本文選題：手性除草劑 + 對(duì)映體　； 參考：《中國(guó)農(nóng)業(yè)大學(xué)》2016年博士論文

【摘要】：手性農(nóng)藥越來(lái)越受到人們的關(guān)注,對(duì)映體具有相同的物理化學(xué)性質(zhì),但生物活性和毒性通常具有較大的差異,在生物體及環(huán)境中的吸收、分布和降解等行為也通常不同。開(kāi)發(fā)和使用光學(xué)純的手性農(nóng)藥可以提高藥效、減少農(nóng)藥的使用量。而目前對(duì)手性農(nóng)藥環(huán)境行為的研究還不夠全面,缺乏生物活性、毒性及歸趨行為的基礎(chǔ)數(shù)據(jù)。深入研究手性農(nóng)藥的環(huán)境行為,可在對(duì)映體水平上揭示相關(guān)機(jī)理,探索對(duì)映體的污染規(guī)律,為開(kāi)發(fā)光學(xué)純手性農(nóng)藥奠定基礎(chǔ),指導(dǎo)手性農(nóng)藥的合理使用,減輕環(huán)境負(fù)擔(dān)。本文以手性除草劑精異丙甲草胺、乙氧呋草黃、敵草胺及吡氟禾草靈為目標(biāo),研究了對(duì)映體在多種環(huán)境基質(zhì)中的環(huán)境行為、污染規(guī)律及應(yīng)用穩(wěn)定性,具體內(nèi)容如下。建立了精異丙甲草胺的檢測(cè)方法及樣品前處理方法,考察了精異丙甲草胺在安徽和黑龍江土壤及玉米植株中的降解。精異丙甲草胺在土壤中的降解速率小于在玉米植株中降解速率,在土壤中半衰期為12.00-12.40 d,而在玉米植株中僅為0.80-1.10 d,同時(shí)黑龍江玉米植株中的降解速率大于安徽玉米植株中的降解速率。對(duì)精異丙甲草胺的穩(wěn)定性研究結(jié)果表明,其在土壤及玉米植株中均保持構(gòu)型穩(wěn)定,無(wú)異構(gòu)化發(fā)生。建立了乙氧呋草黃對(duì)映體的拆分方法及在基質(zhì)中的殘留分析方法。考察了乙氧呋草黃在寧夏、安徽、黑龍江和內(nèi)蒙古土壤中及甜菜植株中的選擇性降解。結(jié)果表明,乙氧呋草黃在土壤中的降解較慢,半衰期為14.44-63.01 d,四種土壤中的降解速率差別較大,k(安徽土壤)k(黑龍江土壤)k(內(nèi)蒙古土壤)k(寧夏土壤)；乙氧呋草黃在甜菜植株中的降解較快,半衰期在0.75-1.94d之間。乙氧呋草黃對(duì)映體在四種土壤中的降解不具有選擇性,而在寧夏和內(nèi)蒙古甜菜植株中的降解具有選擇性。在寧夏甜菜植株中,(-)-乙氧呋草黃比(+)-乙氧呋草黃降解的快；而在內(nèi)蒙甜菜植株(+)-乙氧呋草黃優(yōu)先降解。制備了光學(xué)純吡氟禾草靈及吡氟禾草靈酸,建立了簡(jiǎn)單、快速的樣品前處理及檢測(cè)方法。在此基礎(chǔ)上研究了吡氟禾草靈在北京、安徽和黑龍江土壤中的選擇性降解及穩(wěn)定性。毗氟禾草靈在北京和安徽土壤中呈現(xiàn)選擇性降解,在北京土壤中R-(+)-毗氟禾草靈的降解較快；而在安徽土壤中,S-(-)-毗氟禾草靈優(yōu)先降解。吡氟禾草靈光學(xué)純單體的轉(zhuǎn)化實(shí)驗(yàn)表明,R-(+)-吡氟禾草靈在三種土壤降解過(guò)程中均保持構(gòu)型穩(wěn)定,不會(huì)發(fā)生對(duì)映體之間的轉(zhuǎn)化；而S-(-)-吡氟禾草靈在北京和黑龍江土壤中除了生成S-(-)-吡氟禾草靈,還有R-(+)-毗氟禾草靈酸的生成。毗氟禾草靈在水環(huán)境中的選擇性降解實(shí)驗(yàn)表明,吡氟禾草靈在堿性水中降解較快,在酸性水中降解緩慢。毗氟禾草靈在上莊水庫(kù)水中的降解具有選擇性,S-(-)-毗氟禾草靈降解較快,而在其他水體中均未發(fā)生選擇性降解。精毗氟禾草靈在幾種水體的降解過(guò)程中均只轉(zhuǎn)化為R-(+)-吡氟禾草靈酸,表明精吡氟禾草靈在水體中的降解具有構(gòu)型穩(wěn)定性。田間條件下,毗氟禾草靈在幾種植物及土壤中的選擇性降解實(shí)驗(yàn)結(jié)果表明,吡氟禾草靈在幾種植物和土壤中的降解均具有選擇性。在番茄和黃瓜中,都是S-(-)-吡氟禾草靈優(yōu)先降解；而在小白菜、油菜及土壤中,R-(+)-毗氟禾草靈降解較快,導(dǎo)致S-(-)-毗氟禾草靈的相對(duì)富集。精毗氟禾草靈在以上幾種基質(zhì)中的降解均保持構(gòu)型穩(wěn)定。此外,考察了毗氟禾草靈在家兔體血漿中的選擇性降解及穩(wěn)定性。吡氟禾草靈在家兔體內(nèi)血漿中快速降解為毗氟禾草靈酸,吡氟禾草靈酸的生成及降解表現(xiàn)明顯的選擇性。同時(shí),吡氟禾草靈在家兔體外血漿中代謝很快,且降解具有選擇性,S-(-)-吡氟禾草靈降解相對(duì)較快。精吡氟禾草靈在家兔體內(nèi)外血漿中的降解均保持構(gòu)型穩(wěn)定,無(wú)異構(gòu)體的轉(zhuǎn)化發(fā)生。建立了敵草胺對(duì)映體的殘留分析方法,研究了敵草胺在番茄、黃瓜、甘藍(lán)、油菜和土壤中的立體選擇性降解行為,結(jié)果表明敵草胺在蔬菜中的降解較快,半衰期為1.13-2.21 d,在土壤中降解相對(duì)較慢,半衰期為11.95 d。敵草胺在甘藍(lán)中的降解呈現(xiàn)明顯的立體選擇性,(-)-敵草胺降解速率大于(+)-敵草胺；在番茄、黃瓜、油菜和土壤中的降解均不具有對(duì)映體選擇性。利用高效液相制備色譜制得了敵草胺兩個(gè)光學(xué)異構(gòu)體,并對(duì)其進(jìn)行旋光測(cè)定,確定構(gòu)型�？疾炝藬巢莅芳捌鋵�(duì)映體對(duì)非靶標(biāo)作物大豆和黃瓜的形態(tài)學(xué)和生理學(xué)的影響,結(jié)果顯示敵草胺明顯抑制大豆和黃瓜的正常生長(zhǎng),并在一定程度上對(duì)大豆和黃瓜造成了氧化損傷,促使大豆和黃瓜體內(nèi)抗氧化酶的活性下降,且(-)-敵草胺的抑制能力遠(yuǎn)遠(yuǎn)高于(+)-敵草胺。同時(shí)測(cè)定了敵草胺及其對(duì)映體對(duì)其靶標(biāo)作物高羊茅和早熟禾的活性作用,結(jié)果表明(-)-敵草胺對(duì)高羊茅和早熟禾的活性遠(yuǎn)遠(yuǎn)高于(+)-敵草胺。