SERS combined with QuEChERS using NBC and Fe3O4 MNPs as cleanup agents to rapidly and reliably detect chlorpyrifos pesticide in citrus.

The surface-enhanced Raman spectroscopy (SERS) technique is being increasingly used for the detection of pesticide residues in agricultural products. However, there are large amounts of fluorescence-producing substances in agricultural products, which seriously affect the Raman signal of the analyte. In this paper, the QuEChERS method was used to remove interfering fluorescent substances in the analyte, and the purification effects of different doses of nano bamboo charcoal (NBC) and Fe3O4 magnetic nanoparticle (Fe3O4 MNP) adsorbents were studied. Meanwhile, the Raman spectral acquisition conditions (AuNPs, test solution, and NaCl) were optimized based on the orthogonal test method. The results showed that 300 µL AuNPs, 40 µL test solution, and 100 µL 1.5% NaCl gave the best SERS response effect. 12.5 mg NBC combined with 10 mg Fe3O4 MNPs could effectively remove the interfering substances from citrus. The Raman spectra of chlorpyrifos molecules were theoretically modeled using density-functional theory (DFT). By comparing the DFT results with the actual tests, five feature peaks, at 338, 522, 558, 672, and 1600 cm-1, were obtained for the detection of chlorpyrifos pesticide residues in citrus. Based on the Raman feature peak intensity at 672 cm-1, the concentration of chlorpyrifos in citrus showed a good linear relationship (R2 = 0.9979) in the concentration range of 3-20 mg kg-1. The recovery rate was 92.12% to 98.38%, and the relative standard deviation (RSD) was 1.77% to 5.29%. The lowest detection concentration was about 3 mg kg-1, and the detection time of a single sample could be completed within 15 min. This study showed that the combination of SERS and QuEChERS preprocessing methods could achieve rapid detection of chlorpyrifos pesticide residues in citrus.

A machine learning strategy-incorporated BiFeO3/Ti3C2 MXene electrochemical platform for simple, rapid detection of Pb2+ with high sensitivity.

The electrochemical technique has been increasingly used for the detection of heavy metal ions in the water system. However, the process for determining the optimum experimental conditions was cumbersome, time-consuming, and unsynchronized, resulting in unsatisfactory detection efficiency. Herein, a new machine learning (ML) strategy combined with BiFeO3/Ti3C2 MXene (BiFeO3/MXene) was used to fabricate a simple but efficient electrochemical Pb2+ sensor. The interconnected BiFeO3/MXene composites prepared by a hydrothermal method possessed an interconnected conductive framework, abundant active sites, and a large surface area, which gave them excellent electronic conductivity and high accumulation of Pb2+. Meanwhile, ML methods such as back-propagation artificial neural network (BPANN) and genetic algorithm (GA) combined with orthogonal experimental design (OED) were used to optimize sensor parameters such as the pH of the supporting electrolyte, the BiFeO3/MXene content, deposition potential, and deposition time. Compared with OED and the one factor at a time (OFAT) methods, the OED-ML method greatly simplified the experimental procedures and improved the electrochemical detection performance. The developed sensor showed superior detection performance for Pb2+ with a detection limit of 0.0001 µg L-1 using the OED-ML method, which was much lower than that of the OED and OFAT methods (0.0003 µg L-1). In addition, the sensor showed good repeatability, reproducibility, stability, and interference capability. The feasibility of the method was verified by detecting Pb2+ in lake samples with recoveries ranging from 98.79% to 101.3%. To our knowledge, the ML strategy was introduced for the first time in an electrochemical sensor for Pb2+ detection, which proved the feasibility and practicality of ML.

Exploring Surface-Enhanced Raman Spectroscopy (SERS) Characteristic Peaks Screening Methods for the Rapid Determination of Chlorpyrifos Residues in Rice.

Surface-enhanced Raman spectroscopy (SERS), coupled with characteristic peak screening methods, was developed for analyzing chlorpyrifos (CM) pesticide residues in rice. Au nanoparticles (AuNPs) were prepared as Raman signal enhancement. Magnesium sulfate (MgSO4), primary secondary amine (PSA), and C18 were used to purify the rice extraction. A successive projections algorithm (SPA) was performed to identify the optimal characteristic peaks of CM in rice from full Raman spectroscopy. Support vector machine (SVM) and partial least squares (PLS) were implemented to investigate the quantitative analysis models. The results demonstrated that six Raman peaks such as 671, 834, 1016, 1114, 1436, and 1444 cm-1 were selected by the SPA and SVM models and had better performance using six peaks (only 0.92% of the full spectra variables) with R2p = 0.97, RMSEP = 2.89 and RPD = 4.26, and the experiment time for a sample was accomplished within 10 min. Recovery for five unknown concentration samples was 97.45-103.96%, and T-test results also displayed no obvious differences between the measured value and the predicted value. The study stated that SERS, combined with characteristic peak screening methods, can be applied to rapidly monitor the chlorpyrifos residue in rice.

Rapid detection of sulfonamide antibiotics residues in swine urine by surface-enhanced Raman spectroscopy.

