本文選題：唑胺菌酯 + 代謝��； 參考：《沈陽農(nóng)業(yè)大學(xué)》2017年博士論文

【摘要】：唑胺菌酯是沈陽化工研究院創(chuàng)制的一種新型甲氧丙烯酸酯類殺菌劑,殺菌譜廣、殺菌活性高,2011年,95%唑胺菌酯原藥與20%唑胺菌酯懸浮劑獲得國內(nèi)臨時(shí)登記,登記的防治對象為黃瓜白粉病。我們以唑胺菌酯為研究對象,建立了該藥劑和兩個代謝產(chǎn)物的在黃瓜、土壤中的痕量檢測方法,研究了唑胺菌酯在黃瓜植株內(nèi)的代謝、傳導(dǎo)過程,以及在土壤中的淋溶、吸附、土壤降解、水-沉積物系統(tǒng)降解、魚類急性毒性和生物富集試驗(yàn),并在田間進(jìn)行了20%唑胺菌酯懸浮劑的土壤和黃瓜的消解試驗(yàn)�；贖PLC-MS/MS建立了唑胺菌酯及其代謝產(chǎn)物唑胺菌酯-Ml、唑胺菌酯-M2在黃瓜、土壤中的簡單、快速、準(zhǔn)確的QuEChERS測定方法。黃瓜樣品經(jīng)乙腈提取,PSA和GCB填料凈化后,HPLC-MS/MS分析;土壤樣品經(jīng)乙腈提取,PSA填料凈化后,HPLC-MS/MS分析。采用MRMESI正離子模式,唑胺菌酯及其代謝產(chǎn)物的定量離子對分別為382.1/164.2、368.1/164.1和352.2/189.1,三個組份在3.2 min-3.9 min之內(nèi)被分離開。唑胺菌酯在0.05?10.0μg/L(唑胺菌酯代謝產(chǎn)物在0.5?100.0μg/L)范圍內(nèi)有良好的線性相關(guān)性,相關(guān)系數(shù)均大于0.9988,在試驗(yàn)土壤和黃瓜中的平均添加回收率為78.8%?93.8%,相對標(biāo)準(zhǔn)偏差均小于6.9%,符合農(nóng)藥殘留檢測要求。采用HPLC-MS/MS技術(shù),對唑胺菌酯在黃瓜苗中的代謝、降解及傳導(dǎo)性進(jìn)行了研究。研究結(jié)果表明唑胺菌酯在黃瓜中消解較快,半衰期為2.0?2.2d。同時(shí)唑胺菌酯在黃瓜苗中具有較好的內(nèi)吸性和傳導(dǎo)性,可以通過根莖和葉片吸收,并可實(shí)現(xiàn)根莖→葉片、葉片→葉片及葉片→根莖傳導(dǎo),因而表現(xiàn)出較好的保護(hù)和治療活性。通過對經(jīng)唑胺菌酯處理的黃瓜苗和未經(jīng)處理的黃瓜苗樣品進(jìn)行分析比較,發(fā)現(xiàn)了唑胺菌酯的2個代謝產(chǎn)物,分子量分別為367.2(唑胺菌酯-Ml)和351.2(唑胺菌酯-M2)。通過對唑胺菌酯及其代謝產(chǎn)物的質(zhì)譜進(jìn)行解析,鑒定了2個代謝產(chǎn)物的可能結(jié)構(gòu)式,并通過合成確證了這兩個代謝產(chǎn)物。采用土壤薄板層析法和土柱淋溶法研究了唑胺菌酯在三種土壤中的淋溶特性,結(jié)果表明:唑胺菌酯在三種土壤中的移動性屬于“不移動”和“難淋溶”,不易隨降水或土壤毛細(xì)作用進(jìn)入地下水中,不易造成地下水的污染。研究了唑胺菌酯在黑土、紅土和水稻土中的吸附特性,在黑土中的吸附率最大,其次是水稻土,紅土中的吸附率最小,并符合Freundlich吸附等溫模型。唑胺菌酯在黑土、紅土和水稻土中的Kf值分別為127.8、49.8和85.2,Koc值分別為7473.7、4742.9和14947.4,唑胺菌酯在黑土和水稻土中的吸附等級為“Ⅱ”級,屬于“較易土壤吸附”,在紅土中的吸附等級為“Ⅲ”級,屬于“中等土壤吸附”。唑胺菌酯在三種土壤中的吉布斯自由能變化均小于40 KJ/mol,屬于物理吸附。有機(jī)質(zhì)含量和陽離子交換量是影響土壤吸附的重要因素。唑胺菌酯好氧條件下在黑土中的降解半衰期為67.3 d,降解特性為“Ⅱ級(中等降解)”;紅土、水稻土中的降解半衰期分別為96.3d和110.0d,降解特性均為“Ⅲ級(較難降解)”;積水厭氣條件明顯縮短了唑胺菌酯的降解半衰期,三種土壤降解特性均為“易降解”。唑胺菌酯土壤降解半衰期與土壤有機(jī)質(zhì)含量呈現(xiàn)出一定的負(fù)相關(guān)性。在田間條件下開展了 20%唑胺菌酯懸浮劑在遼寧沈陽、山東壽光和浙江杭州一年三地的土壤消解試驗(yàn),半衰期為12.9～14.9d,相比實(shí)驗(yàn)室條件下的降解明顯加快,這可能受試驗(yàn)期間光照以及降雨的影響。唑胺菌酯在高碳好氧、高碳厭氧、低碳好氧及低碳厭氧四種條件下的降解半衰期為5.0～6.5d,屬于“易降解”。四種條件下水-沉積物系統(tǒng)水相中唑胺菌酯含量變化與系統(tǒng)降解的總趨勢接近,呈現(xiàn)明顯的消解下降趨勢,唑胺菌酯在水-沉積物系統(tǒng)中的降解主要受水體中濃度變化的影響,而沉積物相對整個水-沉積物系統(tǒng)中的農(nóng)藥降解的影響并不顯著。以斑馬魚為試驗(yàn)用魚,進(jìn)行了唑胺菌酯的急性毒性和生物富集試驗(yàn)。魚類急性毒性試驗(yàn)LC50(96h)為0.20mg/L,95%置信限為0.17～0.23mg/L,對斑馬魚“高毒”。以流水式法進(jìn)行了魚類生物富集試驗(yàn),4.8 h換水一次,以LC50 (96h)的1/10、1/100濃度設(shè)置藥液的濃度處理,即0.02 mg/L和0.002 mg/L,吸收階段進(jìn)行12天,清除階段進(jìn)行4天。配制濃度為0.002 mg/L時(shí),吸收速率常數(shù)為69.3 d-1;清除速率常數(shù)為0.9945 d-1;動態(tài)生物富集系數(shù)為69.7。配制濃度為0.02 mg/L時(shí),吸收速率常數(shù)為45.0 d-1;清除速率常數(shù)為0.8036 d-1;動態(tài)生物富集系數(shù)為56.0,屬于“中等富集性”。
[Abstract]:Azolomide is a new methoxy acrylate fungicide created by Shenyang Chemical Research Institute, which has a wide spectrum of bactericidal spectrum and high bactericidal activity. In 2011, 95% zazolamides and 20% azolomide esters were temporarily registered in China. The control object of the registration was cucumber powdery mildew. The metabolism of the metabolites in cucumber and soil, the metabolism and the conduction process of azolomate in cucumber plants, and the leaching, adsorption, soil degradation, water sediment system degradation in the soil, the acute toxicity and bioaccumulation of fish in the soil, and the soil and cucumber of 20% azolomide ester suspending agent in the field were carried out in the field. Based on HPLC-MS/MS, a simple, fast and accurate QuEChERS method for determination of azzolium ester and its metabolite zazomate ester -Ml and zazolamide ester -M2 in cucumber and soil was established based on a simple, rapid and accurate method for determination of QuEChERS. After purification of PSA and GCB fillers, the cucumber samples were purified by HPLC-MS/MS; the soil samples were extracted by acetonitrile and purified by PSA fillers. By using MRMESI positive ion mode, the quantitative ion pairs of azolomate and its metabolites were 382.1/164.2368.1/164.1 and 352.2/189.1, respectively, and three components were separated within 3.2 min-3.9 min, and zzolamines had good linear correlation in the range of 0.05? 10 micron (azolide metabolites in 0.5? 100 g/ L). The average recovery rate in the experimental soil and cucumber was 78.8%? 93.8%, and the relative standard deviation was less than 6.9%, which was in line with the requirements of pesticide residue detection. The metabolism, degradation and conductivity of azolomate in cucumber seedlings were studied by HPLC-MS/MS technology. The results showed that azolomate was quickly eliminated in Cucumber. The half-life is 2? 