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With the continuous application of new agricultural chemicals in agricultural systems, it is imperative to study the environmental fate and potential transformation products (TPs) of these chemicals to better assess their ecological and health risks, as well as guide scientific application. The dissipation of fluchloraminopyr was firstly evaluated under aerobic/anaerobic condition in four representative soils, with Dissipation Time 50 (DT50) values ranging from 0.107 to 4.76 days. Eight TPs generated by soil degradation were identified via Ultra-High Performance Liquid Chromatography coupled with Quadrupole Time-of-Flight Mass Spectrometry (UHPLC-QTOF/MS) and Density Functional Theory (DFT) calculations. The predominant transformation reactions of fluchloraminopyr in soil include oxidation, dechlorination, hydroxylation, and acetylation. The predictions from toxicological software indicated that the acute and chronic toxicity of TPs to aquatic organisms was significantly lower than that of fluchloraminopyr. Moreover, both M267 and M221 exhibited higher acute oral toxicity to terrestrial organisms compared to the parent compound. Consequently, these findings offer essential ecological risk evaluation data for the judicious application of fluchloraminopyr.

Abstract The residue of atrazine in field soils poses a major threat to crop growth in the rotation system, raising concerns about grain security and food safety. Current agricultural production requires more efficient and cost-effective mitigation measures in response to the emerging threat. This study reported the critical concentration (0.1 mg L−1) of atrazine injury to soybean seedlings in soil pore water and how biochar amendment could influence the distribution of atrazine in different soil environments. The results showed that biochar significantly reduced the concentration of atrazine in soil pore water, for example, 0.5% biochar in red (cinnamon, fluvo-aquic, paddy, black) soil reduced atrazine concentration from 0.31 (0.20, 0.18, 0.12, 0.03) mg L−1 to 0.004 (0.002, 0.005, 0.013, 0.011) mg L−1 in pore water (P

Organophosphorus and organochlorine pesticides, historically or currently widely used in agriculture, are prevalent in the environment and pose significant risks to public health and ecosystems. This study aimed to develop a robust analytical method for quantifying these pesticides in soil and water. By optimizing solid-phase extraction (SPE) and Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) procedures, and utilizing comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC-TOF-MS), we achieved sensitive detection levels of all organophosphorus and organochlorine pesticides at 10 μg/kg for soil and 0.1 μg/kg for water samples. The mean recoveries were in the range of 74.2–118.3 % and 72.3–106.9 % at fortified concentration levels in soil and water, respectively. The method exhibited good linearity (R² ≥ 0.9874) and precision (relative standard deviations from 0.1 % to 29.9 %), providing a reliable approach for environmental monitoring and advancing the capabilities in pesticide residue analysis.

Currently, the precise causes of over 40 % of recurrent spontaneous abortion (RSA) cases cannot be identified, leading to the term “unexplained RSA” (URSA). Through an exploration of the gut microbiota, metabolites, and immune cell subsets in URSA, this study establishes a link between gut microbiota-derived metabolites and immune cells. The results indicate reduced diversity in the gut microbiota of URSA. Targeted metabolomic analyses reveal decreased levels of gut microbiota-derived deoxycholic acid (DCA), glycolithocholic acid (GLCA), acetate, propionate, and butyrate in URSA. Furthermore, elevated frequencies of Th1, Th17, and plasma B cells, along with decreased frequencies of Tregs and Bregs, are observed in the peripheral blood of URSA. The results demonstrate correlations between the levels of gut microbiota-derived bile acids and short-chain fatty acids and the frequencies of various immune cell subsets in circulation. Collectively, this study uncovers an association between gut microbiota-derived metabolites and circulating immune cell subsets in URSA.

In view of the defects in the previous detection of cuaminosulfate, which only focused on the analysis of copper ions, there is currently no analysis method available to determine the actual state of cuaminosulfate as chelated or bound. In order to investigate the dissipation and terminal residues in soil and watermelon of cuaminosulfate for food safety and environmental risk, a highly effective technique was developed to detect cuaminosulfate residues in watermelon and soil, and field experiments were conducted in China. After single-factor experiments, residual cuaminosulfate in samples was extracted by pure water, purified using a liquid–liquid approach combined with a dispersive solid-phase extraction, and detected by liquid chromatography tandem mass spectrometry (LC-MS/MS). The Box–Behnken design (BBD) study was used to find the optimal solutions for the time of liquid–liquid purification, the amount of extraction solvent, and the amounts of cleanup sorbents for the analytical method. The average recovery of the method was in the range of 80.0% to 101.1%, the average relative standard deviation (RSD) was 5.3–9.9%, and the detection limit was lower than 0.05 mg/kg. The BBD study not only improved the extraction rate of the method, but also saved time and was operated easily. The final residues of cuaminosulfate in watermelon at different sampling intervals were all lower than 0.05 mg/kg under field conditions. The cuaminosulfate in soils dissipated following exponential kinetics, with half-life values in the range of 9.39 to 12.58 days, which varied by different locations. Based on the validated method, food safety residues and soil residues can be determined rapidly and accurately.

