不同结构咪唑类离子液体在土壤中对蚕豆幼苗的生态毒性及结构对其毒性的影响

发布时间：2017-12-26 23:25

  本文关键词：不同结构咪唑类离子液体在土壤中对蚕豆幼苗的生态毒性及结构对其毒性的影响　出处：《山东农业大学》2016年博士论文　论文类型：学位论文

  更多相关文章： 高效液相色谱 活性氧 氧化应激 基因表达 阴离子 碳链长度

【摘要】：离子液体是指全部由离子组成的,在室温或低温下为液态的盐,又称为室温离子液体或室温熔融盐。离子液体通常是由有机阳离子和有机或无机阴离子组成的,且离子液体的结构可以轻易的改变。因此,改变阴阳离子的组合可以设计合成出不同的离子液体。正是由于离子液体特殊的结构,使其具有许多独特的理化性质,如蒸气压低、极性高、不易挥发、导电性好和可循环利用等。更重要的是,这些独特的理化性质使离子液体被认为是一种“绿色溶剂”,并逐渐成为传统溶剂的替代品,在许多领域都表现出非常广阔的应用前景,如电化学、有机合成、催化、生物传感器和分离过程等。近几年来,关于离子液体的研究已经成为最热门的领域之一,有大量离子液体被合成并被商业化应用。然而,当离子液体被用作工业溶剂或催化剂,他们将不可避免的流失到环境中去。尽管离子液体被认为是“绿色”的,但是他们一些独特的性质,如不易被光解和良好的水溶性,会提高它们对环境的风险。更重要的是离子液体不易被微生物降解。因此,离子液体一旦经过泄露或废水等途径流失到环境中去,就可能成为一种潜在的土壤和水体污染物。更重要的是离子液体可能会对人体产生危害,它们的毒性甚至比传统溶剂更高。因此,我们必须考虑这种新兴化合物对人类和环境的潜在危害。近几年来,离子液体的毒性也成为了研究的热点,有大量关于离子液体对水生和陆生环境影响的研究被报道,并且离子液体对不同营养级不同生物的毒性效应在个体、细胞和分子水平被全面评估。然而值得注意的是,先前关于离子液体对植物的毒性研究,主要采取水培染毒的方式。在自然界中,植物大多种植在土壤中,而土壤代表了一个更复杂的环境,因此研究离子液体在土壤中对植物,特别是对作物的毒性更具有现实意义。虽然目前也有一些关于离子液体在土壤中对植物的毒性研究,但主要研究的是离子液体对植物生长的抑制作用。然而,植物的生理生化特性可能对离子液体造成的毒性更加敏感,有些情况下污染物可能没有对植物的生长造成显著的抑制作用,但已经导致植物体内理化性质发生改变。如果能从细胞和分子水平更深入的研究离子液体在土壤中对植物的影响将能更好的评估离子液体的毒性。然而目前还没有从生长和生理水平全面评估离子液体在土壤中对植物毒性的报道。此外,值得注意的是组成离子液体的阴阳离子的结构不同,离子液体的毒性大小也不一样,探讨离子液体结构对其毒性大小的影响对设计合成一种无毒或低毒的离子液体具有重要意义。蚕豆是中国及全世界重要的农作物之一,具有很高的经济价值。此外,蚕豆被认为是一种良好的环境指示生物和毒理学实验的模式生物,被广泛用来检测化合物的毒性。本论文研究了两组阴离子不同的咪唑类离子液体和一组碳链长度不同的咪唑类离子液体在土壤中对蚕豆幼苗生长指标和生理指标的影响,从个体、细胞和分子水平全面评估了离子液体的毒性。并采用高效液相色谱法测定了咪唑类离子液体在土壤中的残留动态。通过对比这几种咪唑类离子液体对蚕豆幼苗生长指标的ec50值判断其毒性大小。本论文旨在研究离子液体在土壤中对植物的生态毒性并探讨结构对其毒性大小的影响。本研究为全面评估离子液体毒性提供了理论依据,为设计合成无毒或低毒离子液体提供了理论指导,具有一定的意义。