Large-scale field trials with various dose gradients and application frequencies of iprodione took place at 37 experimental sites on 11 types of specialty fruits and vegetables across China, to accurately portray the environmental fate and comprehensively evaluate its associated exposure risks in typical agricultural system. The initial deposition of iprodione was high as 125.0 mg/kg and final residue levels of chives and lettuce leaves exceeded the maximum residue limit in China after the preharvest intervals (PHIs) application. This should be of significant concern. The bi-exponential model selected through model comparison further revealed that the half-lives of iprodione in crops ranged from 0.8 to 9.4 d under open field cultivation, which were prolonged up to 6.5 times in greenhouse environments. The acute exposure risks in order were dark-colored vegetables, light-colored vegetables, shallots and melons, with certain crops like cos lettuce (324.5%) and green garlic (135.0%) in 1-6 years children exceeding safety thresholds. An integrated deterministic and probabilistic risk assessment model was employed to evaluate total risk quotient (RQt, 132.6%–247.2%) and total hazard quotient (HQt, 142.9%–340.0%), where chives contribute the most and shallots come next. The exposure risks of iprodione for rural populations was significantly higher than that for urban populations at a 95% probability level (P < 0.05), with no significant difference between genders. The findings provide a critical scientific foundation for the targeted management and regulatory oversight of iprodione, with specific emphasis on protecting vulnerable populations and mitigating exposure from high-risk crops.
In this study, the residue dynamics of cyflumetofen (CYF) and its metabolite 2-trifluoromethylbenzoic acid (B-1) throughout strawberry cultivation and processing were investigated using high-performance liquid chromatography-tandem mass spectrometry. This technique enabled precise separation and identification of cyflumetofen (CYF, 2.12 min) and its metabolite B-1 (1.35 min), with LOQs of 0.001 mg/kg for both. CYF and B-1 remained stable under frozen and dark storage conditions, persisting in strawberry tissues for up to 59 days. Affected by climate, environment, and strawberry variety, initial CYF residues during cultivation were 0.20-0.46 mg/kg (degradation half-life:1.92-7.07 days), with final residues stabilizing at 0.03-0.36 mg/kg. Additionally, 0.87-50.0% of CYF metabolized into B-1, both showing toxicological effects. Washing reduced their residues in fresh strawberries. Dietary risk assessments (deterministic models) showed processing significantly reduced the dietary risk of strawberry jam to 0.0013-0.0094%.
Current regulatory frameworks may severely underestimate pesticide exposure risks by ignoring stereochemistry. This study hypothesizes that the chiral neonicotinoid dinotefuran undergoes stereoselective dissipation during cultivation and processing-driven concentration in Chinese tea, leading to human health risks. To investigate this hypothesis, a rapid chiral RPLC-MS/MS method (LOQ: 0.001 mg/kg) was developed. Enantioselective degradation was observed in fresh tea leaves, with (R)-dinotefuran (t₁/₂: 0.10-1.51 d) dissipating faster than (S)-dinotefuran (t₁/₂: 0.20-1.91 d), leading to (S)-enantiomer enrichment. Processing dramatically concentrated residues, particularly in green tea (processing factor up to 49.3), resulting in a final concentration (37.74 mg/kg) exceeding China's maximum residue limit for fresh tea. Acute reference dose (ARfD) and acceptable daily intake (ADI) values for the individual enantiomers were derived from LD50 values obtained in preliminary animal experiments, supplemented by computational toxicology. Integrated deterministic and probabilistic risk assessment revealed that while the racemate posed acceptable risks, the acute dietary risk of (S)-dinotefuran was 2.07-fold and > 55.3-fold higher than its (R)-counterpart and the racemate, respectively. The acute and chronic exposure risks of (S)-dinotefuran in green tea are up to 6.6-fold and 4.5-fold higher than the safety threshold, respectively, and its enantiomer specific risk is 6.2-fold that of (R)-dinotefuran, highlighting strong chiral selective toxicity. Our findings underscore the necessity for enantiomer-specific risk assessments and regulations for chiral pesticides in food commodities.