2.2d., and zolomide ester has good absorbability and conductivity in cucumber seedlings. It can be absorbed through rhizomes and leaves, and can carry out rhizome, leaf, leaf, leaf and rhizome, thus showing good protection and therapeutic activity. The samples of cucumber seedlings were analyzed and compared. 2 metabolites of azolomide ester were found. The molecular weight was 367.2 (zazomate -Ml) and 351.2 (zolomamine ester -M2). By analyzing the mass spectra of azolomide ester and its metabolites, the possible structure of 2 metabolites was identified, and the two metabolites were confirmed by synthesis. The leaching characteristics of azolomate in three soils were studied by soil sheet chromatography and soil column leaching. The results showed that the mobility of azolomate in three soils was "not moving" and "hard to leaching". It was not easy to enter underground water with precipitation or soil capillary action, and it was not easy to cause groundwater pollution. The adsorption characteristics in black soil, laterite and paddy soil are the largest in black soil, followed by paddy soil, the adsorption rate of red soil is the smallest, and the Freundlich adsorption isotherm model is in line with the Kf values of azolomide in black soil, red soil and paddy soil, respectively, 127.8,49.8 and 85.2, Koc values of 7473.74742.9 and 14947.4 respectively, azolomide ester in black soil. The adsorption grade in the paddy soil is "II" grade, which belongs to "easier soil adsorption". The adsorption grade in the red soil is "III" grade and belongs to "medium soil adsorption". The Gibbs free energy of azolomate in three soils is less than 40 KJ/mol, and it belongs to physical adsorption. The content of organic matter and the exchange of cation are affected by the soil. The important factor of adsorption is that the half-life of degradation in the black soil under azolide aerobic condition is 67.3 D, and the degradation characteristic is "grade II (medium degradation)". The degradation half life of red soil and paddy soil is 96.3d and 110.0d respectively, and the degradation characteristics are all "grade III (more difficult to degrade)", and the anaerobic condition of water accumulation obviously shortens the degradation of azolomate. During the period, the degradation characteristics of the three kinds of soil were all "easy to degrade". The half-life of azolomate soil degradation was negatively correlated with the content of soil organic matter. In the field, the soil soil digestion test of 20% azolomide ester suspension agent in Shenyang, Shandong Shouguang and Hangzhou of Zhejiang was carried out in the field, and the half-life was 12.9 ~ 14.9d, compared with the half-life of zolomate ester. The degradation in the laboratory conditions is obviously accelerated, which may be affected by light and rainfall during the experiment. The half-life of azolomate in the four conditions of high carbon aerobic, high carbon anaerobic, low carbon aerobic and low carbon anaerobic conditions is 5 ~ 6.5d, which is "easy to degrade". The change of azolide content in the water phase of the water sediment system and the change of the content of azolomide ester in the water sediment system of the four conditions The overall tendency of the system degradation is close, showing a clear decline trend. The degradation of azolomate in water sediment system is mainly influenced by the change of concentration in the water body, while the influence of the sediment on the degradation of pesticides in the whole water sediment system is not significant. The acute toxicity of zzebrafish as a test fish is carried out. The fish acute toxicity test LC50 (96h) was 0.20mg/L, the 95% confidence limit was 0.17 ~ 0.23mg/L, and the zebrafish "high poison" was "high poison". The fish bioaccumulation test was carried out by flow method, 4.8 h was changed to water once, the concentration of LC50 (96h) 1/10,1/100 concentration was set up, that was 0.02 mg/L and 0.002 mg/L, and the absorption stage was 12 days. When the concentration is 0.002 mg/L, the absorption rate constant is 69.3 D-1 and the clearance rate constant is 0.9945 D-1, and the absorption rate constant is 45 D-1 when the dynamic biological enrichment coefficient is 0.02 mg/L, and the clearance rate constant is 0.8036 D-1, and the dynamic bioaccumulation coefficient is 56, which belongs to "medium enrichment".
【學(xué)位授予單位】：沈陽農(nóng)業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：X592;S481

