本文關(guān)鍵詞：不同結(jié)構(gòu)咪唑類(lèi)離子液體在土壤中對(duì)蠶豆幼苗的生態(tài)毒性及結(jié)構(gòu)對(duì)其毒性的影響　出處：《山東農(nóng)業(yè)大學(xué)》2016年博士論文　論文類(lèi)型：學(xué)位論文

  更多相關(guān)文章： 高效液相色譜 活性氧 氧化應(yīng)激 基因表達(dá) 陰離子 碳鏈長(zhǎng)度

【摘要】：離子液體是指全部由離子組成的,在室溫或低溫下為液態(tài)的鹽,又稱為室溫離子液體或室溫熔融鹽。離子液體通常是由有機(jī)陽(yáng)離子和有機(jī)或無(wú)機(jī)陰離子組成的,且離子液體的結(jié)構(gòu)可以輕易的改變。因此,改變陰陽(yáng)離子的組合可以設(shè)計(jì)合成出不同的離子液體。正是由于離子液體特殊的結(jié)構(gòu),使其具有許多獨(dú)特的理化性質(zhì),如蒸氣壓低、極性高、不易揮發(fā)、導(dǎo)電性好和可循環(huán)利用等。更重要的是,這些獨(dú)特的理化性質(zhì)使離子液體被認(rèn)為是一種“綠色溶劑”,并逐漸成為傳統(tǒng)溶劑的替代品,在許多領(lǐng)域都表現(xiàn)出非常廣闊的應(yīng)用前景,如電化學(xué)、有機(jī)合成、催化、生物傳感器和分離過(guò)程等。近幾年來(lái),關(guān)于離子液體的研究已經(jīng)成為最熱門(mén)的領(lǐng)域之一,有大量離子液體被合成并被商業(yè)化應(yīng)用。然而,當(dāng)離子液體被用作工業(yè)溶劑或催化劑,他們將不可避免的流失到環(huán)境中去。盡管離子液體被認(rèn)為是“綠色”的,但是他們一些獨(dú)特的性質(zhì),如不易被光解和良好的水溶性,會(huì)提高它們對(duì)環(huán)境的風(fēng)險(xiǎn)。更重要的是離子液體不易被微生物降解。因此,離子液體一旦經(jīng)過(guò)泄露或廢水等途徑流失到環(huán)境中去,就可能成為一種潛在的土壤和水體污染物。更重要的是離子液體可能會(huì)對(duì)人體產(chǎn)生危害,它們的毒性甚至比傳統(tǒng)溶劑更高。因此,我們必須考慮這種新興化合物對(duì)人類(lèi)和環(huán)境的潛在危害。近幾年來(lái),離子液體的毒性也成為了研究的熱點(diǎn),有大量關(guān)于離子液體對(duì)水生和陸生環(huán)境影響的研究被報(bào)道,并且離子液體對(duì)不同營(yíng)養(yǎng)級(jí)不同生物的毒性效應(yīng)在個(gè)體、細(xì)胞和分子水平被全面評(píng)估。然而值得注意的是,先前關(guān)于離子液體對(duì)植物的毒性研究,主要采取水培染毒的方式。在自然界中,植物大多種植在土壤中,而土壤代表了一個(gè)更復(fù)雜的環(huán)境,因此研究離子液體在土壤中對(duì)植物,特別是對(duì)作物的毒性更具有現(xiàn)實(shí)意義。雖然目前也有一些關(guān)于離子液體在土壤中對(duì)植物的毒性研究,但主要研究的是離子液體對(duì)植物生長(zhǎng)的抑制作用。然而,植物的生理生化特性可能對(duì)離子液體造成的毒性更加敏感,有些情況下污染物可能沒(méi)有對(duì)植物的生長(zhǎng)造成顯著的抑制作用,但已經(jīng)導(dǎo)致植物體內(nèi)理化性質(zhì)發(fā)生改變。如果能從細(xì)胞和分子水平更深入的研究離子液體在土壤中對(duì)植物的影響將能更好的評(píng)估離子液體的毒性。然而目前還沒(méi)有從生長(zhǎng)和生理水平全面評(píng)估離子液體在土壤中對(duì)植物毒性的報(bào)道。此外,值得注意的是組成離子液體的陰陽(yáng)離子的結(jié)構(gòu)不同,離子液體的毒性大小也不一樣,探討離子液體結(jié)構(gòu)對(duì)其毒性大小的影響對(duì)設(shè)計(jì)合成一種無(wú)毒或低毒的離子液體具有重要意義。蠶豆是中國(guó)及全世界重要的農(nóng)作物之一,具有很高的經(jīng)濟(jì)價(jià)值。此外,蠶豆被認(rèn)為是一種良好的環(huán)境指示生物和毒理學(xué)實(shí)驗(yàn)的模式生物,被廣泛用來(lái)檢測(cè)化合物的毒性。本論文研究了兩組陰離子不同的咪唑類(lèi)離子液體和一組碳鏈長(zhǎng)度不同的咪唑類(lèi)離子液體在土壤中對(duì)蠶豆幼苗生長(zhǎng)指標(biāo)和生理指標(biāo)的影響,從個(gè)體、細(xì)胞和分子水平全面評(píng)估了離子液體的毒性。并采用高效液相色譜法測(cè)定了咪唑類(lèi)離子液體在土壤中的殘留動(dòng)態(tài)。通過(guò)對(duì)比這幾種咪唑類(lèi)離子液體對(duì)蠶豆幼苗生長(zhǎng)指標(biāo)的ec50值判斷其毒性大小。本論文旨在研究離子液體在土壤中對(duì)植物的生態(tài)毒性并探討結(jié)構(gòu)對(duì)其毒性大小的影響。本研究為全面評(píng)估離子液體毒性提供了理論依據(jù),為設(shè)計(jì)合成無(wú)毒或低毒離子液體提供了理論指導(dǎo),具有一定的意義。本論文的主要研究結(jié)果如下:(1)在本研究中,[c8mim]cl、[c8mim]br和[c8mim]bf4在土壤中的標(biāo)準(zhǔn)添加回收率分別為80.1%-85.2%、78.4%-84.4%和81.4%-86.3%。[c10mim]cl、[c10mim]br和[c10mim]no3在土壤中的標(biāo)準(zhǔn)添加回收率分別為71.0%-81.1%、72.4%-80.3%和70.2%-79.4%。[c4mim]cl、[c6mim]cl和[c12mim]cl在土壤中的標(biāo)準(zhǔn)添加回收率分別為85.5%-89.1%、80.3-85.4%和69.7%-79.0%。此外,在暴露后第10d,各處理組離子液體濃度與第0d相比出現(xiàn)降低趨勢(shì),但變化率不超過(guò)10%。(2)在100mg/kg濃度時(shí),[c8mim]cl、[c8mim]br和[c8mim]bf4對(duì)蠶豆幼苗的生長(zhǎng)沒(méi)有顯著影響。