Racemic,R-, and S-tebuconazole altered chitinase and chitobiase activity of Daphnia magna

Tebuconazole is a chiral trizole fungicide and widely used in many crops for controlling disease. Tebuconazole is potential toxic to some aquatic organisms but relative information of its isomers is scarce. To detect the endocrine disrupting effects and difference of rac-, R-, and S-tebuconazole, the chitinase activity in Daphnia magna and chitobiase activity in each test medium were used as biomonitors after a 14-day exposure. Results showed that chitinase activity was significantly reduced by rac-, R-, and S-tebuconazole. The chitobiase activity in the test medium was reduced by rac- and R-tebuconazole before day 10, and only one peak was observed at day 10 or day 12 compared with two obvious peaks in the control group (days 6 and 12). S-tebuconazole delayed and reduced the reproduction of D. magna, but did not delay the first chitobiase activity peak, whereas the second peak could not be characterized as the exposure concentration and time increased. Compared with chitinase activity, chitobiase activity can still be used as a rudimentary model for identifying molt-interfering xenobiotics, and further studies should focus on the analysis of correlations between these parameters.     

Distribution of thifluzamide,fenoxanil and tebuconazole in rice paddy and dietary risk assessment

Distribution behaviors of thifluzamide, fenoxanil, and tebuconazole applied to rice were investigated in South China. Analysis was by a modified QuEChERS method with gas chromatography (thifluzamide and fenoxanil) and liquid chromatography mass spectrometry (tebuconazole). Thifluzamide and tebuconazole partitioned mainly into the soil, with half-lives in the paddy soil of 12–14 and 5.3–7.8 days, respectively. Fenoxanil partitioned mainly into the rice plants, with half-lives of 3.3–4.4 days. The half-lives of thifluzamide, fenoxanil, and tebuconazole in paddy water were 0.17–0.89, 1.8–3.0, and 1.6–4.0 days, respectively. The residues in rice grains at the pre-harvest interval of 14 days were all below the established maximum limit values. The dietary risks assessed as hazard quotients at the pre-harvest interval were less than 1.     

戊唑醇残留分析方法实验室内质量控制研究

文章确立了小麦、香蕉中戊唑醇残留检测方法,小麦样品加水10 mL用丙酮为萃取溶剂,石油醚液液分配,中性氧化铝柱层析净化,用气相色谱(GC-NPD)检测。香蕉样品加水5 mL用丙酮为萃取溶剂,石油醚液液分配,浓缩后用气相色谱(GC-NPD)检测。分别设置不同时间批次,同一批次间的平行样及实验室内人员分析,分别从方法灵敏度、方法准确度、方法精密度及其质量控制图、标准工作液的稳定性来探讨该方法的可靠性,结果表明该方法可以作为香蕉和小麦种戊唑醇残留检测的标准分析方法。     

戊唑醇粉尘最小点火能试验研究

采用1.2 L哈特曼管爆炸装置分别对粒径小于54μm、74μm、150μm及大于150μm的戊唑醇粉尘进行测试。针对戊唑醇粉尘浓度及粒径范围对其最小点火能的影响,分别进行单因素试验,并对其危险性进行分级。结果表明,保持粒径小于150μm,环境温度为20℃,喷粉压力为0.7 MPa,在质量浓度100~1 300 g/m~3之间,戊唑醇粉尘的最佳敏感质量浓度ρ_m为983.71 g/m~3,此时的最小点火能为404.74 mJ。保持戊唑醇粉尘质量浓度为900 g/m~3,环境温度为20℃,喷粉压力为0.7 MPa不变,粒径小于54μm、74μm、150μm及大于150μm的戊唑醇粉尘的最小点火能分别为10 mJ、100 mJ、400 mJ和1 000 mJ以上。因此,判定戊唑醇粉尘最小点火能属于M2级,为特别着火敏感性。     

Persistence and dissipation kinetics of trifloxystrobin and tebuconazole in onion and soil

