Vinegar, a widely used processed agricultural product and common dietary condiment, raises concerns regarding pesticide residues due to potential contamination from its raw materials. This study developed a modified QuEChERS sample preparation method combined with UHPLC-MS/MS for the simultaneous quantification of 13 target pesticide residues in vinegar. Method validation showed satisfactory accuracy and precision, with mean recoveries ranging from 70% to 104% and relative standard deviation (RSD) between 1.2% and 16.0% across three spiked levels (0.002, 0.02, and 0.2 mg/kg). The method demonstrated a limit of quantification (LOQ) of 0.002 mg/kg, with limit of detection (LOD) between 5.2 & times; 10-5 and 8.6 & times; 10-4 mg/kg, indicating high sensitivity. This study applied the analytical method to vinegar samples sourced from Shanxi Province, China. Pesticide residues at concentrations above the LOQ were detected in 46.2% of the analysed samples. However, the total residue concentrations were consistently low, with all measurements below 0.0220 mg/kg. This study developed a novel, efficient, and reliable method for monitoring multi-pesticide residues in vinegar, thereby enhancing food safety oversight.

Although pesticides play a critical role in sorghum cultivation, their residual presence poses significant risks to human health. A rapid and sensitive UHPLC-MS/MS method was developed for the simultaneous determination of residues from 11 fungicides, 3 herbicides, and 2 insecticides in sorghum. The three key phases of the QuEChERS method-extraction, salting-out, and clean-up-were systematically optimized using a three-stage approach with blank matrix controls. The method showed good recovery (82-107%) at three spiked levels (0.001, 0.01, 0.1 mg/kg) with relative standard deviations (RSD) below 18.8%, and the limit of quantification (LOQ) was 0.001 mg/kg. Three insecticides (chlorantraniliprole, clothianidin, and imidacloprid) and two fungicides (azoxystrobin and tebuconazole) were detected in the 38 sorghum samples, with concentrations ranging from < 0.001-0.6409 mg/kg. Moreover, the dietary risk assessment results showed that the chronic hazard quotient (HQc) for pesticide residues in sorghum was 0.00003-0.04051%, well below 1. Overall, this study offers a method for monitoring pesticide residues in sorghum and a valuable reference for evaluating the safety of agricultural products.

Amyloid-beta (A beta) protein is a notable blood biomarker of Alzheimer's disease, and achieving its sensitive detection is a current research hotspot in medicine. Herein, a sandwich-type electrochemical sensor is developed to detect A beta oligomer 42 (A beta O-42, abbreviated as A beta O) sensitively. It uses peptide and aptamer as the recognition element, and the laccase-mimicking nanozyme assemblies (denoted as CH-Cu-NAs) as the signal amplifier. A beta O is captured by specific peptide pre-modified using gold nanoparticles. Next, the CH-Cu-NAs are modified using an aptamer that binds to targets, resulting in a peptide/target/aptamer sandwich-type sensor. The CH-Cu-NAs are used as an amplification unit, which can oxidize hydroquinone into benzoquinone, and stripping peak currents of the oxidation reaction are used to monitor the A beta O level. The proposed method achieves a detection range of 0.05-5 nM with a limit of detection at 0.0192 nM, representing over a 10-fold enhancement in sensitivity relative to conventional peptide-based electrochemical biosensors for A beta O. This good sensitivity is attributed to the threedimensional arrangement of the CH-Cu-NAs enhances the capture efficiency. The sensor also achieves satisfactory results in actual serum samples. The orderly binding of nanozyme monomers and their application as signal amplifiers can offer novel strategies for electrochemically sensitive detection of biomarkers.

Apples are widely favored by consumers, but the presence of pesticide residues can pose risks to their quality and safety. This study investigated the residual levels of pesticides in commercial apples from 11 cities in Shanxi Province, using analytical methods to detect 102 pesticides. A total of 34 pesticides were detected, with the highest detection rate observed for carbendazim (78.95%), tebuconazole (57.14%), and acetamiprid (53.38%). Pesticide concentrations ranged from below 2 μg/kg to 522.96 μg/kg, with all levels remaining within the maximum residue limits (MRLs) in China. The retention factors, which characterize the distribution pattern, exhibited a significantly positive correlation with the base-10 logarithms of the octanol-water partition coefficient (pKow). All detected pesticides showed acceptable acute dietary risks, with values below 21.33% for different consumer groups, as assessed by deterministic and probabilistic models. This study enhances the understanding of residual pesticide levels and dietary risks of pesticides in apples at the provincial scale and promotes the rational application of pesticides.