建立了甲霜靈和甲霜靈酸的手性拆分方法及在番茄中的殘留分析方法,考察了精甲霜靈在黑龍江和湖南番茄中的降解行為,同時(shí)研究了精甲霜靈的手性穩(wěn)定性,研究結(jié)果表明精甲霜靈在黑龍江和湖南番茄中的降解半衰期分別為8.7 d和1.6d,表明精甲霜靈在湖南番茄中降解較快。精甲霜靈在黑龍江和湖南番茄中均降解為精甲霜靈酸,同時(shí)檢測(cè)到了S-甲霜靈及S-甲霜靈酸。雖然精甲霜靈在黑龍江和湖南番茄中的降解過(guò)程中發(fā)生的構(gòu)型轉(zhuǎn)化,但是其S異構(gòu)體的含量微乎其微,不足以影響精甲霜靈的藥效。本論文工作確定了幾種手性除草劑對(duì)映體的環(huán)境行為,揭示了對(duì)映體的污染規(guī)律,對(duì)于指導(dǎo)相關(guān)農(nóng)藥的合理使用、減小環(huán)境污染、準(zhǔn)確評(píng)價(jià)手性農(nóng)藥的污染風(fēng)險(xiǎn)具有一定的指導(dǎo)意義。
[Abstract]:Chiral pesticides have attracted more and more attention. The enantiomers have the same physical and chemical properties, but the biological activity and toxicity usually differ greatly. The absorption, distribution and degradation of the organisms and the environment are usually different. The development and use of optical pure chiral pesticides can improve the efficacy and reduce the use of pesticides. At present, the research on environmental behavior of adversary pesticide is not comprehensive, and it lacks the basic data of biological activity, toxicity and convergence behavior. The study of environmental behavior of chiral pesticides can reveal the mechanism of enantiomers, explore the rules of enantiomers, lay the foundation for the development of optically pure chiral pesticides, and guide the rational of chiral pesticides. In this paper, the environmental behavior, pollution law and application stability of enantiomers in a variety of environmental substrates were studied in this paper, with the target of chiral herbicides, methoprololamine, ethoxylum yellow, dioxamine and piopalazine, and the specific contents were as follows. The degradation rate of methoprolone in soil and maize plants in Anhui and Heilongjiang was investigated. The degradation rate of methoprolone in soil was less than that in maize plants, the half-life in soil was 12.00-12.40 D, but only 0.80-1.10 D in maize plants, and the degradation rate of Heilongjiang maize plants was greater than that of Anhui. The degradation rate in maize plants. The stability of methoprololamine showed that the structure remained stable in the soil and maize plants. The method for enantiomers of ethoxylum yellow enantiomers and the residue analysis in the matrix were established. The ethoxylum yellow was found in Ningxia, Anhui, Heilongjiang and Inner Mongolia. The degradation of palaeosol and beet plants showed that ethoxy yellow was degraded slowly in the soil, the half-life was 14.44-63.01 D, and the degradation rate of the four soils was different, K (Anhui soil) K (Heilongjiang soil) K (Inner Mongolia soil) K (Ningxia soil), and the degradation of ethoxylate yellow in Sugarbeet plants was faster and semi