【摘要】：手性農(nóng)藥的對映體在環(huán)境化學(xué)行為和生態(tài)毒理方面顯示出的選擇差異性,在人和動物體內(nèi)普遍存在。水胺硫磷(isocarbophos,ICP)屬有機磷農(nóng)藥中的一種,是一硫代磷酰胺類的殺蟲、殺螨劑,被廣泛應(yīng)用在農(nóng)業(yè)上。水胺硫磷是手性化合物,但關(guān)于水胺硫磷不同對映體的毒性研究報道的文獻有限。本課題前期工作探討了丙酮溶劑對水華微囊藻(Microcystis flos-aquae)和蛋白核小球藻(Chlorella pyrenoidsa)的光合活性影響,找到敏感藻類及其最大無觀察效應(yīng)值,為手性農(nóng)藥毒理研究提供更可靠的數(shù)據(jù)依據(jù)。課題組將手性農(nóng)藥水胺硫磷進行拆分,得到單一對映體,通過測定水胺硫磷對水華微囊藻葉綠素a含量和光合作用的相關(guān)參數(shù),水華微囊藻的抗氧化酶活性和MDA含量,以及大型蚤(Daphnia magna)的抗氧化酶活性和MDA含量,揭示水胺硫磷對水生生物的毒性影響,闡述兩種對映體對水生生物毒性的選擇性差異,從而為手性農(nóng)藥的環(huán)境安全和人體健康風(fēng)險評價提供技術(shù)支持和科學(xué)依據(jù)。實驗結(jié)果表明:(1)丙酮對水華微囊藻和小球藻的NOEC值分別為0.5%和0.05%,說明水華微囊藻對丙酮更為敏感。(2)在測定水胺硫磷及其對映體對水華微囊藻葉綠素a含量及光合活性的毒性實驗中發(fā)現(xiàn),(+)-ICP的毒性最強;Rac-ICP次之,(-)-ICP毒性最弱。(+)-ICP降低了水華微囊藻葉綠素a的含量,同時也抑制了水華微囊藻的光合活性,降低了藻細胞的光能利用率、最大電子傳遞速率以及強光耐受能力;而(-)-ICP和Rac-ICP則促進了光系統(tǒng)II的電子傳遞和光能利用率,提高了光合活性,使藻細胞對強光耐受能力增強。故這一結(jié)果可以說明,手性水胺硫磷對水華微囊藻細胞葉綠素a含量及光合作用的影響均存在顯著的對映體選擇性。(3)水胺硫磷對水華微囊藻產(chǎn)生的氧化損傷效應(yīng)的實驗結(jié)果顯示了手性水胺硫磷顯著的對映體差異。在暴露期間,Rac-,(+)-和(-)-ICP三者均未引起水華微囊藻細胞膜的脂質(zhì)過氧化。但(+)-ICP處理組的MDA含量高于(-)-ICP,并且對SOD和CAT酶活性的影響存在“低促高抑”的現(xiàn)象。(-)-ICP處理組對SOD酶活性無影響,對CAT酶活性也存在“低促高抑”,但程度沒有(+)-ICP處理組明顯。(4)水胺硫磷對大型蚤產(chǎn)生的氧化損傷效應(yīng)結(jié)果顯示了顯著的對映體差異。高濃度(2.5~20μg/L)下的處理組,(+)-ICP導(dǎo)致大型蚤體內(nèi)脂質(zhì)過氧化,(-)-ICP和ICP的MDA含量則明顯低于空白組,無脂質(zhì)過氧化現(xiàn)象。在各濃度處理下,(-)-ICP的SOD酶活性均大于ICP和(+)-ICP。而濃度在2.5~20μg/L時,(+)-ICP的CAT酶活性要大于ICP和(-)-ICP。
[Abstract]:Enantiomeric enantiomers of chiral pesticides show different selection in environmental chemical behavior and ecotoxicology, which are common in humans and animals. Isocarbophos,ICP is a kind of organophosphorus pesticide. It is an insecticide and acaricidal agent of phosphorothioamides, which is widely used in agriculture. Water sulphos are chiral compounds, but there is limited literature on the toxicity of different enantiomers. The effects of acetone solvent on photosynthetic activity of microcystis Shui Hua (Microcystis flos-aquae) and Chlorella Proteinus (Chlorella pyrenoidsa) were studied in this paper. The sensitive algae and its maximum non-observed effect were found, which provided a more reliable data basis for the study of chiral pesticide toxicology. A single enantiomer was obtained by separating the chiral pesticide, glyphosate. The contents of chlorophyll a and photosynthesis of microcystis Shui Hua, the antioxidant enzyme activity and the content of MDA were determined by determining the content of chlorophyll a and photosynthesis of microcystis Shui Hua. The antioxidant enzyme activity and MDA content of (Daphnia magna) revealed the toxicity of sulphos to aquatic organisms, and