The persistence and dissipation kinetics of trifloxystrobin and tebuconazole on onion were studied after application of their combination formulation at a standard and double dose of 75 + 150 and 150 + 300 g a.i. ha^?1. The fungicides were extracted with acetone, cleaned-up using activated charcoal (trifloxystrobin) and neutral alumina (tebuconazole). Analysis was carried out by gas chromatograph (GC) and confirmed by gas chromatograph mass spectrometry (GC-MS). The recovery was above 80% and limit of quantification (LOQ) 0.05 mg kg^?1 for both fungicides. Initial residue deposits of trifloxystrobin were 0.68 and 1.01 mg kg^?1 and tebuconazole 0.673 and 1.95 mg kg^?1 from standard and double dose treatments, respectively. Dissipation of the fungicides followed first-order kinetics and the half life of degradation was 6–6.6 days. Matured onion bulb (and field soil) harvested after 30 days was free from fungicide residues. These findings suggest recommended safe pre-harvest interval (PHI) of 14 and 25 days for spring onion consumption after treatment of Nativo 75 WG at the standard and double doses, respectively. Matured onion bulbs at harvest were free from fungicide residues.     

Antifungal activity of P3HB microparticles containing tebuconazole

In this study, tebuconazole (TEB)-loaded poly-3-hydroxybutyrate (P3HB)-based microparticles were developed and comprehensively characterized. TEB-loaded microparticles with the initial loading amounts of the fungicide of 10, 25, and 50% of the polymer mass (TEB 10, TEB 25, and TEB 50%) were prepared using emulsion technique. Encapsulation efficiency of TEB varied from 59 to 86%. As the loading amount was increased, the average diameter of microparticles increased too, from 41.3 to 71.7?µm, while zeta potential was not influenced by TEB loading, varying between –32.6 and –35.7?mV. TEB was gradually released from the microparticles to the model medium, and after 60?d, from 25 to 43% of TEB was released depending on the content of the encapsulated fungicide. The data obtained from in vitro TEB release were fitted to different mathematical models. It was shown that the release profiles of TEB could be best explained by the Zero-order, Higuchi, and Hixson–Crowell models. The antifungal activity of the P3HB/TEB microparticles against phytopathogenic fungi Fusarium moniliforme and Fusarium solani was demonstrated by in vitro tests conducted in Petri dishes. Thus, hydrophobic agrochemicals (TEB) can be effectively encapsulated into P3HB microparticles to construct slow-release formulations.     

戊唑醇对斑马鱼的急性毒性及生物富集效应

为评价杀菌剂戊唑醇对水生生态系统的影响,以斑马鱼(Brachydanio rerio)为试验生物,采用半静态法分别研究了戊唑醇原药和其6种不同剂型对斑马鱼的急性毒性以及戊唑醇原药对斑马鱼的生物富集效应。结果表明:97.4%戊唑醇原药、25%戊唑醇水乳剂、430 g·L-1戊唑醇悬浮剂、25%戊唑醇可湿性粉剂、80 g·L-1戊唑醇悬浮种衣剂、250 g·L-1戊唑醇乳油、80%戊唑醇水分散粒剂对斑马鱼96 h-LC50分别为8.73、3.35、6.44、9.68、4.60、0.892和6.81 mg·L-1;选择97.4%戊唑醇原药进行斑马鱼生物富集试验,在9.00×10-2和0.900 mg·L-12个处理浓度下连续暴露8 d,相应的富集系数(BCF8 d)分别为27.7和25.4。根据《化学农药环境安全评价试验准则》毒性划分标准,除250 g·L-1戊唑醇乳油对斑马鱼急性毒性属于高毒,其他剂型均为中毒,且戊唑醇属于中等富集性农药。该研究为戊唑醇田间安全使用提供理论依据。     