In this study, ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to establish a rapid and sensitive detection method for spirotetramat and its metabolites B-enol, B-keto, B-Mono, and B-glu in vegetables and soil matrices. The limit of quantification was 0.01 mg kg-1 and the retention time ranged from 1.8 to 3.5 minutes. The behavioral characteristics of spirotetramat and its metabolites on various substrates in the two absorption pathways were investigated. The degradation rate of spirotetramat in root irrigation mode was higher than that observed in foliage spray applications. Subsequently, the ecological risk of spirotetramat to soil earthworms was evaluated using both Risk Quotient (RQ) and Toxicity Exposure Ratio (TER) frameworks, while dietary and non-carcinogenic risks to various population groups were assessed via deterministic and probabilistic models. The assessment revealed that spirotetramat posed a potential ecological risk under worst-case scenarios, with RQ values ranging from 1.906 to 11.546, consistently exceeding the critical threshold of 1. Notably, the ecological risk associated with root irrigation was 3.6–4.9 times higher than that of foliar spraying. Conversely, spirotetramat did not pose unacceptable acute (0.060–3.113%) or chronic (0.144–87.779%) dietary exposure risks to the Chinese population, indicating that dietary intake remains within safe regulatory margins. Based on the evaluated exposure levels ranging from 0.063% to 33.250%, the current data suggests that the non-carcinogenic risk of spirotetramat to the exposed populations in China remains within acceptable safety margins under the studied application conditions. These results underscore the urgency of establishing tomato-specific MRLs and prioritizing application methods that balance pest control with soil safety.
Elucidating the degradation fate and risk characteristics of chlorfluazuron, chlorfenapyr, and its metabolite in chives in both open-field and greenhouse cultivations is crucial for safeguarding the ecosystem and humans from their hazardous effects. This study shows that the dissipation pattern and concentration variations of these pesticides are governed by multiple factors, including cultivation patterns and climatic conditions. A biexponential model revealed that the half-lives of chlorfluazuron and chlorfenapyr were 5.4–11.8 d and 3.3–11.6 d in chives, respectively, as indicated by lower akaike information criterion values and the residual mass closer to zero. Additionally, 0.2%–7.9% of chlorfenapyr was metabolized to tralopyril effects after application. A novel risk assessment framework was developed by integrating deterministic modeling with probabilistic Monte Carlo simulation.
Pice quality is often required to monitor the routine pesticide residues.However,there are matrix sensitivity variations during operation.In this study,the UHPLC-MS/MS approach was developed to simultaneously determine the thiodicarb and methomyl in spices(chili,pepper,and spearmint).A systematic optimization of the chromatographic system was undertaken for the optimal separation,sensitivity,and robustness.Sample preparation was commenced with the acetonitrile extraction of the homogenized spice samples,followed by a clean-up step using a modified QuEChERS-based dispersive solid-phase extraction(d-SPE)procedure.Specifically,the materials were also employed as the 50 mg of primary secondary amine(PSA),10 mg of graphitized carbon black(GCB),and 150 mg of anhydrous magnesium sulfate per 1.5mL of the extract.Three analytical columns with the stationary phases were evaluated after optimization under chromatographic conditions:A BEH C18 column(1.7 μm,100 mm×2.1 mm),a BEH HILIC column(1.7 μm,100 mm×2.1 mm),and an HSS T3 column(1.8 μm,100 mm×2.1 mm).The HSS T3 column was specifically designed to retain the polar compounds,indicating the markedly superior performance,thus providing for the excellent peak shape and sufficient retention for both analytes.Subsequent optimization was focused on the mobile phase