosphorous pesticide aptamers were adsorbed on the surface of AuNPs to stabilize the AuNP solution against high concentrations of salt to prevent AuNP aggregation. After the addition of targets, the aptamers binding to the targets are detached from the AuNPs, resulting in aggregation of AuNPs and a color change from red to purple-blue. The proposed method can detect 6 organophosphorous pesticides with good recoveries from 72% to 135% in environmental river water samples. The present study provides a new way for simple, rapid, and multiplex detection of organophosphorous pesticides., (© 2015 SETAC.)

Cyromazine (CYR) can cause serious damage to the organs of animals or human beings, and it was found to bind to polythymine (polyT10) via multiple hydrogen bonding interactions. Based on this novel finding, a highly sensitive and simple colorimetric method was developed for CYR detection by using label-free gold nanoparticles (AuNPs) and polyT10. Under the optimized conditions, excellent linearity was acquired for CYR within the range of 1-500 ng mL(-1). In addition, the spectra and color changes of the AuNP solution were measured by spectrophotometry and observed by the naked eye, and the results showed that as low as 1 and 5 ng mL(-1) of CYR could be detected, depending upon the measurement methods. Afterwards, cucumber was selected to investigate the sample matrix effect and a sample pretreatment procedure was developed with simple homogenization and filtration. Even after 200 times dilution, the limit of detection (LOD) and limit of quantitation (LOQ) reached 252 ng g(-1) and 500 ng g(-1), respectively. The LOD and LOQ satisfied the Chinese requirement for the maximum residue limit (MRL), which is 0.5-1 μg g(-1) of CYR in most vegetables. The assay also showed a good average recovery of 83.7-104.8% with the RSD of less than 7% and good selectivity for cyromazine over other pesticides that may exist in vegetable samples. The method proposed in this study was simple, fast, and highly sensitive and accurate, and the test result with this method was visible to the naked eye. Therefore, it could be used for routine determination of CYR residues in cucumber samples.

Realizing accurate pesticide multiresidue detection in a complex matrix is still a challenge for point-of-care sensing methods. Herein, we introduced background-free and multicolor aptasensors based on bioorthogonal surface-enhanced Raman scattering (SERS) tags and successfully applied them to analyze multiple pesticide residues. The excellent anti-interference and multiplex capability are due to the application of three bioorthogonal Raman reporters involving 4-ethenylbenzenamine (4-EBZM), Prussian blue (PB) and 2-amino-4-cyanopyridine (AMCP) with alkynyl and cyano groups, which demonstrated apparent Raman shift peaks at 1993 cm−1, 2160 cm−1, and 2264 cm−1 in the biologically Raman-silent region, respectively. Ultimately, a detection range of 1–50 nM for acetamiprid, atrazine and malathion was achieved with detection limits of 0.39, 0.57 and 0.16 nM, respectively. The developed aptasensors were successfully used to determine pesticide residues in real samples. These proposed multicolor aptasensors offer an effective strategy for pesticide multiresidue detection with advantages of anti-interference, high specificity and high sensitivity. [Display omitted] • Aptasensors for Pesticide Multi-residues detection Using Bioorthogonal SERS tags. • Bioorthogonal tags demonstrated Raman peaks at 1993, 2160 and 2264 cm−1. • Aptasensors showed LODs of 0.39, 0.57 and 0.16 nM for three pesticides respectively. • Aptasensors were efficiently applied to detect pesticide multi-residues in real samples. [ABSTRACT FROM AUTHOR]