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MOLECULES · 2019 ·Vol. 24 ·期 17 ·3060 · IF 3.06

Protective Responses Induced by Chiral 3-Dichloroacetyl Oxazolidine Safeners in Maize (Zea mays L.) and the Detoxification Mechanism

Shuang Gao,Yan-Yan Liu,Jing-Yu Jiang,Ying Fu,Li-Xia Zhao,Chun-Yan Li,Fei Ye

Herbicide safeners selectively protect crops from herbicide injury while maintaining the herbicidal effect on the target weed. To some extent, the detoxification of herbicides is related to the effect of herbicide safeners on the level and activity of herbicide target enzymes. In this work, the expression of the detoxifying enzyme glutathione S-transferase (GST) and antioxidant enzyme activities in maize seedlings were studied in the presence of three potential herbicide safeners: 3-dichloroacetyl oxazolidine and its two optical isomers. Further, the protective effect of chiral herbicide safeners on detoxifying chlorsulfuron in maize was evaluated. All safeners increased the expression levels of herbicide detoxifying enzymes, including GST, catalase (CAT), and peroxidase (POD) to reduce sulfonylurea herbicide phytotoxicity in maize seedlings. Our results indicate that theR-isomer of 3-(dichloroacetyl)-2,2,5-trimethyl-1,3-oxazolidine can induce glutathione (GSH) production, GST activity, and the ability of GST to react with the substrate 1-chloro-2,4-dinitrobenzene (CDNB) in maize, meaning that theR-isomer can protect maize from damage by chlorsulfuron. Information about antioxidative enzyme activity was obtained to determine the role of chiral safeners in overcoming the oxidative stress in maize attributed to herbicides. The interaction of safeners and active target sites of acetolactate synthase (ALS) was demonstrated by molecular docking modeling, which indicated that both isomers could form a good interaction with ALS. Our findings suggest that the detoxification mechanism of chiral safeners might involve the induction of the activity of herbicide detoxifying enzymes as well as the completion of the target active site between the safener and chlorsulfuron.Keywords:chiral safener;biological activity;antioxidative enzyme activity;protection mechanism;chlorsulfuron

研究领域: 植物生理学 · 分子生物学 · 农药科学
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CANADIAN JOURNAL OF PLANT SCIENCE · 2015 ·Vol. 95 ·期 5 · IF 0.919

Alleviation of injury from chlorimuron-ethyl in maize treated with safener 3-dichloroacetyl oxazolidine

ZhaoLi-Xia,QuHai-Tao,FuYing,GaoShuang,YeFei

Zhao, L.-X., Qu, H.-T., Fu, Y., Gao, S. and Ye, F. 2015. Alleviation of injury from chlorimuron-ethyl in maize treated with safener 3-dichloroacetyl oxazolidine. Can. J. Plant Sci. 95: 897–903. The protective effects of herbicide safeners, including 3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine (R-28725), 3-dichloroacetyl-2,2-dimethyl-4-ethyl-1,3-oxazolidine (Racemate), and its two enantiomers (R)-3-dichloroacetyl-2,2-dimethyl-4-ethyl-1,3-oxazolidine (R-enantiomer) and (S)-3-dichloroacetyl-2,2-dimethyl-4-ethyl-1,3-oxazolidine (S-enantiomer), on reducing the phytotoxicity of chlorimuron-ethyl to maize were investigated. Soaking the seeds in safeners increased the endogenous glutathione (GSH) content and glutathione-S-transferase (GST) activity of maize. When induced by R-enantiomer, the GST activity in vivo and in vitro increased 180 and 192% compared with control, respectively. R-28725 and R-enantiomer also increased the acetolactate synthase (ALS) activity inhibited by chlorimuron-ethyl from 45 to 100 and 97% compared with the control, respectively. The kinetic parameter Vmax of GST in the maize treated with R-28725 and R-enantiomer increased by 103 and 92%, respectively, compared with the control. Our results suggest that R-28725 and R-enantiomer could significantly improve the GSH content, GST activity, and ALS activity of maize. Overall, maize could be protected from the injury caused by chlorimuron-ethyl.