在25mg/kg濃度時(shí),[c10mim]cl、[c10mim]br和[c10mim]no3對(duì)蠶豆幼苗的生長(zhǎng)沒(méi)有顯著影響。在1000mg/kg、500mg/kg和10mg/kg濃度時(shí),[c4mim]cl、[c6mim]cl和[c12mim]cl對(duì)蠶豆幼苗的生長(zhǎng)也沒(méi)有顯著影響。然而,在800mg/kg處理組,[c8mim]cl、[c8mim]br和[c8mim]bf4處理組蠶豆幼苗幾乎停止生長(zhǎng)。在400mg/kg處理組,[c10mim]cl、[c10mim]br和[c10mim]no3處理組蠶豆幼苗幾乎停止生長(zhǎng)。[c4mim]cl、[c6mim]cl和[c12mim]cl導(dǎo)致蠶豆幼苗幾乎停止生長(zhǎng)的濃度分別是8000mg/kg、3000mg/kg和400mg/kg。(3)在200mg/kg濃度時(shí),[c8mim]cl、[c8mim]br和[c8mim]bf4導(dǎo)致蠶豆幼苗葉片中色素含量顯著降低。在50mg/kg濃度時(shí),[c10mim]cl、[c10mim]br和[c10mim]no3導(dǎo)致蠶豆幼苗葉片中色素含量顯著降低。[c4mim]cl和[c6mim]cl導(dǎo)致蠶豆幼苗葉片中色素含量顯著降低的濃度分別是2500mg/kg和1000mg/kg。此外,在40mg/kg濃度時(shí),[c12mim]cl導(dǎo)致蠶豆幼苗葉片中希爾反應(yīng)活性顯著降低。(4)在1500mg/kg和20mg/kg濃度時(shí),[C_4mim]Cl和[C_(12)mim]Cl分別導(dǎo)致蠶豆幼苗體內(nèi)脯氨酸含量顯著升高。且這兩種離子液體濃度越高,蠶豆幼苗體內(nèi)脯氨酸含量升高的越顯著,這是蠶豆幼苗抗逆境的表現(xiàn)。(5)在本研究中,經(jīng)這9種離子液體暴露后,蠶豆幼苗體內(nèi)活性氧含量均出現(xiàn)不同程度的升高。多余的活性氧破壞了蠶豆幼苗細(xì)胞的結(jié)構(gòu)和功能,最終導(dǎo)致脂質(zhì)過(guò)氧化、蛋白質(zhì)羰基化和DNA損傷。此外,抗氧化酶活性、基因表達(dá)量以及抗氧化物含量發(fā)生顯著變化。更重要的是,氧化損傷可能是離子液體產(chǎn)生毒性的主要機(jī)制之一。(6)彗星實(shí)驗(yàn)是本實(shí)驗(yàn)中最敏感的指標(biāo)。采用組織染色法能更直觀的反應(yīng)出植物葉片中活性氧含量的變化情況。此外,從分子層面研究離子液體對(duì)植物的毒性將能更好的闡述離子液體的毒性作用機(jī)理。(7)當(dāng)碳鏈長(zhǎng)度相同,陰離子不同時(shí),各離子液體對(duì)蠶豆幼苗的毒性作用相似,即陰離子對(duì)離子液體毒性影響較小。當(dāng)陰離子相同,碳鏈長(zhǎng)度不同時(shí),離子液體對(duì)蠶豆幼苗的毒性作用隨著碳鏈長(zhǎng)度的增加而顯著升高,即碳鏈長(zhǎng)度對(duì)離子液體毒性影響較大。在本研究中,[C_4mim]Cl對(duì)蠶豆幼苗的毒性作用最小,[C_(12)mim]Cl對(duì)蠶豆幼苗的毒性作用最大。(8)高濃度的離子液體可能會(huì)對(duì)農(nóng)業(yè)生產(chǎn)造成危害,應(yīng)該減小離子液體的使用濃度。此外,應(yīng)該從改變陰離子入手,設(shè)計(jì)一種碳鏈短、功能多、低毒害的新型離子液體。
[Abstract]:An ionic liquid is a salt that is made up of all ions and is liquid at room temperature or low temperature, also known as a room temperature ionic liquid or a room temperature molten salt. Ionic liquids are usually composed of organic cations and organic or inorganic anions, and the structure of ionic liquids can be easily changed. Therefore, the change of the combination of the ions and ions can be designed to produce different ionic liquids. Because of the special structure of ionic liquid, it has many unique physical and chemical properties, such as low vapor pressure, high polarity, no volatilization, good conductivity and recyclable use. More importantly, these unique physicochemical properties of the ionic liquid is considered to be a kind of "green solvents", and gradually become the substitute of conventional solvent, in many areas have shown a very broad application prospects, such as electrochemistry, organic synthesis, catalysis, biosensor and separation process. In recent years, the research on ionic liquids has become one of the most popular fields, and a large number of ionic liquids have been synthesized and commercially