N-doped biochar is widely used for activating persulfate to degrade organic pollutants. Which type of N atom is the key factor for activation is still unclear and needs to be further explored and analyzed. In this study, four kinds of biochar were prepared using urea and rice husk as precursors, and tested for the catalytic degradation of dimethomorph. Increasing the nitrogen doping level caused the catalytic removal efficiency of dimethomorph in the presence of peroxymonosulfate increased from 16.6% to 86.8%. A correlation analysis showed that the ability of N-doped biochar to activate PMS is mainly related to the content of pyrrole N, graphite N and carbonyl and the degree of defects. In experiments on electron paramagnetic resonance and free radical suppression, the reactive species of SO4•-, 1O2,·OH and O2.− were detected, among which 1O2 was found to be the main agent in the nonradical pathway. The degradation pathways for dimethomorph were analyzed based on a total of 8 degradation products identified by high-performance liquid chromatography-time of flight mass spectrometry (HPLC-Q-TOFMS). The results of this study provide a fundamental basis for using agricultural waste to produce inexpensive and efficient nonmetal catalysts that are highly effective in reducing dimethomorph levels in agricultural lands.

A fast and sensitive analytical method based on UHPLC coupled with tandem mass spectrometry was established to investigate the dissipation and final residual amounts of mefentrifluconazole in rice, and dietary risk to consumers was evaluated. The method provided good linearity (R2 ≥ 0.9979), accuracy (recovery range, 79.0–101.5%), precision (relative standard deviation range, 1.3–13.9%), and sensitivity (limit of quantification, 0.005 mg/kg). The dissipation dynamics of mefentrifluconazole in rice followed first-order kinetics, with half-lives of 2.8–16.6 days. The final residues of mefentrifluconazole in various samples of harvested brown rice ranged from less than the limit of quantification to 0.092 mg/kg, the latter value being higher than the maximum residue limit recommended by the European Union. Comparative dietary exposure of mefentrifluconazole was assessed using field data and Chinese dietary patterns for different genders, regions, and age data. Although the results showed acceptable levels of risk for both acute exposure (the percentage of the acute reference dose ≤ 0.7483%) and chronic dietary intake (the percentage of acceptable daily intake ≤ 31.8516%), more studies of children are needed because they are at higher risk than other groups. This work provides the necessary data for registering and establishing the maximum residue limit for mefentrifluconazole in rice in China and reveals the potential risks to different groups of long-term application of mefentrifluconazole to rice and other crops.

As new agrochemicals are continuously introduced into agricultural systems, it is essential to investigate their uptake and metabolism by plants to better evaluate their fate and accumulation in crops and the subsequent risks to human exposure. In this study, the uptake and elimination kinetics and transformation of a novel insecticide, cyetpyrafen, in two model crops (lettuce and rice) were first evaluated by hydroponic experiments. Cyetpyrafen was rapidly taken up by plant roots and reached a steady state within 24 h, and it was preferentially accumulated in root parts with root concentration factors up to 2670 mL/g. An uptake mechanism study suggested that root uptake of cyetpyrafen was likely to be dominated by passive diffusion and was difficult to transport via xylem and phloem. Ten phase I and three phase II metabolites of cyetpyrafen were tentatively identified in the hydroponic-plant system through a nontarget screening strategy. The structures of two main metabolites (M-309 and M-391) were confirmed by synthesized standards. The metabolic pathways were proposed including hydroxylation, hydrolysis, dehydrogenation, dehydration and conjugation, which were assumed to be regulated by cytochrome P450, carboxylesterase, glycosyltransferase, glutathione S-transferases and peroxidase. Cyetpyrafen and its main metabolites (M-409, M-309 and M-391) were estimated to be harmful/toxic toward nontarget organisms by theoretical calculation. The high bioaccumulation and extensive transformation of cyetpyrafen highlighted the necessity for systematically assessing the crop uptake and metabolism of new agrochemicals.

Deoxynivalenol (DON) is an important virulence factor of the Fusarium head blight of wheat and threatens the health of humans. The effect of fungicides on DON production after stressing wheat to produce H2O2 and the effect of nontarget pesticides on DON accumulation are largely unknown. Five pesticides were selected to explore the effect of pesticide-induced oxidative stress on DON production in vitro and in vivo. Epoxiconazole and hexaconazole significantly induced an increase in H2O2 in vitro, and H2O2 further stimulated the production of DON and the expression of the Tri5 gene. Imidacloprid, isoproturon, and mesosulfuron-methyl had no direct effect in vitro. All pesticides activated the activities of superoxide dismutase, catalase, and peroxidase in wheat and caused the excessive accumulation of H2O2. However, excessive H2O2 did not stimulate the accumulation of DON. Imidacloprid indirectly stimulated the production of DON in vivo, which may be due to its impact on the secondary metabolism of wheat. In brief, pesticide-induced H2O2 in vitro is an important factor in stimulating DON production, but the stressed physiological H2O2 in wheat is not sufficient to stimulate DON production. The bioaccumulation results indicated that imidacloprid and epoxiconazole increase the risk of DON contamination, especially under field spraying conditions.

