Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry
Penflufen fungicide is widely used as a racemate, which has potential ecological risks to aquatic organisms, while its enantioselective toxicity data is limited. This study aimed to differentiate the enantioselective toxicity difference of penflufen enantiomers, and illuminate the enantioselective m...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2021-10-01
|
| Series: | Ecotoxicology and Environmental Safety |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S0147651321006461 |
| _version_ | 1819096297586556928 |
|---|---|
| author | Shanshan Di Zhiwei Wang Tao Cang Yunye Xie Huiyu Zhao Peipei Qi Xiangyun Wang Hao Xu Xinquan Wang |
| author_facet | Shanshan Di Zhiwei Wang Tao Cang Yunye Xie Huiyu Zhao Peipei Qi Xiangyun Wang Hao Xu Xinquan Wang |
| author_sort | Shanshan Di |
| collection | DOAJ |
| description | Penflufen fungicide is widely used as a racemate, which has potential ecological risks to aquatic organisms, while its enantioselective toxicity data is limited. This study aimed to differentiate the enantioselective toxicity difference of penflufen enantiomers, and illuminate the enantioselective mechanism from the insight of enantiomer-protein specific binding. The semipreparative separation and absolute configuration of penflufen enantiomers were conducted. The acute toxicity of S-(+)-penflufen was 54 times higher than R-(-)-penflufen to Danio rerio, and the coexistence of R-(-)-penflufen could increase the exposure risk of S-(+)-penflufen. For chronic toxicity, after low-dose long-term exposure, rac-penflufen and S-(+)-penflufen inducted more serious oxidative stress than R-(-)-penflufen in D. rerio, and inhibited the succinate dehydrogenase (SDH) activity significantly. For target phytopathogen, the toxicity difference of S-(+)-penflufen and R-(-)-penflufen was up to 148 times for Rhizoctonia solani. Based on the toxic unit analysis, the toxic interactions of antagonistic effect and concentration addition were found between penflufen enantiomers, indicating the coexistence of R-(-)-penflufen could increase overuse and environmental risks. Computational chemistry was used to illuminate the enantioselectivity mechanism, and the lower binding energy between the active site of SDH and S-(+)-penflufen contributed to the higher toxicity. The higher target toxicity might be due to the hydrophobic pocket of CybL in R. solani was more benefited to S-(+)-penflufen binding SDH than Botrytis cinerea. These results could be helpful for further understanding the potential risk of chiral penflufen in the environment, demonstrating the importance of understanding the enantioselective difference of chiral pesticides, and providing a new insight for analyzing the enantioselective mechanism. |
| first_indexed | 2024-12-21T23:56:58Z |
| format | Article |
| id | doaj.art-beabe4163e8c45d4822be90c4693d1f9 |
| institution | Directory Open Access Journal |
| issn | 0147-6513 |
| language | English |
| last_indexed | 2024-12-21T23:56:58Z |
| publishDate | 2021-10-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Ecotoxicology and Environmental Safety |
| spelling | doaj.art-beabe4163e8c45d4822be90c4693d1f92022-12-21T18:45:48ZengElsevierEcotoxicology and Environmental Safety0147-65132021-10-01222112534Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistryShanshan Di0Zhiwei Wang1Tao Cang2Yunye Xie3Huiyu Zhao4Peipei Qi5Xiangyun Wang6Hao Xu7Xinquan Wang8State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaInstitute of Plant Protection and Microbiology, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR ChinaState Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-products/ Key Laboratory of Detection for Pesticide Residues and Control of Zhejiang, Institute of Agro-product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, PR China; Agricultural Ministry Key Laboratory for Pesticide Residue Detection, Hangzhou 310021, PR China; Correspondence to: Desheng Middle Road 298, Hangzhou 310021, Zhejiang, PR China.Penflufen fungicide is widely used as a racemate, which has potential ecological risks to aquatic organisms, while its enantioselective toxicity data is limited. This study aimed to differentiate the enantioselective toxicity difference of penflufen enantiomers, and illuminate the enantioselective mechanism from the insight of enantiomer-protein specific binding. The semipreparative separation and absolute configuration of penflufen enantiomers were conducted. The acute toxicity of S-(+)-penflufen was 54 times higher than R-(-)-penflufen to Danio rerio, and the coexistence of R-(-)-penflufen could increase the exposure risk of S-(+)-penflufen. For chronic toxicity, after low-dose long-term exposure, rac-penflufen and S-(+)-penflufen inducted more serious oxidative stress than R-(-)-penflufen in D. rerio, and inhibited the succinate dehydrogenase (SDH) activity significantly. For target phytopathogen, the toxicity difference of S-(+)-penflufen and R-(-)-penflufen was up to 148 times for Rhizoctonia solani. Based on the toxic unit analysis, the toxic interactions of antagonistic effect and concentration addition were found between penflufen enantiomers, indicating the coexistence of R-(-)-penflufen could increase overuse and environmental risks. Computational chemistry was used to illuminate the enantioselectivity mechanism, and the lower binding energy between the active site of SDH and S-(+)-penflufen contributed to the higher toxicity. The higher target toxicity might be due to the hydrophobic pocket of CybL in R. solani was more benefited to S-(+)-penflufen binding SDH than Botrytis cinerea. These results could be helpful for further understanding the potential risk of chiral penflufen in the environment, demonstrating the importance of understanding the enantioselective difference of chiral pesticides, and providing a new insight for analyzing the enantioselective mechanism.http://www.sciencedirect.com/science/article/pii/S0147651321006461Penflufen enantiomersAbsolute configurationEnantioselective toxicityComputational chemistryEnantioselective mechanism |
| spellingShingle | Shanshan Di Zhiwei Wang Tao Cang Yunye Xie Huiyu Zhao Peipei Qi Xiangyun Wang Hao Xu Xinquan Wang Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry Ecotoxicology and Environmental Safety Penflufen enantiomers Absolute configuration Enantioselective toxicity Computational chemistry Enantioselective mechanism |
| title | Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| title_full | Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| title_fullStr | Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| title_full_unstemmed | Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| title_short | Enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| title_sort | enantioselective toxicity and mechanism of chiral fungicide penflufen based on experiments and computational chemistry |
| topic | Penflufen enantiomers Absolute configuration Enantioselective toxicity Computational chemistry Enantioselective mechanism |
| url | http://www.sciencedirect.com/science/article/pii/S0147651321006461 |
| work_keys_str_mv | AT shanshandi enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT zhiweiwang enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT taocang enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT yunyexie enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT huiyuzhao enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT peipeiqi enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT xiangyunwang enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT haoxu enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry AT xinquanwang enantioselectivetoxicityandmechanismofchiralfungicidepenflufenbasedonexperimentsandcomputationalchemistry |