composition.Four systems were compared:acetonitrile with 0.05%formic acid in water,methanol with 0.05%formic acid in water,pure acetonitrile with water,and pure methanol with water.The optimal methanol-water system was selected without the acid modification.There was a significant increase in the peak area,approximately 57%higher for the thiodicarb.The methomyl was improved to maintain the excellent peak symmetry,compared with the acidified systems.The flow rate was optimized in a range from 0.15 to 0.55 mL/min.A flow rate of 0.35 mL/min was identified as the ideal compromise,indicating a significant enhancement in the peak area,compared with the higher flow rates.The total time was also maintained.The column temperature was examined from 25℃ to 65℃.A temperature of 55℃ was found to maximize the detector response for both compounds.The thiodicarb shared a particularly significant 31.4%increase in the peak area,compared with 25℃.The injection volume was 2 μL,as the excessive volume compromised the chromatographic integrity.Mass spectrometric detection was performed using electrospray ionization in the positive mode(ESI+)with multiple reaction monitoring(MRM).The optimal performance was achieved by the effective separation of the thiodicarb and methomyl within 3 min,with the reproducible retention times of 2.68 and 2.10 min,respectively.The slope ratio of the matrix-matched versus solvent-based calibration curves revealed that there was extreme signal enhancement in the significant matrix,particularly for the methomyl in chili(ME=1815.6%).Matrix-matched calibration was therefore essential for the accurate quantification.There was excellent linearity from 0.001 to 1 mg/L in all spice matrices,with the correlation coefficients(r)≥0.9980.The accuracy and precision were validated after recovery tests at three fortification levels(0.002,0.01,and 0.5 mg/kg)with five replicates.Mean recoveries ranged from 84.3%to 107.7%,with the CV of 3.0%-8.8%.The high sensitivity was obtained with an LOQ of 0.002 mg/kg and LOD of 0.16×10-3 μg/kg,below the regulatory limits.The optimal,sensitive,and robust UHPLC-MS/MS can be expected to simultaneously quantify the thiodicarb and methomyl in the complex spice matrices.The systematic optimization of the chromatographic system,particularly the selection of the HSS T3 column and the methanol-water mobile phase,effectively mitigated the analytical challenges and detection sensitivity.Its suitability was also verified for the routine application in the regulatory monitoring and quality control laboratories,thereby strengthening the safety of the spices in the global food supply chain.
Background and Objectives Highland barley polyphenols demonstrate potent alpha-glucosidase inhibitory activity, showcasing their potential in regulating postprandial glucose homeostasis. However, the key phenolic monomer responsible for this hypoglycemic effect remains to be systematically investigated. Findings Comprehensive metabolomic profiling of highland barley polyphenol extract revealed 25 phenolic monomers. These compounds underwent molecular docking against human and yeast alpha-glucosidase. The docking results identified nine phenolic monomers with superior binding affinities. In vitro assays revealed that quercetin, apigenin, and phloretin exhibited the highest alpha-glucosidase inhibitory activity. Moreover, starch digestion assays demonstrated that supplementing highland barley whole flour with these phenolic monomers (1%, 3%, 5%, w/w) led to a dose-dependent reduction in starch digestibility, specifically reducing the content of rapidly digestible starch (RDS) and increasing resistant starch (RS). Conclusions Quercetin, apigenin, and phloretin are identified as the key phenolic monomers in highland barley responsible for effective alpha-glucosidase inhibition and modulation of starch digestibility. Significance and Novelty The findings provide a theoretical basis for functional food formulations utilizing these natural phenolic monomers as alpha-glucosidase inhibitors.