研究领域: 植物科学 · 农业化学
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PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY · 2022 · IF 4.966

Diazabicyclo derivatives as safeners protect cotton from injury caused by flumioxazin

Ling Jia,Li-Xia Zhao,Fang Sun,Jie Peng,Jia-Yu Wang,Xin-Yu Leng,Shuang Gao,Ying Fu,Fei Ye

Flumioxazin, a protoporphyrinogen oxidase (PPO; EC 1.3.3.4) inhibitor, has been used in soybean, cotton, grapes, and many other crops to control broad leaf weeds. Unfortunately, it can cause damage to cotton. To ameliorate phytotoxicity of flumioxazin to cotton, this work assessed the protective effects of diazabicyclo derivatives as potential safeners in cotton. A bioactivity assay proved that the phytotoxicity of flumioxazin on cotton was alleviated by some of the compounds. In particular, the activity of glutathione S-transferases (GSTs) was significantly enhanced by Compound 32 , which showed good safening activity against flumioxazin injury. The physicochemical properties and absorption, distribution, metabolism, excretion and toxicity (ADMET) predictions proved that the pharmacokinetic properties of Compound 32 are similar to those of the commercial safener BAS 145138. The present work demonstrated that diazabicyclo derivatives are potentially efficacious as herbicide safeners, meriting further investigation.

CAS / MDL: 103361-09-7
研究领域: 农业科学 · 植物生理学 · 药理学
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Environmental Science-Nano · 2023 ·Vol. 10 ·期 4 ·1016-1029 · IF 7.3

A MOF-based pH-responsive dual controlled-release system for herbicide pretilachlor and safener AD-67 delivery that enhances the herbicidal efficacy and reduces side effects

Kunyan Guo,Xile Deng,Yajun Peng,Ni Yang,Kun Qian,Lianyang Bai

Pretilachlor (Pre) is an efficient and broad-spectrum pre-seedling herbicide; however, the excessive use of the Pre traditional formulation causes phytotoxicity to rice seedlings (Oryza sativa), toxicity to soil organisms, and great environmental pollution. 4-(Dichloroacetyl)-1-oxa-4-azospiro[4,5]decane (AD-67) is a herbicide safener and it can reduce the phytotoxicity of herbicides to plants, but it degrades slowly in the aquatic environment, and extensive application leads to a wide range of negative environmental impacts. To reduce the frequency of application and increase the safety of non-target organisms, for the first time, an herbicide-safener nano-double controlled release system AD-67@Pre@ZIF-67 was successfully constructed. Pre was encapsulated in ZIF-67, metal–organic framework (MOF), and the safener AD-67 was adsorbed by self-assembly on the surface of the MOF. The release rates of Pre and AD-67 increased with the decrease in the pH value. With the lowest pH value (5.8), Pre and AD-67 were released 57% and 78% rapidly in the first 2 h, respectively, then were slowly released, and the overall releases were 86% and 96% on the 7th day, respectively. Hence, the safener AD-67 can be released quickly to protect the rice seedlings from injury caused by Pre, while Pre can release slowly from nano-double controlled release for a longer duration and show lower phytotoxicity to rice. Compared to the pre-treatment, the relative root length, relative plant height, and relative fresh weight values of rice seedlings treated with AD-67@Pre@ZIF-67 were increased by 50%, 40%, and 62%, respectively. AD-67@Pre@ZIF-67 also had lower acute toxicity to earthworms (Eisenia foetida), with the 24 h and 48 h LC50 values, which were 6 times and 5 times than that of Pre, respectively. The results showed that AD-67@Pre@ZIF-67 did not only improve the herbicidal activity to target weed barnyard grass (Echinochloa crusgalli) but also met the requirements of minimizing the adverse effects of herbicides on crop plants and environments. This shows the great application prospects in modern agriculture.