Surface enhanced Raman spectroscopy (SERS) combined with rapid pretreatment technique was used to determine sulfonamide antibiotics (sulfadiazine and sulfathiazole) residue in swine urine. Au nanoparticles (AuNPs) were synthesized as Raman enhance substrate and the extraction of swine urine was purified with primary secondary amine (PSA), octadecyl silane (C18) and graphitized carbon (GCB) to eliminate the interference of the matrix and different dosages of adsorbents (PSA, C18, GCB) were investigated. The results showed that the treatment with C18 of 150 mg, GCB of 200 mg and PSA of 200 mg were an excellent approach for rapidly detecting sulfonamide antibiotics residue in swine urine. Combined with density functional theory calculation (DFT), Raman characteristic peaks of 819, 1102, 1173, 1588 cm-1 and 825, 1127 cm-1 were selected for qualitative and quantitative assessment of sulfadiazine and sulfathiazole in swine urine, respectively. Based on raman characteristic peak of 819 cm-1, a good linear relationship between sulfadiazine concentration and Raman intensity was developed with R2 = 0.9912, and based on raman characteristic peak of 825 cm-1, a good linear relationship between sulfathiazole concentration and Raman intensity was developed with R2 = 0.9941. And recoveries for five unknown concentration samples predicted were 98.47 âˆ¼ 105.18% with relative standard deviation (RSD) of 1.53% ∼ 5.18%. This study demonstrated that SERS coupled with a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method could be employed to rapidly examine the sulfonamide antibiotics residue in swine urine towards its quality and safety monitoring.

Intelligent analysis of maleic hydrazide using a simple electrochemical sensor coupled with machine learning.

A simple electrochemical sensing platform based on a low-cost disposable laser-induced porous graphene (LIPG) flexible electrode for the intelligent analysis of maleic hydrazide (MH) in potatoes and peanuts coupled with machine learning (ML) was successfully designed. The LIPG electrode was patterned by a simple one-step laser-induced procedure on commercial polyimide film using a computer-controlled direct laser writing micromachining system and displayed excellent flexibility, 3D porous structure, large specific surface area, and preferable conductivity. A data partitioning technique was proposed for the optimal MH concentration ranges by selecting the size of datasets, including the size of the training set and the size of the test set combined with the performance metrics of ML models. Different algorithms such as artificial neural networks (ANN), random forest (RF), and least squares support vector machine (LS-SVM) were selected to build the ML models. Three ML models were evaluated, and the LS-SVM model displayed unique superiority. Both the recoveries and RSD of practical application were further measured to assess the feasibility of the selected LS-SVM model. This will have important theoretical and practical significance for the intelligent analysis of harmful residuals in agro-product safety using an electrochemical sensing platform.

Rapid detection of chlorpyrifos pesticide residue in tea using surface-enhanced Raman spectroscopy combined with chemometrics.

Surface enhanced Raman spectroscopy based on rapid pretreatment combined with Chemometrics was used to determine chlorpyrifos residue in tea. Au nanoparticles were used to as enhance substrate. Different dosages of PSA and NBC were investigated to eliminate the tea substrate influence. Competitive adaptive reweighted sampling (CARS) was used to optimize the characteristic peaks, and compared to full spectra variables and the experiment selected variables. The results showed that PSA of 80 mg and NBC of 20 mg was an excellent approach for rapid detecting. CARS - PLS had better accuracy and stability using only 1.7% of full spectra variables. SVM model achieved better performance with R2p = 0.981, RMSEP = 1.42 and RPD = 6.78. Recoveries for five unknown concentration samples were 98.47 ~ 105.18% with RSD - 1.53% ~ 5.18%. T-test results showed that t value was 0.720, less than t0.05,4 = 2.776, demonstrating that no clear difference between the real value and predicted value. The detection time of a single sample is completed within 15 min. This study demonstrated that SERS coupled with Chemometrics and QuEChERS may be employed to rapidly examine the chlorpyrifos residue in tea towards its quality and safety monitoring.

Identification Study of Edible Oil Species with Laser Induced Fluorescence Technology Based on Liquid Core Optical Fiber.

A laser- induced fluorescence detection set based on liquid core optical fiber was established in this study. Eight edible oils were discriminated by using this detection set combined with chemometrics method. The effect of length of liquid core optical fiber on laser induced fluorescence spectrum was explored, and the differences between the spectra of different edible oils were analyzed. The fluorescence spectra of 320 samples covering 8 types of edible oil were measured in 1 meter liquid core optical fiber. Principal component analysis was used in fluorescence data dimensionality reduction process. Partial least squares discriminant analysis (PLS-DA) method was used to develop the identification model to distinguish edible oil species. The results showed that the oil fluorescence intensity is greatly enhanced when liquid core optical fiber was used. With the increase of liquid core optical fiber length，the peaks of laser induced edible oil fluorescence spectra increased and the fluorescence spectra will produce red shift. The red shift tended to a constant value when the fiber length was more than 80 cm. The fluorescence spectra of different edible oils were quite different, its can be used to distinguish different types of edible oil. Principal component scores chart were get using PC1 and PC2 of edible oils fluorescence data which result in a trend of certain gather of same type of edible oil. The recognition rates of PLS-DA model for the calibration set and prediction set were both 100%. The study shows that the developed device in this study has high accuracy for identifying the edible oil species.