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 ext...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 0.01mg/kg to 1.0mg/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 0.01mg/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
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 0.01mg/kg to 1.0mg/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 0.01mg/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.