Application of atoxigenic strains of Aspergillus flavusto soils is the most successful aflatoxin biological control approach. The objective of this study was to evaluate the efficacies of native non-aflatoxin producing (atoxigenic) strains as a biocontrol agent in peanut field in China. The competitive atoxigenic A. flavus strains (JS4, SI1and SXN) isolated from different crops, in China were used for field evaluation. The strains applied during the growing season (June – October, 2016) in the field at rate of 25 kg inoculum/hectare. The colonization of these biocontrol agents has been investigated and the population of A. flavus communities in soil were determined. The incidences of toxin producing (toxigenic) A. flavus strains and aflatoxin contamination in peanuts were also determined. Treated plots produced significant reductions in the incidence of toxigenic isolates of A. flavus in soil. However, the total fungal densities were not significantly different (p > 0.05) after treatments. Large percentage of aflatoxin reductions, ranging from 82.8% (SXN) up to 87.2% (JS4) were recorded in treated plots. Generally, the results suggest that the strategy can be used to control aflatoxin contamination and continuous evaluation should be done.

Mycotoxin contamination of food and feed is a major concern in sub-Sahara African countries, particularly Nigeria. It represents a significant limit to health of human, livestock as well as the international trade. Aflatoxins, fumonisins, ochratoxin, zearalenone, deoxynivalenol and beauvericin are the major mycotoxins recognised in the aetiology of food safety challenges that precipitated countless number of diseases. In Nigeria, aflatoxins and fumonisin found in nearly all crops are the most common mycotoxins of economic and health importance such as sorghum, maize and groundnuts. Thus, consumption of food contaminated with mycotoxins are inevitable, hence the need for adequate regulation is necessary in these frontier economies as done in many developed economies to ensure food safety for human and animals. In low and middle-income countries, especially Nigeria, there is lack of awareness and sufficient information on the risk associated with consequent of mycotoxin contamination on wellbeing of human, animals health and the economy. It is based on the foregoing that this paper summarized the status of mycotoxin present in Nigerian food and feeds relative to the global regulatory standards. This aimed at preventing consuming mycotoxin contaminated food stuff while confronting its associated challenges. Suggestions on some possible control strategies to mitigate vending mycotoxin food and feeds were made.

It has been reported that drug-drug interactions (DDIs) can affect the pharmacokinetics and pharmacodynamics of various oral drugs. To better understand the effects of azole antifungal drugs (ketoconazole, fluconazole, and itraconazole) on pyrotinib’s pharmacokinetics, DDIs between pyrotinib and three azoles were studied with Sprague-Dawley (SD) rat liver microsomes in vitro. Additionally, in vivo pyrotinib metabolic experiment was also performed. Twenty-four male SD rats were randomly divided into four groups: the ketoconazole (40 mg/kg), fluconazole (40 mg/kg), itraconazole (40 mg/kg), and the control group. UPLC-MS/MS was used for the determination of Pyrotinib’s plasma concentration in rats. In vitro experiments showed that IC50 values of ketoconazole, fluconazole and itraconazole were 0.06, 11.55, and 0.27 μM, respectively, indicating that these drugs might reduce the clearance rate of pyrotinib at different degrees. In rat studies, coadministration of pyrotinib with ketoconazole or fluconazole could dramatically increase the Cmax and AUC(0-t) values and decrease the clearance rate of pyrotinib, especially for ketoconazole. However, coadministration with itraconazole had no impact on the pharmacokinetic characters of pyrotinib. These data indicated that ketoconazole and fluconazole could significantly decrease the metabolism of pyrotinib both in vitro and in vivo. More attentions should be paid when pyrotinib is combined with azole antifungal drugs in clinic although further investigation is still required in future.

Fluopyram and trifloxystrobin are widely used for controlling various plant diseases in cucumbers and cowpeas. However, data on residue behaviors in plant cultivation and food processing are currently lacking. Our results showed that cowpeas had higher fluopyram and trifloxystrobin residues (16.48–247.65 μg/kg) than cucumbers (877.37–3576.15 μg/kg). Moreover, fluopyram and trifloxystrobin dissipated faster in cucumbers (half-life range, 2.60–10.66 d) than in cowpeas (10.83–22.36 d). Fluopyram and trifloxystrobin were the main compounds found in field samples, and their metabolites, fluopyram benzamide and trifloxystrobin acid, fluctuated at low residue levels (≤76.17 μg/kg). Repeated spraying resulted in the accumulation of fluopyram, trifloxystrobin, fluopyram benzamide and trifloxystrobin acid in cucumbers and cowpeas. Peeling, washing, stir-frying, boiling and pickling were able to partially or substantially remove fluopyram and trifloxystrobin residues from raw cucumbers and cowpeas (processing factor range, 0.12–0.97); on the contrary, trifloxystrobin acid residues appeared to be concentrated in pickled cucumbers and cowpeas (processing factor range, 1.35–5.41). Chronic and acute risk assessments suggest that the levels of fluopyram and trifloxystrobin in cucumbers and cowpeas were within a safe range based on the field residue data of the present study. The potential hazards of fluopyram and trifloxystrobin should be continuously assessed for their high residue concentrations and potential accumulation effects.

