A determination method for dinotefuran residue in paddy plants, brown rice, husk, soil and paddy water was established using high performance liquid chromatography （HPLC）. The simples of brown rice, plants, and soil...A determination method for dinotefuran residue in paddy plants, brown rice, husk, soil and paddy water was established using high performance liquid chromatography （HPLC）. The simples of brown rice, plants, and soil were extracted with acetonitrile ＋ ammonia solution, while the simple of husk was extracted with dichloromethane ＋ ammonia solution. After liquid-liquid extraction, the solutions were concentrated and set to constant volume, and then quantified by external standard method. The results showed that when the adding level ranged from 0.01 mg/kg to 1.0 mg/kg, the average recoveries of dinotefuran in rice plants, brown rice, husk, soil and water were 86.4% -99.3% ; the relative standard deviations were 0.44% -3.60%, and the minimum detectable concentration was 0. 01 mg/kg.展开更多
Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemica...Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemically investigated.Firstly,reversedphase chromatography-high resolution mass spectrometry was developed to quantify the content of DIN R/S chiral enantiomer with pg level sensitivity,revealing a lower elimination rate constant(K_(e))of S-DIN(0.730 h^(-1))than R-DIN(0.746 h^(-1)).Secondly,the interaction mechanism between DIN metabolism and important endogenous bioactive molecules,such as aldehyde oxidase(AOX)and neurotransmitters,was revealed.The DIN nitro-group was converted into a guanidine group by the reducing site of nearby flavin adenine dinucleotide(FAD)in AOX with the preferred higher affinity of S-configuration.Meanwhile,the endogenous tryptophan(Trp)aldehyde metabolic intermediate,5-hydroxyindoleacetaldehyde(5-HIAL),provides a persistent electron donor for DIN reduction via the oxidation-catalyzed site in AOX,resulting in remarkable up-regulation of monoamine neurotransmitters such as serotonin and dopamine.Thirdly,the higher level of neurotransmitters further mediated dysregulation of oxylipin homeostasis via the serotonergic pathway,where S-DIN exhibited more pronounced liver lipid damage and environmental health risk with the accumulated lipid biomarkers,oxidized triglyceride(OxTG)and oxidized sphingomyelin(OxSM).This study elucidates the AOX-mediated enantioselectivity metabolic pathway of DIN,providing a new analytical method for chiral pollutants and paves the way for their health risk assessments.展开更多
以桑蚕业废弃物蚕沙为原料,氯化锌为活化剂,在900℃下高温活化得到蚕沙基生物多孔炭(biochar of silkworm excrement,BCSE)。利用氮气吸脱附、扫描电子显微镜、X射线衍射及傅里叶变换红外光谱对BCSE的理化性质进行表征分析,并测试其对...以桑蚕业废弃物蚕沙为原料,氯化锌为活化剂,在900℃下高温活化得到蚕沙基生物多孔炭(biochar of silkworm excrement,BCSE)。利用氮气吸脱附、扫描电子显微镜、X射线衍射及傅里叶变换红外光谱对BCSE的理化性质进行表征分析,并测试其对农药杀虫单和呋虫胺的协同吸附与脱附性能,以及吸附农药后的贮藏稳定性。结果表明:BCSE具有丰富的孔道结构,其最优材料BCSE-3的BET比表面积可达833.0m^(2)/g,对杀虫单和呋虫胺的单独吸附分别可达0.83mmol/g和1.43mmol/g,双组分协同吸附时两种农药的吸附容量和吸附速率与单组分相比都显著提升。同时贮藏稳定性结果也证明在54℃下两种农药在BCSE-3中都拥有长达35d以上的稳定性(农药降解率<2%),远超农业农村部对农药贮藏稳定性的要求。最后通过分子模拟计算发现,呋虫胺上高电子密度的含氧五元杂环与BCSE上苯环形成π-π相互作用是呋虫胺具有更高吸附量和更快吸附速率的主要原因,而杀虫单和呋虫胺间的氢键作用是二者混合吸附量大于单组分吸附量的主要原因。展开更多
基金Supported by Industrialization Cultivation Project of Colleges and Universities in Hunan Province(13CY030)Industry-University-Research Project of Hunan University of Humanities,Science and Technology(2013CXY04)
文摘A determination method for dinotefuran residue in paddy plants, brown rice, husk, soil and paddy water was established using high performance liquid chromatography （HPLC）. The simples of brown rice, plants, and soil were extracted with acetonitrile ＋ ammonia solution, while the simple of husk was extracted with dichloromethane ＋ ammonia solution. After liquid-liquid extraction, the solutions were concentrated and set to constant volume, and then quantified by external standard method. The results showed that when the adding level ranged from 0.01 mg/kg to 1.0 mg/kg, the average recoveries of dinotefuran in rice plants, brown rice, husk, soil and water were 86.4% -99.3% ; the relative standard deviations were 0.44% -3.60%, and the minimum detectable concentration was 0. 01 mg/kg.