applied. However, when ionic liquids are used as industrial solvents or catalysts, they will inevitably be lost to the environment. Though ionic liquids are considered to be "green", their unique properties, such as not being easily photodecomposition and good water solubility, will increase their environmental risk. More importantly, ionic liquids are not easily degraded by microbes. Therefore, once the ionic liquid is leaked or waste water and other ways to the environment, it may become a potential contaminant in the soil and water. More importantly, ionic liquids may be harmful to the human body, and their toxicity is even higher than that of traditional solvents. Therefore, we must consider the potential hazards of this new compound to the human and the environment. In recent years, the toxicity of ionic liquid has become a hot research topic, there are a large number of ionic liquids environment effects on aquatic and terrestrial research was reported, and the ionic liquid to the toxic effects of different nutritional level of different organisms in individual, cellular and molecular levels by comprehensive assessment. However, it is worth noting that the previous studies on the toxicity of ionic liquids to plants were mainly used in the way of hydroponics. In nature, plants are mostly planted in soil, and soil represents a more complex environment. Therefore, it is more practical to study the toxicity of ionic liquids to plants, especially crops. Although there are some studies on the toxicity of ionic liquids to plants in soil, the main research is the inhibitory effect of ionic liquids on plant growth. However, the physiological and biochemical characteristics of plants may be more sensitive to the toxicity caused by ionic liquids. In some cases, pollutants may not significantly inhibit the growth of plants, but have resulted in changes in physical and chemical properties of plants. The toxicity of ionic liquids can be better evaluated if the effects of ionic liquids in soil on plants can be studied more deeply from the cellular and molecular levels. However, there has not been a comprehensive assessment of the toxicity of ionic liquids in soil from the growth and physiological levels. In addition, it is noteworthy that the structure of ionic liquids that are composed of ionic liquids is different from that of ionic liquids, and the toxicity of ionic liquids is also different. It is of great importance to explore the effect of ionic liquid structure on the toxicity of ionic liquids to design and synthesize a non-toxic or low toxic ionic liquid. Vicia faba is one of the most important crops in China and all over the world, and has a high economic value. In addition, Vicia faba