Gibberellic acid(GA_(3))is widely used in agriculture and maybe transfer with groundwater flow,which is an endocrine disruptor,but few studies have focused on the transformation pathway and toxicity assessment of GA_(...Gibberellic acid(GA_(3))is widely used in agriculture and maybe transfer with groundwater flow,which is an endocrine disruptor,but few studies have focused on the transformation pathway and toxicity assessment of GA_(3)and its products.Here,GA_(3)and its transformation products in aqueous solution were identified and quantified by liquid chromatography mass spectrometry hybrid ion trap time-of-flight(LCMS-IT-TOF)and high-performance liquid chromatography(HPLC),respectively.The results showed that the half-life of GA_(3)transformation in ultrapure water was 16.1–24.6 days at p H=2.0–8.0,with the lowest half-life occurring at p H=8.0 and highest half-life occurring at p H=3.3.Isomerized gibberellic acid(Iso-GA_(3))and gibberellenic acid(GEA)were the main transformation products with a little hydroxy gibberellic acid(OH-GA_(3)).In North China groundwater,the mass balance of GA_(3)and its products was 76.2%,including Iso-GA_(3)(58%),GEA(7.9%),GA_(3)(7.3%)and OH-GA_(3)(3%)after reaching transformation equilibrium.Using Gaussian 09 for chemical computation,it was found that the transformation mechanism of GA_(3)was dependent upon the bond energy and the stereochemical feature of its molecular structure.GA_(3)always isomerized from theγ-lactone ring due to the lowest bond energy between the oxygen terminus of theγ-lactone ring and A ring.While GA_(3)and its transformation products all had developmental toxicity,the predicated LC 50(96 hr)and LD 50 of the main products of GA_(3)were much lower than those of GA_(3),indicating GA_(3)would be transformed into higher toxicity derivatives in water environments,posing a significant health risk to humans and the environment.展开更多
Uncariae Ramulus Cum Uncis(Gou-Teng),the dried hook-bearing stems of several Uncaria plants(Rubiaceae),is a wellknown herbal medicine in China.The clinical application of Gou-Teng is bewildered for the morphological a...Uncariae Ramulus Cum Uncis(Gou-Teng),the dried hook-bearing stems of several Uncaria plants(Rubiaceae),is a wellknown herbal medicine in China.The clinical application of Gou-Teng is bewildered for the morphological and chemical similarity between diferent species.In order to discern their chemical and biological diference,an ultra-fast liquid chromatography equipped with ion trap time-of-fight mass spectrometry(UFLC-IT/TOF-MS)combining with melatonin(MT1 and MT2)and 5-hydroxytryptamine(5-HT1A and 5-HT2C)receptors agonistic assay in vitro was conducted on seven Uncaria species.As a result,57 compounds including 35 indole alkaloids,ten favonoids,fve triterpenoids,fve chlorogenic analogues,and two other compounds were characterized based on their MS/MS patterns and UV absorptions.Specifcally,cadambine-type and corynanthein-type alkaloids were exclusively present in U.rhynchophylla and U.scandens,whereas corynoxine-type alkaloids were commonly detected in all the seven Uncaria plants.Three Uncaria species,U.rhynchophylla,U.macrophylla,and U.yunnanensis showed obviously agnostic activity on four neurotransmitter receptors(MT1,MT2,5-HT1A,and 5-HT_(2C)).This frst-time UFLCMS-IT-TOF analyses integrated with biological assay on seven Uncaria plants will provide scientifc viewpoints for the clinical application of Gou-Teng.展开更多
基金supported by the National Natural Science Foundation of China(No.41772245)the National Key Research and Development Program of China(No.2019YFC1805400)the Fundamental Research Funds for the Central Universities(No.2020ZDPY0201)。
文摘Gibberellic acid(GA_(3))is widely used in agriculture and maybe transfer with groundwater flow,which is an endocrine disruptor,but few studies have focused on the transformation pathway and toxicity assessment of GA_(3)and its products.Here,GA_(3)and its transformation products in aqueous solution were identified and quantified by liquid chromatography mass spectrometry hybrid ion trap time-of-flight(LCMS-IT-TOF)and high-performance liquid chromatography(HPLC),respectively.The results showed that the half-life of GA_(3)transformation in ultrapure water was 16.1–24.6 days at p H=2.0–8.0,with the lowest half-life occurring at p H=8.0 and highest half-life occurring at p H=3.3.Isomerized gibberellic acid(Iso-GA_(3))and gibberellenic acid(GEA)were the main transformation products with a little hydroxy gibberellic acid(OH-GA_(3)).In North China groundwater,the mass balance of GA_(3)and its products was 76.2%,including Iso-GA_(3)(58%),GEA(7.9%),GA_(3)(7.3%)and OH-GA_(3)(3%)after reaching transformation equilibrium.Using Gaussian 09 for chemical computation,it was found that the transformation mechanism of GA_(3)was dependent upon the bond energy and the stereochemical feature of its molecular structure.GA_(3)always isomerized from theγ-lactone ring due to the lowest bond energy between the oxygen terminus of theγ-lactone ring and A ring.While GA_(3)and its transformation products all had developmental toxicity,the predicated LC 50(96 hr)and LD 50 of the main products of GA_(3)were much lower than those of GA_(3),indicating GA_(3)would be transformed into higher toxicity derivatives in water environments,posing a significant health risk to humans and the environment.
基金supported by the National Natural Science Foundation of China(81573322)the Yunnan Wanren Project(YNWR-QNBJ-2018-061)+1 种基金the Youth Innovation Promotion Association,CAS(2013252)the Program of Yunling Scholarship,the Yunnan Science Fund for Excellent Young Scholars(2019FI017)。
文摘Uncariae Ramulus Cum Uncis(Gou-Teng),the dried hook-bearing stems of several Uncaria plants(Rubiaceae),is a wellknown herbal medicine in China.The clinical application of Gou-Teng is bewildered for the morphological and chemical similarity between diferent species.In order to discern their chemical and biological diference,an ultra-fast liquid chromatography equipped with ion trap time-of-fight mass spectrometry(UFLC-IT/TOF-MS)combining with melatonin(MT1 and MT2)and 5-hydroxytryptamine(5-HT1A and 5-HT2C)receptors agonistic assay in vitro was conducted on seven Uncaria species.As a result,57 compounds including 35 indole alkaloids,ten favonoids,fve triterpenoids,fve chlorogenic analogues,and two other compounds were characterized based on their MS/MS patterns and UV absorptions.Specifcally,cadambine-type and corynanthein-type alkaloids were exclusively present in U.rhynchophylla and U.scandens,whereas corynoxine-type alkaloids were commonly detected in all the seven Uncaria plants.Three Uncaria species,U.rhynchophylla,U.macrophylla,and U.yunnanensis showed obviously agnostic activity on four neurotransmitter receptors(MT1,MT2,5-HT1A,and 5-HT_(2C)).This frst-time UFLCMS-IT-TOF analyses integrated with biological assay on seven Uncaria plants will provide scientifc viewpoints for the clinical application of Gou-Teng.