The analysis of pesticide residues in aquatic products is challenging due to low residue levels and the complex matrix interference. In this study, we developed a simple, fast method for the trace analysis of 90 pesticides and metabolites in aquatic products. The analytes covered a wide polarity range with log Kow (log octanol-water partition coefficient) ranging from −1.2 to 6.37. Grass carp (Ctenopharyngodon idellus) and prawn (Penaeus chinensis) samples were chosen to validate the quantification method. The samples were extracted by 0.2% formic-acetonitrile, cleaned by solid-phase extraction (PRiME HLB), and analyzed by high performance liquid chromatography−tandem mass spectrometry. The results showed good linearities for the analytes and were observed in the range of 0.05–50 μg/L. The recoveries of the method were within 50.4–118.6%, with the relative standard deviations being lower than 20%. The limits of quantifications (LOQs) of the method were in the range of 0.05–5.0 μg/kg, which were superior to values compared with other research. The developed method was applied to detect pesticide residues in prawn samples from eastern coastal areas of China. Three herbicide residues of diuron, prometryn, and atrazine were detected in prawn samples. The method was sensitive and efficient, which is of significance in expanding the screening scope and improving the quantitative analysis efficiency in aquatic products.

Atrazine is a widely used triazine herbicide, which poses a serious threat to human health and aquatic ecosystem. A montmorillonite–biochar composite (MMT/BC) was prepared for atrazine remediation. Biochar samples were characterized by using scanning electron microscope (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectrometer (XPS). Structural and morphological analysis of raw biochar (BC) and MMT/BC showed that MMT particles have been successfully coated on the surface of biochar. Sorption experiments in aqueous solution indicated that the MMT/BC has higher removal capacity of atrazine compared to BC (about 3.2 times). The sorption of atrazine on the MMT/BC was primarily controlled by both physisorption and chemisorption mechanisms. The amendment of MMT/BC increased the sorption capacity of soils and delayed the degradation of atrazine. Findings from this work indicate that the MMT/BC composite can effectively improve the sorption capacity of atrazine in aquatic environment and farmland soil and reduce the environmental risk.

Growth differentiation factor-8 (GDF-8) is a member of the transforming growth factor-beta superfamily. Studies in vitro and in vivo have shown GDF-8 to be involved in the physiology and pathology of ovarian reproductive functions. In vitro experiments using a granulosa-cell model have demonstrated steroidogenesis, gonadotrophin responsiveness, glucose metabolism, cell proliferation as well as expression of lysyl oxidase and pentraxin 3 to be regulated by GDF-8 via the mothers against decapentaplegic homolog signaling pathway. Clinical data have shown that GDF-8 is expressed widely in the human ovary and has high expression in serum of obese women with polycystic ovary syndrome. GDF-8 expression in serum changes dynamically in patients undergoing controlled ovarian hyperstimulation. GDF-8 expression in serum and follicular fluid is correlated with the ovarian response and pregnancy outcome during in vitro fertilization. Blocking the GDF-8 signaling pathway is a potential therapeutic for ovarian hyperstimulation syndrome and ovulation disorders in polycystic ovary syndrome. GDF-8 has a regulatory role and potential importance in ovarian reproductive activity and may be involved in folliculogenesis, ovulation, and early embryo implantation.

A 3-month experiment was designed to research the impact of trifluralin (TFL) on soil microbial communities and functions under the condition of greenhouse. In this work, silty loam from Langfang was treated with three doses of TFL (1,260, 12,600, and 126,000 g ha−1) and incubated for 90 days. The half-lives of TFL were 15–23 days in all cases. The bacterial and fungal diversities and community structures were impacted by TFL. The bacterial functions of chemoheterotrophy and sulfur oxidation were decreased shortly, but the hydrocarbon degradation ability was significantly increased in the results of functional annotation of prokaryotic taxa (FAPROTAX). For the predicted results of Tax4Fun, amino acid (arginine and proline) metabolism and ABC transporter were decreased significantly, while nitrogen metabolism and ribosome translation were significantly increased. In conclusion, this work aids us to understand the risk of TFL in soil more comprehensively.

Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the first time using in-source fragmentation. The results confirmed that m/z 251 was the only precursor ion of dicofol after in-source fragmentation, and m/z 139 and m/z 111 were reasonable product ions. The main factors triggering the in-source fragmentation were the H+ content and solution conductivity when dicofol entered the mass spectrometer. Density functional theory can be used to analyze and interpret the mechanism of dicofol fragmentation reaction in ESI source. Dicofol reduced the molecular energy from 8.8 ± 0.05 kcal/mol to 1.0 ± 0.05 kcal/mol, indicating that the internal energy release from high to low was the key driving force of in-source fragmentation. A method based on HPLC-MS/MS was developed to analyze dicofol residues in environmental water. The LOQ was 0.1 μg/L, which was better than the previous GC or GC-MS methods. This study not only proposed an HPLC-MS/MS analysis method for dicofol for the first time but also explained the in-source fragmentation mechanism of compounds in ESI source, which has positive significance for the study of compounds with unconventional mass spectrometry behavior in the field of organic pollutant analysis and metabonomics.