the selectivity of the two enantiomers to aquatic organisms was discussed. It provides technical support and scientific basis for environmental safety and human health risk assessment of chiral pesticides. The results showed that: (1) the NOEC values of acetone to microcystis Shui Hua and Chlorella microcystis were 0.5% and 0.05, respectively, which indicated that Shui Hua microcystis were more sensitive to acetone. (2) the contents of chlorophyll a and photosynthesis of Sac_person2# microcystis were determined by spectrophot2#. In the active toxicity test, () ICP was the most toxic, Rac-ICP was the second, and (-) ICP was the weakest. () ICP, which decreased the content of chlorophyll a in microcystis Shui Hua. At the same time, it also inhibited the photosynthetic activity of microcystis Shui Hua, decreased the utilization rate of light energy, the maximum electron transfer rate and the ability of strong light tolerance of algal cells, while (-)-ICP and Rac-ICP promoted the electron transport and light energy utilization of II in the light system. The photosynthetic activity was increased, and the ability of algal cells to strong light tolerance was enhanced. So this result shows that, There was significant enantioselectivity on chlorophyll a content and photosynthesis in microcystis cells of Shui Hua. (3) the oxidative damage effect of isocyanidophos on Sac_person1# microcystis showed chiral effect. There is significant enantiomeric difference in sulphos. During exposure, Rac-, ()-and (-)-ICP did not induce lipid peroxidation of microcystis cell membrane. However, the content of MDA in (-)-ICP treatment group was higher than that in (-)-ICP, treatment group, and the effect on the activity of SOD and CAT enzyme was "low promoting high inhibition". (-)-ICP treatment group had no effect on SOD enzyme activity, and "low promoting high inhibition" on CAT enzyme activity. But the degree was not obvious in ()-ICP treatment group. (4) the oxidative damage effect of siderophos on flea Magna showed significant enantiomeric difference. At high concentration (2.5 渭 g / L), () ICP resulted in lipid peroxidation in flea, and the MDA contents of (-) ICP and ICP were significantly lower than those of control group, and there was no lipid peroxidation. The SOD enzyme activity of (-)-ICP was higher than that of ICP and ()-ICP. under different concentrations. The CAT activity of, ()-ICP was higher than that of ICP and (-)-ICP. at the concentration of 2.5 渭 g / L and 20 渭 g / L.
【學(xué)位授予單位】：華僑大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X171.5;X592

