Raman silent region - based method for detection of pesticides with cyano group.

Based on the fact that not all chemical substances possess good Raman signals, this article focuses on the Raman silent region signals of pesticides with cyano group. Under the optimized conditions of methanol-water (1:1, v/v) as the solvent, irradiation at 302 nm light source for 20 min, and the use of 0.5 mol/L KI as the aggregating agent, Surface-enhanced Raman spectroscopy (SERS) method for azoxystrobin detection was developed by the Raman silent region signal of 2230 cm-1, and verified by detecting the spiked grapes with different concentrations of azoxystrobin. Other four pesticides with cyano group also could be identified at the peak of 2180 cm-1, 2205 cm-1, 2125 cm-1, and 2130 cm-1 for acetamiprid, phoxim, thiacloprid and cymoxanil, respectively. When azoxystrobin or acetamiprid was mixed respectively with chlorpyrifos without cyano group, their SERS signals in the Raman silent region of chlorpyrifos were not interfered, while mixed with cymoxanil in different ratios (1:4, 1:1 and 4:1), respectively, each two pesticides with cyano group could be distinguished by the changes in the Raman silent region. In further, four pesticides with or without cyano group were mixed together in 1:1:1:1 (acetamiprid, cymoxanil, azoxystrobin chlorpyrifos), and each pesticide still could be identified even at 0.5 mg/L. The results showed that the SERS method combined with UV irradiation may provide a new way to monitor the pesticides with C≡N performance in the Raman silent region without interference from the food matrix.

The impact of modified polystyrene on lysozyme fibrillation studied by surface-enhanced Raman spectroscopy (SERS).

Nanoplastics could modulate the fibrillation of amyloid proteins. However, many chemical functional groups are adsorbed to change the interfacial chemistry of nanoplastics in the real world. Herein, this study aimed to investigate the effects of polystyrene (PS), carboxyl modified PS (PS-COOH), and amino modified PS (PS-NH2) on the fibrillation of hen egg-white lysozyme (HEWL). Due to the differences in the interfacial chemistry, concentration was considered an essential factor. PS-NH2 (10 µg/mL) could promote the fibrillation of HEWL similar to PS (50 µg/mL) and PS-COOH (50 µg/mL). Moreover, promoting the primary nucleation step of amyloid fibril formation was the primary reason. The differences in spatial conformation of HEWL were characterized by Fourier transform-infrared spectroscopy and surface enhanced Raman spectroscopy (SERS). Strikingly, a particular signal of SERS of HEWL incubated with PS-NH2 at 1610 cm-1 was found due to the interaction between amino group of PS-NH2 and tryptophan (or tyrosine) of HEWL. Therefore, a new perspective was provided to understand the regulation of interfacial chemistry of nanoplastics on the fibrillation of amyloid proteins. Additionally, this study suggested that SERS could be a powerful method to investigate the interactions between proteins and nanoparticles.

Core-shell Au@MIL-100 (Fe) as an enhanced substrate for flunixin meglumine ultra-sensitive detection.

This study aimed to develop and validate a simple and efficient surface-enhanced Raman spectroscopy (SERS) method to determine flunixin meglumine (FM) residues in animal tissues through using core-shell Au@MIL-100 (Fe) as enhanced substrate. Au@MIL-100 (Fe) composite material was synthesized by coating metal-organic framework materials (MOFs) on the surface of gold nanoparticles using the solvothermal method. Transmission electron microscopy (TEM), UV-vis spectrum, SERS spectrum, X-ray diffraction (XRD), Infrared spectrum (FT-IR), and EDX elemental mapping results revealed that the structural composition of the compound has good properties with localized surface plasmon resonance (LSPR) properties, high adsorption capacity, excellent SERS sensitivity and stability. When it was used as SERS substrate, the results of quantitative analysis of FM in pork showed a linear range of 0.10-50 mg·L-1 with a correlation coefficient (R2) of 0.9819, the limit of detection (LOD) of 0.15 mg·g-1, the recovery rate of 88.94%∼104.77%, the intra- and inter- batch relative standard deviation (RSD) of 3.57%∼14.22% and 0.18%∼3.44% respectively. Further verification results of the existing standard methods showed no significant difference between the SERS and UV methods (P < 0.05), as well as demonstrating that the SERS method has optimal precision, accuracy, and practicality. These results exposed that Au@MIL-100 (Fe) as a SERS substrate has great potential in rapid and on-site detection analysis.

Zero-Background Surface-Enhanced Raman Scattering Detection of Cymoxanil Based on the Change of the Cyano Group after Ultraviolet Irradiation.

A zero-background method based on surface-enhanced Raman scattering (SERS) was developed for the rapid determination of cymoxanil residue in food. Because of the influence of complex matrices, conventional Raman spectroscopy has multiple peaks that overlap with those of target molecules, which makes qualitative and quantitative detection difficult. However, the cyano group (C≡N) of cymoxanil after ultraviolet irradiation has a special characteristic peak in the Raman-silent region (1800-2800 cm-1), which eliminates the possible background interference. The intensity of the characteristic peak at 2130 cm-1 exhibited a good linear relationship (R2 = 0.9907) with the concentration of cymoxanil in the range of 1.0-50.0 mg/L, whose limit of detection was 0.5 mg/L. The novel method was also applied to the detection of cymoxanil residue in real samples such as cucumber and grape, and the results were in good agreement with those from high-performance liquid chromatography analysis. This revealed that the SERS method has great potential in the detection of cymoxanil in fruits and vegetables. Moreover, ultraperformance liquid chromatography-quadrupole-time-of-flight-mass spectrometry (UPLC-QTOF/MS) was adopted to identify the photoproducts of cymoxanil. The photolysis mechanism was explored by SERS and the UPLC-QTOF/MS technique, which provided basic information on photodegradation of cymoxanil.