With the acceleration of the process of agricultural modernization, many pesticides (insecticides, fungicides, and herbicides) are applied to the field and finally brought into the soils, causing serious damage to the environment. The problem of pesticide pollution has become increasingly prominent. This has highlighted the urgent need for effective and efficient remediation treatment technology for pesticide-contaminated soils. Biochar has a high specific surface area, high porosity, and strong adsorption capacity, making it a soil amendment agent and carbon fixation agent that can improve soil health and enhance adsorption capacity for pesticides to remediate contaminated soils. Recently, efforts have been made to enhance the physicochemical and adsorption properties of biochar by preparing modified biochar, and it has been developed to expand the application of biochar. Specifically, the following aspects were reviewed and discussed: (i) source and modification methods of biochar for pesticide remediation; (ii) the effect of biochar on the environmental fate of remediating pesticides; (iii) the effect of biochar on pesticide-contaminated soils; and (iv) potential problems for the large-scale promotion and application of biochar remediation of pesticides. In conclusion, this review may serve as a reference and guide for pesticide remediation, hence reducing the environmental concerns associated with pesticides in soil.

Given the key role of bees as indicators for environmental assessment, residues in bees and bee products have attracted great interest. In this regard, an improved, highly sensitive method for quantifying the insecticide pyriproxyfen and its four metabolites (4′-OH-Pyr, DPH-Pyr, 2-OH-PY, 4′-OH-POP) in honeybees, larvae, and bee products (honey, pollen, royal jelly and wax) should be established. For this purpose, we used ultra-performance liquid chromatography coupled with triple-quadrupole mass spectrometry for rapid quantification (≤5 min). Recoveries for various matrices ranged from 73.77% to 114.97%, with satisfactory intra-day and inter-day precision (relative standard deviations of 0.03–8.61% and 0.10–7.25%, respectively). The results demonstrated excellent linearity (R2 > 0.9903) with a limit of quantification of 1 μg/kg for six different matrices. We collected and analyzed 597 samples (honey, bees and wax) from four major beekeeping areas in China. Only 47 of these samples contained residues of pyriproxyfen and two of its metabolites (2-OH-PY, 4′-OH-Pyr), and high levels of contamination were found in bee samples (2–739 μg/kg), with substantive accumulation in wax (levels were 9.49% higher than in other samples). The result demonstrate that the method provides a reliable and convenient means of monitoring pyriproxyfen and its metabolites in bee products for better product quality, human health, and international commercial competition and also lays a foundation for risk assessment of potential pyriproxyfen contamination in China.

Silica-based nanoframeworks have been extensively studied for diagnosing and treating hepatocellular carcinoma (HCC). Several reviews have summarized the advantages and disadvantages of these nanoframeworks and their use as drug-delivery carriers. Encouragingly, these nanoframeworks, especially those with metal elements or small molecular drugs doping into the skeleton structure or modifying onto the surface of nanoparticles, could be multifunctional components participating in HCC diagnosis and treatment rather than functioning only as drug-delivery carriers. Therefore, in this work, we described the research progress of silica-based nanoframeworks involved in HCC diagnosis (plasma biomarker detection, magnetic resonance imaging, positron emission tomography, photoacoustic imaging, fluorescent imaging, ultrasonography, etc.) and treatment (chemotherapy, ferroptotic therapy, radiotherapy, phototherapy, sonodynamic therapy, immunotherapy, etc.) to clarify their roles in HCC theranostics. Further, the future expectations and challenges associated with silica-based nanoframeworks were highlighted. We believe that this review will provide a comprehensive understanding for researchers to design novel, functional silica-based nanoframeworks that can effectively overcome HCC.

In 2018, we conducted a cross-sectional study to investigate azole resistance in environmental Aspergillus fumigatus isolates obtained from different agricultural fields in China. Using 63 soil cores, we cultured for azole-resistant A. fumigatus and characterized isolates by their cyp51A gene type, short tandem repeat genotype, and mating type. Of 206 A. fumigatus isolates, 21 (10.2%) were azole resistant. Nineteen of 21 had mutations in their cyp51A gene (5 TR34/L98H, 8 TR34/L98H/S297T/F495I, 6 TR46/Y121F/T289A). Eighteen were cultured from soil samples acquired from strawberry fields, suggesting this soil type is a potential hotspot for azole resistance selection. Twenty resistant isolates were mating type MAT1-1, suggesting asexual sporulation contributed to their evolution. Prochloraz, difenoconazole, and tebuconazole were the most frequently detected fungicides in soil samples with azole-resistant fungus. Our study results suggest that managing the fungicides used in agriculture will help contain the problem of antifungal drug resistance in clinics.