基金supported by the National Natural Science Foundation of China(22276076,22306074,22361132536,22236002)the Fundamental Research Funds for the Central Universities(JUSRP622032)the Jiangsu Association for Science and Technology Youth Science and Technology Talent Support Project(TJ2021-049)。
文摘Chiral pollutants often pose significant differential environmental health risks.In this study,the biotransformation of chiral dinotefuran(DIN)and its enantioselective metabolic toxicity mechanisms have been systemically investigated.Firstly,reversedphase chromatography-high resolution mass spectrometry was developed to quantify the content of DIN R/S chiral enantiomer with pg level sensitivity,revealing a lower elimination rate constant(K_(e))of S-DIN(0.730 h^(-1))than R-DIN(0.746 h^(-1)).Secondly,the interaction mechanism between DIN metabolism and important endogenous bioactive molecules,such as aldehyde oxidase(AOX)and neurotransmitters,was revealed.The DIN nitro-group was converted into a guanidine group by the reducing site of nearby flavin adenine dinucleotide(FAD)in AOX with the preferred higher affinity of S-configuration.Meanwhile,the endogenous tryptophan(Trp)aldehyde metabolic intermediate,5-hydroxyindoleacetaldehyde(5-HIAL),provides a persistent electron donor for DIN reduction via the oxidation-catalyzed site in AOX,resulting in remarkable up-regulation of monoamine neurotransmitters such as serotonin and dopamine.Thirdly,the higher level of neurotransmitters further mediated dysregulation of oxylipin homeostasis via the serotonergic pathway,where S-DIN exhibited more pronounced liver lipid damage and environmental health risk with the accumulated lipid biomarkers,oxidized triglyceride(OxTG)and oxidized sphingomyelin(OxSM).This study elucidates the AOX-mediated enantioselectivity metabolic pathway of DIN,providing a new analytical method for chiral pollutants and paves the way for their health risk assessments.
文摘以桑蚕业废弃物蚕沙为原料,氯化锌为活化剂,在900℃下高温活化得到蚕沙基生物多孔炭(biochar of silkworm excrement,BCSE)。利用氮气吸脱附、扫描电子显微镜、X射线衍射及傅里叶变换红外光谱对BCSE的理化性质进行表征分析,并测试其对农药杀虫单和呋虫胺的协同吸附与脱附性能,以及吸附农药后的贮藏稳定性。结果表明:BCSE具有丰富的孔道结构,其最优材料BCSE-3的BET比表面积可达833.0m^(2)/g,对杀虫单和呋虫胺的单独吸附分别可达0.83mmol/g和1.43mmol/g,双组分协同吸附时两种农药的吸附容量和吸附速率与单组分相比都显著提升。同时贮藏稳定性结果也证明在54℃下两种农药在BCSE-3中都拥有长达35d以上的稳定性(农药降解率<2%),远超农业农村部对农药贮藏稳定性的要求。最后通过分子模拟计算发现,呋虫胺上高电子密度的含氧五元杂环与BCSE上苯环形成π-π相互作用是呋虫胺具有更高吸附量和更快吸附速率的主要原因,而杀虫单和呋虫胺间的氢键作用是二者混合吸附量大于单组分吸附量的主要原因。