Clothianidin is significant toxicity to non-target organisms, underscoring the necessity for a simple and highly sensitive biosensor for on-site detection. Herein, a pH responsive biotin-tagged horseradish peroxidase (HRP)encapsulated nanoliposome (HRP@liposome) was synthesized and applied to a colorimetric immunosensor as signal amplification generator. In the presence of clothianidin, it competes with coated antigens for binding to biotinylated antibodies, thereby reducing the number of HRP@liposome due to biotin-streptavidin-biotin interactions. Upon addition of substrate solution, the HRP@liposome are lysed, releasing a substantial amount of HRP, which catalyzes the oxidation of substrate. Under optimal conditions, the colorimetric immunosensor exhibited a 50% inhibition concentration of 4.75 ng mL(-1), with a limit of detection of 0.24 ng mL(-1), and a linear range of 0.24-66.23 ng mL(-1), respectively. The average recoveries were 86.1%-103.6% in spiked environmental and food samples. Compared with conventional enzyme-linked immunosorbent assays, the proposed immunosensor demonstrates higher sensitivity. This research provides a promising reference for rapid assessment in environmental health and food safety.
Goji berry bud tea, known for its high medicinal and nutritional value, is widely consumed. However, limited attention has been given to pesticide residues in this product. An analytical method was optimized for determining 102 analytes in goji berry bud tea, which showed good linearity in the range of 0.001-0.1 mg/L with the coefficients of determination (R-2) > 0.99, and limit of quantitation (LOQ) was 0.05 mg/kg. The average recoveries ranged from 67.90 %-122.45 % with relative standard deviations (RSDs) of 0.58 %-13.74 % at three spiked levels of 0.05 mg/kg, 0.3 mg/kg, and 3 mg/kg. Analysis of 30 tea samples from China revealed the presence of 23 pesticides at concentrations of 0.05-2.63 mg/kg. A representative sample containing twelve pesticides was utilized to determine the transfer rates from dried goji berry bud tea into the infusion. Among these, seven pesticides were transferred during brewing, with acetamiprid, clothianidin, imidacloprid, and thiamethoxam exhibiting high transfer rates. This behavior can be attributed to infusion repetitions and duration, which were potentially related to their log Kow and water solubility. Dietary risk assessments for goji berry bud tea indicated that the acute and chronic risk quotients were significantly lower than 100 %, suggesting that potential risks associated with tea infusion consumption are acceptable. The findings offer novel insights into pesticide residues in goji berry bud tea and their transfer during brewing with the aim of ensuring food safety.
Diabetes is characterized by impaired glucolipid metabolism and chronic inflammation. Aucubin, a natural compound, has shown potential for improving metabolic disorders, but its mechanisms remain unclear. To investigate the effects of aucubin on glucolipid metabolism and the underlying mechanisms in diabetic mice. Diabetic mice were induced by a high-fat diet and streptozotocin. Aucubin was administered, and its effects on metabolic parameters, tissue injury, and molecular profiles were assessed. Fasting blood glucose, insulin, lipid levels, and inflammatory markers were measured. Liver and pancreatic tissues were examined for histological changes. MiRNA and mRNA expression profiles were analyzed using sequencing, and miRNA-mRNA regulatory pairs were identified. Cell transfection and western blotting were performed to validate the regulatory mechanisms. Aucubin significantly reduced fasting blood glucose, triglycerides, total cholesterol, and inflammatory factors, while increasing fasting insulin, pancreatic β-cell function, and high-density lipoprotein cholesterol. It also alleviated liver and pancreatic tissue injury. Transcriptomic analysis identified 143 differentially expressed miRNAs and 2835 differentially expressed mRNAs, with 69 mRNAs enriched in the PI3K/AKT and insulin resistance pathways. Aucubin downregulated miR-505-5p, which negatively regulated IGF1 expression, thereby affecting the FIT1/IRS1/PI3K signaling pathway. Aucubin exerts anti-diabetic effects by mediating miR-505-5p targeting IGF1 to regulate the FIT1/IRS1/PI3K signaling pathway, offering a potential therapeutic strategy for diabetes.