The antioxidant activities of baicalein, wogonin, baicalin, and wogonoside as representative ingredients in Scutellaria baicalensis have been evaluated by radical scavenging activity and enzyme inhibition.

Apple (Malus x domestica Borkh.) is a globally significant fruit in terms of both production and consumption. Metabolomics characteristics of 22 apple cultivars collected from five major apple-growing regions in Shanxi Province (China) were investigated by using 1H nuclear magnetic resonance (NMR) metabolomics. The analysis revealed significant variations in metabolite profiles among the cultivars, particularly in sugars (glucose, fructose, sucrose), asparagine, quinic acid, L-rhamnitol, phenylalanine, and condensed polyphenols. Notably, the cultivars 'Xinhongxing' and 'NY543' exhibited high levels of asparagine and quinic acid. 'Xinhongxing' had higher glucose levels but lower sucrose and fructose levels than other cultivars. 'Hongjiangjun' from higher altitudes showed elevated malate levels, indicating that environmental factors significantly influence malate metabolism in apple fruits. The study also revealed correlations between metabolites. For example, the content of condensed polyphenols was positively correlated with the level of asparagine, and that of quinic acid with phenylalanine. The study provides valuable insights on factors influencing apple composition and quality, underlining the importance of both genetic and environmental factors. Future research using transcriptomic and proteomic approaches could reveal the impact of geneenvironment interaction on biochemical pathways involved in the primary and secondary metabolism of apples.

An efficient screening method was developed for the detection of 18 pesticide residues (Difenoconazole, Hexaconazole, Paclobutrazol, Triadimefon, Propamocarb, Azoxystrobin, Pyraclostrobin, Fenarimol, Dimethomorph, Metalaxyl, Prochloraz, Pirimicarb, Tolfenpyrad, Chlorfenapyr, Diazinon, Malathion, Ametryn, and Metolachlor) in the Chinese herbal medicine Polygala Radix. The method is based on QuEChERS pretreatment coupled with ultra-high-performance liquid chromatography-tandem triple quadrupole mass spectrometry (UHPLC-MS/MS). The pesticides in Polygala Radix samples were extracted using acetonitrile containing 1% acetic acid, salinised with sodium chloride, and purified using N-primary secondary amine (PSA) and octadecylsilane (C18). All 18 pesticides exhibited good linearity within the 0.001-0.2 mg L-1 concentration range, with coefficients of determination (R2) greater than 0.99. The recoveries at three spiked levels (0.001, 0.01, and 0.1 mg kg-1) ranged from 80.7% to 112.0%, with relative standard deviations (RSDs) between 2.28% and 20.92%. The limits of detection (LODs) were below 0.36 mu g kg-1, and the limit of quantitation (LOQ) was set at the lowest spiked level (0.001 mg kg-1). This method is sensitive, stable, simple, and rapid, making it suitable for detecting pesticide residues in Polygala Radix. Furthermore, it can serve as a valuable reference for analysing pesticide residues in other root-based herbal medicines, contributing to the quality control and safety assessment of herbal products.

The sensitive and efficient detection of ochratoxin A (OTA) is critical for protecting agricultural ecosystems and public health. A dual-mode plasmonic colorimetric/photothermal aptasensor, based on a Mn2+-powered DNA walker for mediating gold nanobipyramid (AuNB) growth, is proposed for OTA detection in this study. In sensing the target OTA, the walking DNA (W-DNA) on the magnetic walker probe was independent and then the environment-friendly Mn2+ powered the generation of DNAzyme, where abundant thiol-modified DNA (DNA-SH) was produced by autonomous walking. The positively related DNA-SH level could mediate AuNB growth and reflect dual-mode plasmonic signals. Ultrasensitivity is demonstrated with a limit of detection (LOD) value of 48.6 pg mL−1 for colorimetric mode and 37.6 pg mL−1 for photothermal mode. The aptasensor exhibited high specificity (with cross-reactivity values below 6.2% for other analytes) and high reliability for OTA detection. The requisite practicability and accessibility are verified via its application in agricultural byproduct samples. The findings of this study offer an alternative and efficient biosensing pathway for improving detection performance, enabling green, enzyme-free, homogeneous, and dual-mode strategies for monitoring other pollutants.