Enantioseletive bioaccumulation of tebuconazole in earthworm Eisenia fetida

Methods of extraction and determination of tebuconazole enantiomers in earthworm (Eisenia fetida) were developed by capillary electrophoresis (CE) and high performance liquid chromatography (HPLC). Both CE and HPLC have excellent resolution and recovery. The linearity ranges were 2.9-102.4 mg/kg and 3.0-99.6 mg/kg for (+)-R-tebuconazole and (-)-S-tebuconazole respectively in CE, and from 0.56 to 1000 mg/kg for both enantiomers in HPLC. Enantioselective bioaccumulation in earthworms from soil was investigated under laboratory condition at concentrations of 10 and 50 mg/kg dw in soil. The uptake kinetics of (+)-R-tebuconazole fitted the first-order kinetics well with r² 0.97 and 0.94 under 10 and 50 mg/kg dw exposure condition, respectively, while (-)-S-tebuconazole with r² 0.75 and 0.22 did not show the same. Bioaccumulation of tebuconazole in earthworm tissues was enantioselective with a preferential accumulation of (+)-R-tebuconazole. The (+)-R-tebuconazole might also have biomagnifying effect potential in earthworm food chain with biota-sediment accumulation factor (BSAF) of 1.64 kg OC/kg lip in 10 mg/kg dw exposure group and 2.61 kg OC/kg lip in 50 mg/kg dw exposure group from soil to earthworm after 36 days. Although (-)-S-tebuconazole shares the same physicochemical properties with (+)-R-tebuconazole, it did not biomagnify. BSAFs of (-)-S-tebuconazole were 0.50 kg OC/kg lip (10 mg/kg dw tebuconazole exposure) and 0.28 kg OC/kg lip (50 mg/kg dw tebuconazole exposure) after 36 days, which was possibly owing to biotransformation or metabolism in earthworm tissues.     

戊唑醇在环境中的降解迁移和生物富集性研究

戊唑醇属于内吸性三唑类杀菌农药,在国内广泛用于田间病虫防治,故其在环境中的归趋备受关注。采用室内模拟试验方法,研究了戊唑醇在水-沉积物中的降解特性、土壤中的吸附性和在斑马鱼中的生物富集性。结果表明:好氧条件下,戊唑醇在河流与湖泊水-沉积物系统中农药总量的降解半衰期分别为533.2、433.2 d;厌氧条件下,河流与湖泊水-沉积物系统中降解半衰期分别为364.8、1 732.9 d;沉积物系统降解半衰期较长,降解速率主要受水中戊唑醇的降解速率影响。戊唑醇在江西红壤、太湖水稻土、常熟乌杉土、东北黑土中的吸附性符合Freundlich方程,Kd值分别为7.4、11.8、11.2和15;吸附性大小次序为东北黑土太湖水稻土常熟乌杉土江西红壤;以有机碳含量表示的土壤吸附常数KOC在698.9~1 635.5之间;影响戊唑醇土壤吸附性的主要因素为土壤有机质含量和p H。戊唑醇在斑马鱼中的生物富集系数BCF8 d为21.52~25.30,具有中等富集性。戊唑醇在水体环境中具有较强稳定性,不易被土壤吸附,且具有一定的生物富集性,可能会对水体和水体生物造成一定的污染。     

Interaction of tebuconazole with bovine serum albumin: determination of the binding mechanism and binding site by spectroscopic methods

Abstract

This study investigates the interaction between tebuconazole and bovine serum albumin (BSA) in a physiological buffer (pH = 7.4) using the fluorescence quenching method to obtain the apparent binding constants (K) and number of binding sites (n) in the interaction between tebuconazole and BSA. The results revealed that tebuconazole can quench the intrinsic fluorescence of BSA through a static quenching procedure. It also shows that the thermodynamic parameters of enthalpy change (ΔH) and entropy change (ΔS) are negative, indicating that the interaction of tebuconazole with BSA is mainly driven by van der Waals forces and hydrogen bonds. The process of binding was a spontaneous process in which Gibbs free energy change was negative. The distance of r between the donor (BSA) and acceptor (tebuconazole) was calculated to be 0.68?nm based on Forster’s non-radiative energy transfer theory. Analysis of synchronous fluorescence, three-dimensional fluorescence and circular dichroism (CD) spectra demonstrates that tebuconazole can induce conformational changes of BSA.