Neonicotinoid pesticide residues are ubiquitous in various foodstuffs and may adversely affect human health. We performed a nationwide survey of neonicotinoid residues in foodstuffs collected from Chinese markets and evaluated the risks of chronic and acute exposure in 1–6-year-old children and the general population. Among the 3406 samples of 13 commodities, 62.21% contained neonicotinoids with concentrations ranging from 0.1 to 1471.43 μg/kg, and 37.58% were simultaneously contaminated with 2–7 neonicotinoids. Acetamiprid, thiamethoxam, and imidacloprid were the top three detected neonicotinoids (22.14–34.32% of samples). Chronic and acute cumulative risk assessment using the relative potency factor method revealed that exposure to neonicotinoids was within established safety limits (below 1); however, the acute risk was much greater than the chronic risk (chronic hazard index range, 1.40 × 10−6–2.33 × 10−3; acute hazard index range, 1.75 × 10−6–0.15). A relatively greater acute cumulative risk was found for children with respect to consumption of grapes, mandarins, and cowpeas (acute hazard index range, 0.11–0.15). Despite the low health risk, the potential health hazards of neonicotinoids should be continuously assessed, given their ubiquity and cumulative effects.

Increasing evidence shows that the extracellular matrix (ECM) is an important regulator of breast cancer (BC). The ECM comprises of highly variable and dynamic components. Compared with normal breast tissue under homeostasis, the ECM undergoes many changes in composition and organization during BC progression. Induced ECM proteins, including fibrinogen, fibronectin, hyaluronic acid, and matricellular proteins, have been identified as important components of BC metastatic cells in recent years. These proteins play major roles in BC progression, invasion, and metastasis. Importantly, several specific ECM molecules, receptors, and remodeling enzymes are involved in promoting resistance to therapeutic intervention. Additional analysis of these ECM proteins and their downstream signaling pathways may reveal promising therapeutic targets against BC. These potential drug targets may be combined with new nanoparticle technologies. This review summarizes recent advances in functional nanoparticles that target the ECM to treat BC. Accurate nanomaterials may offer a new approach to BC treatment.

Due to its high persistence in soil, oxyfluorfen has negative effects on environmental and human health. To reduce soil contamination and impacts on non-target organisms, biochar is introduced into soils to immobilize and sequestrate oxyfluorfen as a remediation practice. Three types of soils common in China were selected and biochar (rice hull, BCR) was added to investigate the desorption and bioavailability of oxyfluorfen after aging BCR for 0, 1, 3, and 6 months. Four chemical extraction methods were used to predict oxyfluorfen bioavailability. Results indicated that after addition of 0.5–2% unaged BCR, the desorption values of oxyfluorfen increased from 64–119 to 176–920 (μg/g)/(mg/L)n in the three soils compared with unamended soil. The bioaccumulation factor (BCF) values of oxyfluorfen in earthworms decreased from 0.80–1.7 to 0.10–1.56 after BCR addition. However, the desorption values decreased from 170–868 to 144–701 (μg/g)/(mg/L)n after aging. The bioavailability of oxyfluorfen in earthworms also increased after the aging treatments, while the BCF was still lower than with unaged BCR. The reduced BCF indicated lower exposure risk of oxyfluorfen to earthworms after amendment with biochar, even after aging 6 months. The bioavailability after extraction by Tenax showed a high linear correlation with uptake in earthworms, even after the 6-month aging treatment (R2 > 0.80). Consequently, BCR could be a practical method to remediate contaminated soil and the 6h Tenax method could be a sensitive and feasible tool to assess the bioavailability of oxyfluorfen in soil.

Abstract In this study, the residues of beta-cypermethrin, pyriproxyfen, avermectin, diflubenzuron and chlorothalonil in button mushrooms were investigated. The dietary risks of ingesting button mushrooms that have had these pesticides applied by two different methods under normal plant conditions were evaluated. The dissipation of these pesticides into the soil was also studied. According to the maximum residue limits (MRLs) and acceptable daily intakes (ADIs), the final residues of beta-cypermethrin, pyriproxyfen, avermectin, diflubenzuron, and chlorothalonil were safe for human consumption after these pesticides were applied by spraying 2 times at the dosages of 900, 750, 540, 562.5, and 540 g a.i.ha−1. The dissipation experiment results demonstrated that these pesticides dissipated rapidly after spraying, and there were no residues that could be detected at harvest time when the pesticides were mixed with substrates. According to this work, the application methods of spraying and incorporation with these pesticides at 1 and 1.5 times of the recommended dosage are safe and proper in cultivating button mushrooms.