研究领域: 农业科学 · 环境科学 · 纳米技术 · 植物科学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2023 · IF 6.1

Design, Synthesis, and Bioactivity of Novel Ester-Substituted Cyclohexenone Derivatives as Safeners

Bo-Wen Ye,Li-Xia Zhao,Zi-Wei Wang,Juan Shi,Xin-Yu Leng,Shuang Gao,Ying Fu,Fei Ye

Tembotrione, a 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor, has been widely used in many types of plants. Tembotrione has been reported for its likelihood of causing injury and plant death to certain corn hybrids. Safeners are co-applied with herbicides to protect certain crops without compromising weed control efficacy. Alternatively, herbicide safeners may effectively improve herbicide selectivity. To address tembotrione-induced Zea mays injury, a series of novel ester-substituted cyclohexenone derivatives were designed using the fragment splicing method. In total, 35 title compounds were synthesized via acylation reactions. All the compounds were characterized using infrared spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy, and high-resolution mass spectrometry. The configuration of compound II-15 was confirmed using single-crystal X-ray diffraction. The bioactivity assay proved that tembotrione phytotoxicity to maize could be reduced by most title compounds. In particular, compound II-14 exhibited the highest activity against tembotrione. The molecular structure comparisons as well as absorption, distribution, metabolism, excretion, and toxicity predictions demonstrated that compound II-14 exhibited pharmacokinetic properties similar to those of the commercial safener isoxadifen-ethyl. The molecular docking model indicated that compound II-14 could prevent tembotrione from reaching or acting with Z. mays HPPD (PDB: 1SP8). Molecular dynamics simulations showed that compound II-14 maintained satisfactory stability with Z. mays HPPD. This research revealed that ester-substituted cyclohexenone derivatives can be developed as potential candidates for discovering novel herbicide safeners in the future.

研究领域: 农业化学 · 植物科学 · 药理学
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Agronomy-Basel · 2022 ·Vol. 12 ·期 11 ·2870 · IF 3.949

Fenclorim Increasing Butachlor Selectivity between Wheat and Roegneria kamoji by Seed Soaking

Wei Tang,Jinqiu Sun,Xiaoyue Yu,Fengyan Zhou,Shengnan Liu,Mengjie Liu,Yongliang Lu,Yongjie Yang

Roegneria kamojiOhwi (Poaceae), a wild relative plant of wheat which is widely distributed across China, has become a dominant and problematic weed in wheat fields in some regions. We have previously confirmed thatR. kamojiis highly tolerant to foliar-applied acetyl-CoA carboxylase (ACCase) and acetolactate synthase (ALS) inhibitors in wheat (Triticum aestivumL.). The sensitivity ofR. kamojito pre-emergence (PRE) herbicides and the basis of fenclorim increase selectivity to butachlor between wheat andR. kamojiwere evaluated in this study. Screenhouse bioassay showed thatR. kamojiexhibited similar sensitivity to wheat to PRE herbicides at their recommended field doses (RFD); it also showed that buatchlor provides the highest relative control forR. kamoji(53.4% emergence and 81.5% fresh weight reduction, respectively), while it had no impact on seedling emergence of wheat among the six PRE herbicides. When butachlor was applied at four-fold RFD, noR. kamojiseedlings emerged; however, it significantly reduced the above-ground biomass of wheat compared with the non-treated control. Pre-treatment with herbicide safener fenclorim by seed soaking increased the ED10value of butachlor to wheat from 221.8 to 1600.1 g a.i. ha−1, thus increasing the selectivity index from 9.6 to 68.9 between wheat andR. kamoji. The activities of α-amylase activity and protein content during germination, and glutathione-S-transferase (GST) and β-ketoacyl-CoA synthase (KCS) in the seedlings, could be induced by butachlor in both wheat seeds with or without fenclorim pre-soaking. These results suggested that butachlor provides the highest control forR. kamojiand did not affect germination and emergence in wheat. The basis of fenclorim-increased selectivity to butachlor was associated with the induced GST and KCS-mediated enhanced herbicide metabolism in wheat.Keywords:Roegneria kamoji;wheat;herbicide safener;fenclorim;selectivity

CAS / MDL: 3740-92-9
研究领域: 农业科学 · 杂草科学 · 植物生理学 · 药理学
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