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 朱峰;董豐收;劉新剛;徐軍;鄭永權(quán);;新型殺菌劑苯菌酮在3種典型土壤中的淋溶行為[J];農(nóng)藥學(xué)學(xué)報(bào);2015年06期

2 趙建江;陳治芳;韓秀英;孟潤杰;馬志強(qiáng);王文橋;畢秋艷;;啶酰菌胺與唑胺菌酯混配對灰葡萄孢毒力的增效作用[J];農(nóng)藥學(xué)學(xué)報(bào);2015年04期

3 李蓉;儲大可;高永清;張憲臣;張朋杰;王靜;;復(fù)合分子印跡固相萃取-HPLC-MS/MS法測定植物源性食品中多種農(nóng)藥殘留[J];分析試驗(yàn)室;2015年08期

4 余斐;陳黎;艾丹;潘立寧;胡斌;劉惠民;;多壁碳納米管分散固相萃取-LC-MS/MS法分析煙草中114種農(nóng)藥殘留[J];煙草科技;2015年05期

5 張鵬;慕衛(wèi);劉峰;賀敏;羅梅梅;;噻蟲嗪在土壤中的吸附和淋溶特性[J];環(huán)境化學(xué);2015年04期

6 鞠超;徐軍;董豐收;劉新剛;吳小虎;張競戈;鄭永權(quán);;磺草酮在土壤中的淋溶特性研究[J];農(nóng)藥學(xué)學(xué)報(bào);2015年02期

7 廖和菁;張雪春;胡禮淵;鐘海翠;孫高英;劉瑞芳;;氣相色譜法同時(shí)測定茶葉中10種有機(jī)磷農(nóng)藥殘留[J];中國食品衛(wèi)生雜志;2015年01期

8 楊梅;;固相萃取-氣質(zhì)聯(lián)用測定茶葉中的26種農(nóng)藥殘留[J];農(nóng)藥科學(xué)與管理;2015年01期

9 韓蘭芳;孫可;康明潔;吳豐昌;Baoshan XING;;有機(jī)質(zhì)官能團(tuán)及微孔特性對疏水性有機(jī)污染物吸附的影響機(jī)制[J];環(huán)境化學(xué);2014年11期

10 段亞玲;李景壯;趙亞洲;席培宇;譚紅;;氟環(huán)唑在貴州土壤中淋溶特性研究[J];中國農(nóng)學(xué)通報(bào);2014年29期

，

本文編號：1986004