Imidacloprid (IMI) is a typical neonicotinoid with the largest usage in agricultural orchards in China. The long-term repeated use and the lack of proper protective measures may result in rural farmers and people living near orchards to be inevitably exposed to IMI. Excessive exposure may cause potential adverse effects on human health. To explore the characteristics of human exposure to IMI in urine, different groups of people, including pesticide applicators and their family members, and kindergarten children near IMI-applied orchards were investigated. The IMI and metabolite, 6-chloronicotinic acid (6-CNA), concentrations in urine were creatinine-adjusted to compensate for a possible dilution effect. Target analytes were detected in 100% of 1926 urine samples. The results showed that the IMI concentration in the 1-d urine from the rural residents significantly increased after a spraying event (p 0.05). Females had higher exposure concentrations than that of males. People from different villages demonstrated diverse exposure levels with Geomean differences of 1.13–3.28 fold. For 3–6 years-old children, urinary concentrations from the rural group (Geomean: 3.73 μg/g creatinine for IMI; 3.95 μg/g creatinine for 6-CNA) were significantly higher than that of the urban group (Geomean: 1.13 μg/g creatinine for IMI; 0.88 μg/g creatinine for 6-CNA) (p = 0.00001), and the younger children tended to have higher exposure risk. Our findings showed that people in the Henan orchard areas were likely exposed to IMI to varying degrees. Further research on the health risk evaluation of IMI and controlling the exposure risks is needed. Keywords: Neonicotinoids, Imidacloprid, Metabolite, 6-Chloronicotinic acid, Urine, Human exposure

In last decade, there has been a concerted effort to reduce the potential threats of honeybees' population due to exposure to neonicotinoid pesticides. A new perspective was put forward to reduce the potential ecological toxicity of neonicotinoid dinotefuran to honeybee in terms of an enantiomeric level in the study. Toxicity of dinotefuran was enantioselective, and S-dinotefuran was 41.1- to 128.4-fold more toxic than R-dinotefuran to honeybee Apis mellifera (Apis mellifera Linnaeus), whereas R-dinotefuran exhibited comparative insecticidal activities (1.7–2.4 times) to typical sucking pests Aphis gossypii and Apolygus lucorum compared to racemic mixtures. Our data suggested that use of R-dinotefuran could have a good efficacy in controlling target pests while minimizing hazard to honeybees. The mechanism for chiral specific toxicity to honeybee was further characterized by electrophysiological studies and molecular docking. S-dinotefuran appears to be more toxic by binding to α8 subunit of nAChR of Apis mellifera. The α8 also have a more stable, functional binding cavity to S-dinotefuran with a higher binding score of 7.15, primarily due to an extensive hydrogen bond network. Therefore, new chiral products with a high proportion of or an enantiomeric pure R-dinotefuran are recommended to achieve effective pests control reducing hazard to honeybee populations. Keywords: Chiral neonicotinoid, Toxicity reduction, Dinotefuran enantiomers, Enantioselective toxicology, Honeybee

Ochratoxin A (OTA) usually contaminates agricultural products such as grapes, oatmeal, coffee and spices. Light was reported as an effective strategy to control spoilage fungi and mycotoxins. This research investigated the effects of light with different wavelengths on the growth and the production of OTA in Aspergillus ochraceus and Aspergillus carbonarius. The results showed that the growth of both fungi were extremely inhibited by UV-B. Short-wavelength (blue, violet) significantly inhibited the production of OTA in both fungi, while the inhibitory effect of white was only demonstrated on A. ochraceus. These results were supported by the expression profiles of OTA biosynthetic genes of A. ochraceus and A. carbonarius. To clarify, the decrease in OTA production is induced by inhibition or degradation; therefore, the degradation of OTA under different wavelengths of light was tested. Under UV-B, the degradation rate of 10 μg/mL OTA standard pure-solution samples could reach 96.50% in 15 days, and the degradation effect of blue light was relatively weak. Furthermore, infection experiments of pears showed that the pathogenicity of both fungi was significantly decreased under UV-B radiation. Thus, these results suggested that light could be used as a potential target for strategies in the prevention and control of ochratoxigenic fungi.

Cognitive dysfunction is a central nervous system (CNS) complication of diabetes mellitus (DM) that is characterized by impaired memory and cognitive ability. An in-depth understanding of metabolic alterations in the brain associated with DM will facilitate our understanding of the pathogenesis of cognitive dysfunction. The present study used an in vitro culture of primary neurons in a high-glucose (HG) environment to investigate characteristic alterations in neuron metabolism using nuclear magnetic resonance (NMR)-based metabonomics. High performance liquid chromatography (HPLC) was also used to measure changes in the adenosine phosphate levels in the hippocampal regions of streptozotocin (STZ)-induced diabetic rats. Our results revealed significant elevations in phosphocholine and ATP production in neurons and decreased formate, nicotinamide adenine dinucleotide (NAD+), tyrosine, methionine, acetate and phenylalanine levels after HG treatment. However, the significant changes in lactate, glutamate, taurine and myo-inositol levels in astrocytes we defined previously in astrocytes, were not found in neurons, suggested cell-specific metabolic alterations. We also confirmed an astrocyte-neuron lactate shuttle between different compartments in the brain under HG conditions, which was accompanied by abnormal acetate transport. These alterations reveal specific information on the metabolite levels and transport processes related to neurons under diabetic conditions. Our findings contribute to the understanding of the metabolic alterations and underlying pathogenesis of cognitive decline in diabetic patients.