Evaluating the potential chronic health risks posed by pesticides to consumers is essential for ensuring food safety and protecting public health. An ultra-high-performance liquid chromatography–tandem mass spectrometry (UHPLC-MS/MS) method coupled with modified QuEChERS extraction was developed to simultaneously determine 26 pesticide residues in wheat grain and bran. Samples were extracted with acetonitrile with 2% (v/v) acetic acid and cleaned up using C18 sorbent. Method validation demonstrated excellent linearity, accuracy, and precision. When applied to 48 wheat grain and 24 bran samples collected from major wheat-growing regions in China, 12 and 21 pesticides were detected at concentrations ranging from <0.005 to 1.785 mg kg−1 and <0.01 to 2.188 mg kg−1, respectively. Chronic hazard quotients (HQc) and acute hazard quotients (HQa) for all pesticides for grain and bran were far below the safety threshold of 100%. These results indicate that pesticide residues in wheat grain and bran present negligible chronic dietary risks to consumers across all age groups.

Trifloxystrobin and bupirimate are widely used as fungicides for controlling powdery mildew in cucumber cultivation. Supervised field trials were conducted in 12 representative regions across China, following Good Agricultural Practices (GAP) guidelines, to investigate their residue patterns and potential dietary exposure risks. Cucumber samples were analyzed using a validated method involving extraction with acidified acetonitrile (2% acetic acid, v/v), cleanup with primary secondary amine (PSA) and graphitised carbon black (GCB), and quantification by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The method demonstrated excellent recovery rates (85–103%) throughout four spiking levels (0.01, 0.1, 0.3, and 1 mg/kg), with relative standard deviations (RSD) ≤ 4.8%. At 3 days after treatment, the residues of trifloxystrobin (including trifloxystrobin acid), bupirimate, and ethirimol in cucumbers were found to range from <0.01 to 0.013 mg/kg, <0.01 to 0.076 mg/kg, and <0.01 to 0.04 mg/kg, respectively. A chronic dietary risk assessment was conducted using a probabilistic model. The results showed an acceptable chronic risk (RQc ≤ 2.476%) for trifloxystrobin, bupirimate, and ethirimol across different sexes and ages, supporting the conclusion that the use of these fungicides in cucumber cultivation under the tested conditions was safe for Chinese consumers. More research was needed on children because they are at higher risk than other groups.

Aflatoxin B1 (AFB1) is a highly toxic mycotoxin that readily contaminates major food crops. This study presents a novel ratiometric electrochemical paper-based aptasensor for AFB1 detection that utilizes a structure-switching aptamer. The sensor detects AFB1 by folding the DNA aptamer, reducing the electron transfer efficiency between the methylene blue (MB) molecules attached to the DNA and the electrode surface. An inner reference element modified with ferrocene (Fc) is co-assembled on the electrode surface of the paper-based biosensor to enhance the accuracy of AFB1 detection. In the presence of target AFB1, a folded target-aptamer complex is formed, distancing the MB molecules from the electrode and generating a low current signal in a differential pulse voltammetry mode. The ratio of oxidation currents for MB and Fc serves as the metric for monitoring AFB1 levels. The detection range spans from 20.0 to 1000.0 ng mL-1, with a limit of detection of 7.6 ng mL-1. The paper- based aptasensor exhibits excellent specificity and stability. Additionally, its high reliability and applicability are validated by the strong correlation observed between the sensor results and the results obtained using UPLC-MS/MS analysis of real samples. This study offers a low-cost, readily available approach for portable detection of foodborne hazards.

The fungicide pyraclostrobin is the main measure used to control apple alternaria blotch in production. To evaluate the potential dietary risks for consumers, the dissipation and terminal residues of pyraclostrobin were investigated using ultra-high performance liquid chromatography–mass spectrometry (UHPLC–MS/MS). Pyraclostrobin in apples was extracted by acetonitrile with 2% ammonia and then purified using primary secondary amine (PSA) and graphitized carbon black (GCB). The method showed good linearity within the concentration range of 0.005–0.1 mg L−1, with a coefficient of determination (R2) ≥ 0.9958. The recoveries ranged from 96.0% to 103.8%, with relative standard deviations (RSDs) between 0.8% and 2.3%. The limit of quantification (LOQ) was 0.01 mg kg−1. Pyraclostrobin dispersible oil suspension was applied in 12 apple fields across China according to good agricultural practices (GAPs). In Beijing and Shandong, the dissipation of pyraclostrobin followed first-order kinetic equations, with a half-life of 11 days. The terminal residues ranged from <0.01 to 0.09 mg kg−1. The national estimated daily intake (NEDI) of pyraclostrobin was compared with the acceptable daily intake (ADI), resulting in risk quotient (RQc) of 80.8%. These results suggest that pyraclostrobin poses a low health risk to consumers under GAP conditions and according to recommended dosages.