Elucidating the combined exposure of agrochemicals is essential for safeguarding human health and agroecosystem safety. A rapid and high-sensitivity UHPLC-MS/MS method was developed for simultaneous quantification of nine compounds in sorghum by an assembly-line optimization process with a limit of quantitation of 0.001 mg/kg. The concentration variation of atrazine, quinclorac, fluroxypyr-meptyl and metabolites was reflected by terminal magnitudes of <= 0.0665 mg/kg. Additionally, atrazine was dealkylated to deethyl atrazine and desethyl desisopropyl atrazine at concentrations of 0.0014-0.0058 mg/kg during the sorghum harvest. Acceptable health hazardous of atrazine and quinclorac for all life cycle populations were comparatively assessed via deterministic and probabilistic models, in which atrazine gained an 83.55 % share of cumulative dietary risks. Rural residents had significantly higher risks than urban residents, and children were the most sensitive group. Despite the low health risks, combined exposure to herbicides and their metabolites should be continuously stressed, given their cumulative amplification effects.
Elucidating the environmental fate and exposure risk of lufenuron is crucial to ensure food safety and protect human health. In this study, we developed a rapid and sensitive analytical method for tracing lufenuron in cabbages using ultra-high-performance liquid chromatography-tandem mass spectrometry. The occurrence, pharmacokinetic dissipation, and concentration variation of lufenuron were characterized by primary concentrations (0.009-0.420 mg/kg), half-lives (0.3 d-11.7 d), and final magnitude (<LOQ-0.320 mg/kg). A probabilistic model was introduced to assess dietary risks and presented a comprehensive picture of the risk at multi-probabilities. The chronic dietary risk (ADI%) of lufenuron were 1.074-5.609 % from the 50th to the 99.9th percentile. This was compared with deterministic models, which yielded ADI% values ranging from 0.177 % to 0.500 %, both of which were acceptable. The exposure risks of rural females aged 4-6 years were significantly higher than those of the other groups (P < 0.05), which should be taken seriously with the increasing requirement of lufenuron in actual agricultural production.
Understanding the negative effects of agrochemicals on the environment and human health is indispensable for achieving green agriculture. In this study, the optimized UHPLC-MS/MS method achieved a highly sensitive quantification of tolfenpyrad in cabbage within 4.04 min. The occurrence, dissipation, and concentration variation of tolfenpyrad were reflected by the initial deposition of 0.250-2.045 mg/kg, half-lives (T1/2) of 2.4-10.2 d, and terminal magnitudes within 1.134 mg/kg. Furthermore, the fates of tolfenpyrad during processing were elucidated, with processing factors (Pfs) of 0.561-1.282. Among the different processing procedures, soaking in tap water (25 °C) for 5 min removed 43.9 % of tolfenpyrad and was recommended for initial processing. The multidimensional dietary assessment revealed unacceptable levels of short-term risks from tolfenpyrad in children (%ARfD, 160.519-688.725 %) using deterministic and probabilistic models. Fortunately, the risks were minimized to negligible levels (%ARfD, 69.665-98.719 %) through washing and heat processing. Despite the long-term risks (%ADI, 3.310-9.371 %) being within the safety threshold, the cumulative effect of tolfenpyrad in multiple crops (%ADIt, 46.407-121.472 %) and regional differences (p < 0.05) should be emphasized. Our investigation shed light on the fates of tolfenpyrad in raw to processed cabbage with the aim of achieving sustainable agriculture and alerting to the agricultural pollutant's danger to children.
The uptake, translocation, and accumulation of mefentrifluconazole (MFZ), an innovative chiral triazole fungicide, in plants at the enantiomeric level are still unclear. Herein, we investigated the patterns and mechanisms of enantiomeric uptake, bioaccumulation, and translocation through several experiments. Rac-MFZ shows the strongest uptake and bioaccumulation capacity in wheat compared with its enantiomers, while S-(+)-MFZ has the highest translocation potential. Molecular docking provided evidence of the stronger translocation ability of S-(+)-MFZ than R-(-)-MFZ. Split-root experiments showed that MFZ and its enantiomers could undergo long-distance transport within the wheat. Active transport or facilitated and simple diffusion may be involved in the wheat uptake of MFZ. The limited acropetal translocation capability of MFZ may be attributed to the dominant uptake pathway of apoplastic. The concentrations of Rac-MFZ in different subcellular fractions varied greatly. In summary, this study provides novel insights for further understanding the behaviors of MFZ and its enantiomers in plants.