decider. The degradation of ethoxylor yellowish enantiomers in four soils is not selective, but the degradation in Ningxia and Inner Mongolia beet plants is selective. In Ningxia beet plants, (-) - ethoxylf yellow ratio (+) - ethoxyrodine yellow degradation, and in Inner Mongolia beet plants (+) - ethoxyrodine yellow degradation. The selective degradation and stability of piopufluolin in soils of Beijing, Anhui and Heilongjiang were studied. On this basis, the selective degradation and stability of piopufluolin in Beijing, Anhui and Heilongjiang soils were studied. The selective degradation of pifluacolin in Beijing and Anhui soils was found in Beijing soil R- (+) - the degradation of vishlopherol was faster; and in Anhui soil, S- (-) - visharacin was degraded first. The transformation experiment of pioparopine optical pure monomer showed that R- (+) - pylfluacolin maintained stable configuration during the three soil degradation processes and did not transform between enantiomers; and S- (-) - pioparopine was in Beijing and black dragon. In addition to the formation of S- (-) - pioparalin and R- (+) - vishalalic acid, the selective degradation of vishloparalin in water environment shows that pyfluacalin degrades rapidly in alkaline water and degrades slowly in acid water. The degradation of vishalalin in the water of Shanghai reservoir is selective, S- (-) - Vishnu grass The degradation of the spirit is fast, but no selective degradation in other water bodies. In the degradation process of several water bodies, the degrading process is only converted to R- (+) - pioparacinic acid. It shows that the degradation of pylfluopara in water has the structure stability. Under the field conditions, the selective degradation of vishlopara in several plants and soil The results showed that the degradation of pyfluacolin in several plants and soils was selective. In tomato and cucumber, S- (-) - pylfluacoline was degraded first; in Chinese cabbage, rape and soil, the degradation of R- (+) - visharacinin was faster and the relative enrichment of S- (-) - vishloparin was found. The degradation and stability of confluacarin in rabbit plasma was also maintained. In addition, the selective degradation and stability of vishulacarin in rabbit plasma was investigated. Pifluacarin was rapidly degraded into vishularic acid in the plasma of rabbits, and the formation and degradation of piopufluarlic acid showed obvious selectivity. The degradation of S- (-) - pylfluacolin was relatively fast. The degradation of pylflupramol in the plasma of rabbits in and out of the body remained stable, without the transformation of isomers. The residue analysis method of diantiomine