【相似文獻】

相關(guān)期刊論文 前10條

1 鄭卓;手性農(nóng)藥與手性技術(shù)(一)[J];精細與專用化學(xué)品;2001年23期

2 李旭坤,劉鳳玲;手性農(nóng)藥的合成技術(shù)[J];山東化工;2001年04期

3 吳艷芳;;濱農(nóng)科技獲批組建山東省手性農(nóng)藥工程技術(shù)研究中心[J];山東農(nóng)藥信息;2012年02期

4 鄭卓;手性農(nóng)藥與手性技術(shù)(二)[J];精細與專用化學(xué)品;2001年24期

5 楊淑蓮;徐漢虹;李俊凱;侯學(xué)文;;手性農(nóng)藥酶法合成的研究進展[J];世界農(nóng)藥;2005年03期

6 孟磊;袁超;;高效液相色譜在手性農(nóng)藥分析分離上的應(yīng)用研究進展[J];河南農(nóng)業(yè)大學(xué)學(xué)報;2006年02期

7 劉建陽;林春綿;張大同;;超臨界CO_2色譜拆分手性農(nóng)藥的研究進展[J];化學(xué)與生物工程;2007年07期

8 武彤;李朝陽;李巧玲;張炳燭;李景印;王未肖;;三唑類手性農(nóng)藥高效液相色譜分離的研究[J];河北科技大學(xué)學(xué)報;2008年04期

9 武彤;李朝陽;李巧玲;張炳燭;李景印;;手性農(nóng)藥高效液相色譜分離的研究[J];河北師范大學(xué)學(xué)報(自然科學(xué)版);2009年02期

10 唐夢齡;王丹;傅柳松;劉維屏;;手性農(nóng)藥毒性機制的對映體選擇性[J];農(nóng)藥學(xué)學(xué)報;2011年04期

相關(guān)會議論文 前10條

1 張侃侃;宋寶安;楊松;;手性農(nóng)藥分析的研究概況[A];中國化學(xué)會第三屆全國分子手性學(xué)術(shù)研討會論文集[C];2010年

2 劉維屏;徐超;馬云;趙美蓉;周珊珊;文岳中;;手性農(nóng)藥環(huán)境安全的對映體選擇性[A];中國化學(xué)會第三屆全國分子手性學(xué)術(shù)研討會論文集[C];2010年

3 劉維屏;;手性農(nóng)藥與環(huán)境安全[A];第三屆全國環(huán)境化學(xué)學(xué)術(shù)大會論文集[C];2005年

4 王兆霞;祈媛;黃思凱;馬淑娟;李從芬;韓小茜;;手性農(nóng)藥在纖維素-三(4-甲基苯基氨基甲酯)手性固定相上的直接拆分[A];西北地區(qū)第七屆色譜學(xué)術(shù)報告會甘肅省第十二屆色譜年會論文集[C];2012年

5 韓小茜;仇偉;常靜;;手性農(nóng)藥在纖維素-氯苯基氨基甲酸酯手性固定相上的拆分[A];甘肅省化學(xué)會二十六屆年會暨第八屆中學(xué)化學(xué)教學(xué)經(jīng)驗交流會論文集[C];2009年

6 王兆霞;祈媛;任琴;何乃普;李從芬;韓小茜;;纖維素-三(4-氯苯基氨基甲酸酯)手性固定相在正相條件下對五種手性農(nóng)藥的直接拆分[A];西北地區(qū)第七屆色譜學(xué)術(shù)報告會甘肅省第十二屆色譜年會論文集[C];2012年

7 任勇;關(guān)金濤;余廣鰲;劉盛華;;不對稱催化反應(yīng)在手性農(nóng)藥合成中的一些應(yīng)用[A];第三屆湖北湖南植保農(nóng)藥學(xué)術(shù)研討會論文集[C];2004年

8 江正瑾;高如瑜;張鍇;張智超;王琴孫;閻超;;微徑高效液相色譜法分離三唑類手性農(nóng)藥[A];天津市第十四次色譜學(xué)術(shù)交流會論文集[C];2000年

9 韓小茜;趙麗;魏燕;劉艷華;;農(nóng)藥戊唑醇在Chiralcel OJ-H柱上的拆分[A];甘肅省化學(xué)會第二十四屆年會論文集[C];2005年

10 韓小茜;魏燕;劉艷華;常靜;仇偉;;三唑類手性農(nóng)藥在Chiralcel OD-H手性柱上反相、極性有機相模式下的手性拆分[A];西北地區(qū)第五屆色譜學(xué)術(shù)報告會暨甘肅省第十屆色譜年會論文集[C];2008年

相關(guān)重要報紙文章 前1條

1 記者 翁國娟;酶催化升級手性農(nóng)藥合成技術(shù)[N];中國化工報;2013年

相關(guān)博士學(xué)位論文 前6條

1 李玲;兩類手性農(nóng)藥的對映體拆分及對映體選擇性毒理研究[D];浙江工業(yè)大學(xué);2010年

2 黃z，

本文編號：2267506