As a non-coding RNA, microRNA (miRNA) has been proven to play an important role in the development and progression of type 2 diabetes mellitus (T2DM). Highland barley is a whole grain from the Tibetan areas of China. Our previous studies have demonstrated its hypoglycemic effect. To further explore the underlining molecular mechanism, we investigated the effect of highland barley intervention on liver miRNA expression profiles in diabetic mice. Our results showed that ten differentially expressed miRNA among different groups were identified and their target genes were predicted. Remarkably, many glycometabolism-associated genes, including Foxo3, Nras, Rptor, Igf1r, Tsc2 and Braf, were negatively regulated by miR-122-5p, miR-503-5p, miR-455-5p and miR-210-3p, respectively. Pathway enrichment analysis revealed these target genes were mainly involved in AMPK, MAPK and FOXO signaling pathways. Thereby, these miRNA and mRNA were validated using qRT-PCR, and the results were consistent with the small RNA-seq and expectations. Highland barley could regulate the MAPK, AMPK, and FOXO signaling pathways by regulating critical miRNA-mRNA pairs, e.x. miR-210-3p-Tsc2/Braf, miR-122-5p-Foxo3, and miR-455-5p-Igf1r, thereby improving blood glucose metabolism in diabetic mice. The present study preliminarily explored the hypoglycaemic effects of highland barley based on transcriptomics, and more detailed and in-depth studies on this topic are needed in the future.
Background Whole grains emerge preventive or ameliorative effects on type 2 diabetes mellitus as one of the staple foods with abundant polyphenols and dietary fiber. However, there is currently no systematic review elucidating the metabolic mechanisms associated with whole-grain regulation of blood glucose metabolism based on novel disease marker microRNAs. Scope and approach The present paper systematically reviewed the metabolic mechanisms of whole grain for blood glucose regulation based on microRNA. In addition to the conventional mechanisms, including insulin resistance, inflammation, oxidative stress, and insulin signaling, we focused on the potential mechanisms of whole grains and their phytochemicals in modulating type 2 diabetes mellitus through microRNA. Key findings and conclusions Whole grains and their phytochemicals could mediate different miRNAs to improve diabetes by intervening with different targets, such as glycolipid metabolism, inflammation, oxidative stress and gut microbial. This work would enrich our understanding of whole grains improving type 2 diabetes mellitus and promote the consumption of whole grains.
As medicine and food homology substance, goji berry is consumed worldwide in the form of fresh, dried and juice; however, pesticide residues have become one of the problems that essentially threaten its quality during cultivation and processing. In this study, a total of 75 dried goji berries were sampled from markets across China, and for the determination of 62 analytes, 28 pesticides were identified. Nine pesticides with high detectable rates and residual levels were selected for folia spraying, and their half-lives were found to range from 1.04 to 2.21 d. The processing factors (PFs) of juice were between 0.25 and 1.02, and this was mainly related with their octanolwater partition coefficient (logKow values). Washing could reduce pesticides residues to varying degrees with the removal rates between 17.00% and 74.05%. Sun drying with higher PF values in the range of 0.61-5.91 exhibited more obvious enrichment effect compared to oven drying. Commercial goji berry had cumulative chronic dietary risks with the hazard index (HI) values of 1.61%-4.97%. Its acute risk quotients (HQas) for consumers were 543.32%-585.92% and were mainly due to insecticides. These results provide important references for rationalizing pesticide application during goji berry cultivation and for the improvement of process to ensure food safety.