enantiomers was established, and diechamine was studied in tomato, cucumber, Brassica, rape and soil. The stereoselective degradation shows that the degradation of diethylene in vegetables is faster, the half-life is 1.13-2.21 D, the degradation is relatively slow in the soil, the half-life is 11.95 D., and the degradation of acetamide in cabbage is obviously stereoselective, (-) - the degradation rate of diamamine is greater than (+) - diamamine, and in tomatoes, cucumbers, rape and soil The degradation of the enantiomers was not selective. Two optical isomers of diosseamines were prepared by high performance liquid chromatography, and the structure was determined by polarimetry. The effects of diechamine and its enantiomers on the morphology and physiology of non target crops soybean and cucumber were investigated. The results showed that diechamine significantly inhibited soybean and cucumber. Normal growth, and to a certain extent, caused oxidative damage to soybean and cucumber, and reduced the activity of antioxidant enzymes in soybean and cucumber, and (-) - diekamine was far higher than (+) - diekamine. The activity of dianlamine and its enantiomers on the target crops of Tall Fescue and Poa pratensis were measured. The results showed - - The activity of diachlor to tall fescue and Poa pratensis was much higher than (+) - diekamine. The chiral separation method of metalalin and Jia Shuangling acid and the residue analysis method in tomato were established. The degradation behavior of Jing metalin in Heilongjiang and Hunan tomatoes was investigated. The chiral stability of spermetalin was studied. The degradation half-life of Ling in Heilongjiang and Hunan tomatoes were 8.7 D and 1.6d respectively, indicating that the degradation of Jing metalin in Hunan tomatoes was faster. The degrade of Jing metalalin in Heilongjiang and Hunan tomatoes was degrading to metalalinic acid, and S- metalalin and S- methalalinic acid were detected, although metalaldein was degraded in Heilongjiang and Hunan tomatoes. The structure transformation occurred in the process, but the content of the S isomer was very small, and it was not enough to affect the efficacy of metalaxyl. In this paper, the environmental behavior of several chiral herbicides was determined, and the pollution regularity of enantiomers was revealed, the rational use of the related pesticides, the reduction of environmental pollution, and the accurate evaluation of the pollution of chiral pesticides. The risk of dyeing has certain guiding significance.
【學(xué)位授予單位】：中國(guó)農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：X592
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本文編號(hào)：2005513