Neonicotinoids (NEOs) are currently the fastest-growing and most widely used insecticide class worldwide. Increasing evidence suggests that long-term NEO residues in the environment have toxic effects on non-target soil animals. However, few studies have conducted surveys on the effects of NEOs on soil animals, and only few have focused on global systematic reviews or meta-analysis to quantify the effects of NEOs on soil animals. Here, we present a meta-analysis of 2940 observations from 113 field and laboratory studies that investigated the effects of NEOs (at concentrations of 0.001-78,600.000 mg/kg) on different soil animals across five indicators (i.e., survival, growth, behavior, reproduction, and biochemical biomarkers). Furthermore, we quantify the effects of NEOs on different species of soil animals. Results show that NEOs inhibit the survival, growth rate, behavior, and reproduction of soil animals, and alter biochemical biomarkers. Both the survival rate and longevity of individuals decreased by 100 % with NEO residues. The mean values of juvenile survival, cocoon number, and egg hatchability were reduced by 97 %, 100 %, and 84 %, respectively. Both individual and cocoon weights were reduced by 82 %, while the growth rate decreased by 88 % with NEO residues. Our meta-analysis confirms that NEOs pose significant negative impacts on soil animals.

Blueberry production and consumption are gradually increasing in China; however, the potential risks of pesticide residues are essentially unknown. In this study, a modified QuEChERS method was used for the analysis of twenty pesticides and their nine metabolites in blueberry by ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) and gas chromatography with tandem mass spectrometry (GC-MS/MS). This method achieved high linearity (R2 > 0.99), accuracy (average recovery, 70-125%), precision (relative standard deviation, RSD ≤12%), and sensitivity (limit of quantification, LOQ, 0.01mg/kg). The dissipation of most pesticides fitted the first-order model, and the half-lives were in the range of 2.21-35.65 d. The residual levels of the analytes on the first day after application were below maximum residue limits (MRLs) on fruits, and ten pesticides with MRLs in China were categorized as low-risk pesticides according to the risk ranking. This study provides a reference for the rational application of pesticides for blueberry cultivation.

In this study, a simple, rapid, and eco-friendly technique, magnetic deep eutectic solvent-based spontaneous liquid-liquid microextraction (MDES-SLLME), was developed to detect triazole fungicides in water, juice, and wine by UHPLC. The unreported SLLME involves injecting the extractant in the whole liquid-phase microextraction, shortening the extraction and separation time without device assistance. MDES produced by heating bio-derived solvent anisole and metal chloride ferric chloride was used as the extractant to reduce the consumption of toxic solvents. Based on the properties of anisole, MDES spontaneously formed small droplets in samples to complete extraction. Based on the properties of ferric chloride, MDES achieved magnetic separation under an external magnetic field. The method was applied to three matrices (water, juice, and wine). The concentration range was 0.007-0.7 mg L-1, and the matrix effect range was 87.4 %-94.9 %. The limit of detection was 0.002 mg L-1. The spiked recoveries ranged from 85.6 % to 94.7 %. The relative standard deviation ranged from 1.7 %-6.3 %. The SLLME requires attention as a potential complement to single-drop microextraction, hollow fiber liquid-phase microextraction, dispersive liquid-liquid microextraction, homogeneous liquid-liquid microextraction, and emulsive liquid-liquid microextraction.

To investigate the dissipation, terminal residues, and dietary exposure risk of flonicamid, a field trial was conducted in China, and cabbage samples were determined by modified QuEChERS pretreatment and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). The method showed good linearity (R-2 >= 0.99), the mean recoveries ranged from 97% to 103%, with the relative standard deviation (RSD) less than 1.5%, and the matrix effect (ME) was 5%. The field trial showed that the dissipation of flonicamid in Shanxi conformed to the first-order kinetic equation with a half-life of 2.2 days. The terminal residue results showed that the residues of flonicamid in cabbage were all lower than 0.12 mg/kg. The hazard quotient (HQ) and risk quotient (RQ) were applied to dietary exposure risk assessment based on terminal residue and toxicology data. The HQ of different populations ranged from 0.17 to 0.37, and the RQ was 81.4%, indicating low risk of dietary intake of flonicamid in cabbage.