A simple residue analytical method based on the QuEChERS approach and high-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) detection was developed for the analysis of fipronil and its three metabolites in cottonseed, cotton plant and soil. The average recoveries of four test compounds from all three matrices were 78.6-108.9% at the level of 0.005 to 0.5 mg/kg, with an RSD in the range of 0.6 to 13.7%. The limit of quantification (LOQ) of the four test compounds ranged from 0.005 to 0.01 mg/kg. The results of the residual dynamics experiments showed that fipronil dissipated rapidly in cotton plants and soil and that oxidation and photolysis were the main degradation pathways. Moreover, the bi-exponential models demonstrated a good fit of the measured data for fipronil in cotton plants and soil, with R2 in the range of 0.8989 to 0.9989. Furthermore, a total of 40 samples of cottonseed from Shandong Province were analyzed, and all of the samples were free from the four test compound residues.

Exhaustive hydro-distillation of Descurainia sophia (L.) Webb ex Prantl (flixweed) collected from two different locations (Cangzhou city-Sample 1 and Beijing city-Sample 2) gave in both cases yellowish colored oils in 0.31 and 0.26% yield, respectively. Detailed chemical composition of the essential oils was analyzed by GC and GC/MS, and forty and thirty-eight compounds were identified. The results indicated that the most abundant component of Sample 1were cis-β-ocimene (20.1%), menthol (11.27%), neoisomenthyl acetate (3.5%), alloaromadendrene (2.28%) and longicyclene (2.25%). Compared with the constituents of Sample 1, several chemical compounds such as 1,8-cineole, α-eudesmol, cis, trans-farnesol and β-pinene were not detected in Sample 2 although it was similarly dominated by cis-β-ocimene (17.12%), menthol (10.7%) and neoisomenthyl acetate (2.96%). Final analysis of the chemical constituents in the essential oils of the two samples showed similarity in their chemical composition, but the relative content of all shared chemical constituents in Sample 2 was lower than that in Sample 1.

BACKGROUND: Curcuma aromatica oil is a traditional herbal medicine demonstrating protective and anti-fibrosis activities in renal fibrosis patients. However, study of its mechanism of action is challenged by its multiple components and multiple targets that its active agent acts on. METHODOLOGY/PRINCIPAL FINDINGS: Nuclear magnetic resonance (NMR)-based metabonomics combined with clinical chemistry and histopathology examination were performed to evaluate intervening effects of Curcuma aromatica oil on renal interstitial fibrosis rats induced by unilateral ureteral obstruction. The metabolite levels were compared based on integral values of serum 1H NMR spectra from rats on 3, 7, 14, and 28 days after the medicine administration. Time trajectory analysis demonstrated that metabolic profiles of the agent-treated rats were restored to control levels after 7 days of dosage. The results confirmed that the agent would be an effective anti-fibrosis medicine in a time-dependent manner, especially in early renal fibrosis stage. Targeted metabolite analysis showed that the medicine could lower levels of lipid, acetoacetate, glucose, phosphorylcholine/choline, trimethylamine oxide and raise levels of pyruvate, glycine in the serum of the rats. Serum clinical chemistry and kidney histopathology examination dovetailed well with the metabonomics data. CONCLUSIONS/SIGNIFICANCES: The results substantiated that Curcuma aromatica oil administration can ameliorate renal fibrosis symptoms by inhibiting some metabolic pathways, including lipids metabolism, glycolysis and methylamine metabolism, which are dominating targets of the agent working in vivo. This study further strengthens the novel analytical approach for evaluating the effect of traditional herbal medicine and elucidating its molecular mechanism.

BACKGROUND: Elucidation of metabolic profiles during diabetes progression helps understand the pathogenesis of diabetes mellitus. In this study, urine metabonomics was used to identify time-related metabolic changes that occur during the development of diabetes mellitus and characterize the biochemical process of diabetes on a systemic, metabolic level. METHODOLOGY/PRINCIPAL FINDINGS: Urine samples were collected from diabetic rats and age-matched controls at different time points: 1, 5, 10, and 15 weeks after diabetes modeling. (1)H nuclear magnetic resonance ((1)H NMR) spectra of the urine samples were obtained and analyzed by multivariate data analysis and quantitative statistical analysis. The metabolic patterns of diabetic groups are separated from the controls at each time point, suggesting that the metabolic profiles of diabetic rats were markedly different from the controls. Moreover, the samples from the diabetic 1-wk group are closely associated, whereas those of the diabetic 15-wk group are scattered, suggesting that the presence of various of complications contributes significantly to the pathogenesis of diabetes. Quantitative analysis indicated that urinary metabolites related to energy metabolism, tricarboxylic acid (TCA) cycle, and methylamine metabolism are involved in the evolution of diabetes. CONCLUSIONS/SIGNIFICANCE: The results highlighted that the numbers of metabolic changes were related to diabetes progression, and the perturbed metabolites represent potential metabolic biomarkers and provide clues that can elucidate the mechanisms underlying the generation and development of diabetes as well as its complication.