is considered to be a good model organism for biological and toxicological experiments, and is widely used to detect the toxicity of compounds. This paper studied the effect of imidazole ionic liquid ionic liquid two groups of different anions and a group of different length of carbon chain growth and physiological indexes of Vicia faba seedlings in soil, from the individual, the cellular and molecular level comprehensive assessment of the toxicity of ionic liquids. The residual dynamics of imidazole ionic liquids in soil were determined by high performance liquid chromatography. The toxicity of these imidazole ionic liquids on the EC50 value of the growth index of Vicia faba seedlings was compared. The purpose of this paper is to study the ecotoxicity of ionic liquids to plants in soil and to explore the effects of structure on their toxicity. This study provides a theoretical basis for the comprehensive assessment of the toxicity of ionic liquids, and provides a theoretical guidance for the design of non-toxic or low toxic ionic liquids. The main results of this paper are as follows: (1) in this study, the standard addition recovery rates of [c8mim]cl, [c8mim]br and [c8mim]bf4 in soil were 80.1%-85.2%, 78.4%-84.4% and 81.4%-86.3% respectively. The standard addition recovery rates of [c10mim]cl, [c10mim]br and [c10mim]no3 in soil were 71.0%-81.1%, 72.4%-80.3% and 70.2%-79.4% respectively. The standard addition recovery rates of [c4mim]cl, [c6mim]cl and [c12mim]cl in soil were 85.5%-89.1%, 80.3-85.4% and 69.7%-79.0% respectively. In addition, after exposure to 10d, the concentration of ionic liquids in each treatment group decreased compared with that of 0d, but the rate of change was not more than 10%. (2) at the concentration of 100mg/kg, [c8mim]cl, [c8mim]br and [c8mim]bf4 had no significant effect on the growth of Vicia faba seedlings. At the concentration of 25mg/kg, [c10mim]cl, [c10mim]br and [c10mim]no3 had no significant effect on the growth of Vicia faba seedlings. At the concentration of 1000mg/kg, 500mg/kg and 10mg/kg, [c4mim]cl, [c6mim]cl and [c12mim]cl had no significant effect on the growth of Vicia faba seedlings. However, in the 800mg/kg treatment group, the growth of Vicia faba seedlings in [c8mim]cl, [c8mim]br and [c8mim]bf4 treatment groups was almost stopped. In the 400mg/kg treatment group, the growth of broad bean seedlings was almost stopped in the [c10mim]cl, [c10mim]br and [c10mim]no3 treatment groups. [c4mim]cl, [c6mim]cl and [c12mim]cl resulted in the concentration of almost ceased growth of Vicia faba seedlings
【學(xué)位授予單位】：山東農(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)】：X171.5
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本文編號(hào)：1339314