Anthocyanins, typical polyphenol compounds in grape skin, have attracted increasing interest due to their health-promoting properties. In this body of work, five representative anthocyanins (Cy-3-O-glc, Dp-3-O-glc, Pn-3-O-glc, Mv-3-O-glc, and Pt-3-O-glc) were studied using the density functional theory (DFT) to elucidate structure–radical scavenging activity in the relationship and the reaction path underlying the radical-trapping process. Based on thermodynamic parameters involved in HAT, SET-PT, and SPLET mechanisms, along with the structural attributes, it was found that the C4′ hydroxyl group mainly contributes to the radical scavenging activities of the investigated compounds. Pt-3-O-glc exhibits a good antioxidant capacity among the five compounds. The preferred radical scavenging mechanisms vary in different phases. For the Pt-3-O-glc compound, the calculations indicate the thermodynamically favoured product is benzodioxole, rather than o-quinone, displaying considerably reduced energy in double HAT mechanisms. Additionally, the thermodynamic and kinetic calculations indicate that the reaction of •OH into the 4′-OH site of Pt-3-O-glc has a lower energy barrier (7.6 kcal/mol), a higher rate constant (5.72 × 109 M−1 s−1), and exhibits potent •OH radical scavenging properties. Molecular docking results have shown the strong affinity of the studied anthocyanins with the pro-oxidant enzyme xanthine oxidase, displaying their significant role in inhibiting ROS formation.

[目的]建立了 QuEChERS方法结合气相色谱-串联质谱法及超高效液相色谱-串联质谱法同时检测黄花菜鲜菜及干菜中6种农药及其代谢物的分析方法.[方法]样品粉碎后经乙腈涡旋提取,干菜样品需加水后再提取,氯化钠盐析分层,N-丙基乙二胺与石墨化碳黑分散固相萃取净化后分析检测,外标法定量.[结果]6种农药及其代谢物在0.01～0.5 mg/kg质量浓度范围内线性关系良好,相关系数r均＞0.99,0.01、0.1、0.5 mg/kg 3个添加水平下,在鲜黄花菜和干黄花菜基质中的添加回收率分别为79.2％～105.5％和79.4％～112.8％,相对标准偏差分别为0.28％～8.94％和0.39％～7.58％,方法检出限和定量限分别为0.10～0.20、0.25～0.50μg/kg.[结论]该方法简便省时、净化效果好、灵敏度及准确度高,可用于鲜、干黄花菜中6种农药及其代谢物的定性定量分析检测.

Thiamethoxam (TMX) has been registered for use on a wide range of crops due to its versatile application methods, however, there is limited literature evaluating the residue behaviors of TMX applied through root irrigation. In this study, the uptake and translocation of TMX, its degradation to clothianidin (CLO), and dissipation in the tomato plant-soil system were conducted. TMX applied by root irrigation was transferable within the tomato plant, including stems, leaves, and fruits at different heights. TMX concentrations in the four sections of stems were ordered as C lower > C mid > C upper > C top , while in the leaves were ordered as C top > C upper > C mid > C lower . The degradation product CLO was detected in the tomato plant, and concentrations of CLO were even higher than those of TMX in the leaves. The translocation factor (TF) of TMX in the same section generally followed the order of TF leaf > TF stem > TF fruit. Residues of TMX and CLO in tomato on 7 days after application were below maximum residue limits (MRLs) in China and Codex Alimentarius Commission (CAC). This study promotes the evaluation of TMX applied through root irrigation for use in the tomato system from a dietary safety perspective.

建立了QuEChERS/超高效液相色谱-串联质谱(UPLC-MS/MS)同时测定土壤中60种农药和24种抗生素的分析方法.样品用Na2EDTA-Mcllvaine缓冲液(pH 7.20)和5%(体积分数)甲酸乙腈溶液提取,经十八烷基键合硅胶(C18)和N-丙基乙二胺(PSA)净化.采用ACQUITY UPLC BEH C18柱(2.1 mm×100 mm,1.7 μm)分离,在多反应监测(MRM)模式下检测,基质匹配标准溶液外标法定量.结果表明,84种目标化合物在各自质量浓度范围内线性关系良好,相关系数(r2)不小于0.990.除甲基硫菌灵、多西环素和金霉素的定量下限(LOQ)为0.1 mg/kg外,其余化合物的LOQ均为0.01 mg/kg.84种目标化合物在不同加标水平下的回收率为60.9%～118%,相对标准偏差(RSD,n = 5)为0.38%～22%.该方法操作简便、灵敏度高、准确度好,适用于土壤中多种农药和抗生素的检测.