本论文的主要研究结果如下:(1)在本研究中,[c8mim]cl、[c8mim]br和[c8mim]bf4在土壤中的标准添加回收率分别为80.1%-85.2%、78.4%-84.4%和81.4%-86.3%。[c10mim]cl、[c10mim]br和[c10mim]no3在土壤中的标准添加回收率分别为71.0%-81.1%、72.4%-80.3%和70.2%-79.4%。[c4mim]cl、[c6mim]cl和[c12mim]cl在土壤中的标准添加回收率分别为85.5%-89.1%、80.3-85.4%和69.7%-79.0%。此外,在暴露后第10d,各处理组离子液体浓度与第0d相比出现降低趋势,但变化率不超过10%。(2)在100mg/kg浓度时,[c8mim]cl、[c8mim]br和[c8mim]bf4对蚕豆幼苗的生长没有显著影响。在25mg/kg浓度时,[c10mim]cl、[c10mim]br和[c10mim]no3对蚕豆幼苗的生长没有显著影响。在1000mg/kg、500mg/kg和10mg/kg浓度时,[c4mim]cl、[c6mim]cl和[c12mim]cl对蚕豆幼苗的生长也没有显著影响。然而,在800mg/kg处理组,[c8mim]cl、[c8mim]br和[c8mim]bf4处理组蚕豆幼苗几乎停止生长。在400mg/kg处理组,[c10mim]cl、[c10mim]br和[c10mim]no3处理组蚕豆幼苗几乎停止生长。[c4mim]cl、[c6mim]cl和[c12mim]cl导致蚕豆幼苗几乎停止生长的浓度分别是8000mg/kg、3000mg/kg和400mg/kg。(3)在200mg/kg浓度时,[c8mim]cl、[c8mim]br和[c8mim]bf4导致蚕豆幼苗叶片中色素含量显著降低。在50mg/kg浓度时,[c10mim]cl、[c10mim]br和[c10mim]no3导致蚕豆幼苗叶片中色素含量显著降低。[c4mim]cl和[c6mim]cl导致蚕豆幼苗叶片中色素含量显著降低的浓度分别是2500mg/kg和1000mg/kg。此外,在40mg/kg浓度时,[c12mim]cl导致蚕豆幼苗叶片中希尔反应活性显著降低。(4)在1500mg/kg和20mg/kg浓度时,[C_4mim]Cl和[C_(12)mim]Cl分别导致蚕豆幼苗体内脯氨酸含量显著升高。且这两种离子液体浓度越高,蚕豆幼苗体内脯氨酸含量升高的越显著,这是蚕豆幼苗抗逆境的表现。(5)在本研究中,经这9种离子液体暴露后,蚕豆幼苗体内活性氧含量均出现不同程度的升高。多余的活性氧破坏了蚕豆幼苗细胞的结构和功能,最终导致脂质过氧化、蛋白质羰基化和DNA损伤。此外,抗氧化酶活性、基因表达量以及抗氧化物含量发生显著变化。更重要的是,氧化损伤可能是离子液体产生毒性的主要机制之一。(6)彗星实验是本实验中最敏感的指标。采用组织染色法能更直观的反应出植物叶片中活性氧含量的变化情况。此外,从分子层面研究离子液体对植物的毒性将能更好的阐述离子液体的毒性作用机理。(7)当碳链长度相同,阴离子不同时,各离子液体对蚕豆幼苗的毒性作用相似,即阴离子对离子液体毒性影响较小。当阴离子相同,碳链长度不同时,离子液体对蚕豆幼苗的毒性作用随着碳链长度的增加而显著升高,即碳链长度对离子液体毒性影响较大。在本研究中,[C_4mim]Cl对蚕豆幼苗的毒性作用最小,[C_(12)mim]Cl对蚕豆幼苗的毒性作用最大。(8)高浓度的离子液体可能会对农业生产造成危害,应该减小离子液体的使用浓度。此外,应该从改变阴离子入手,设计一种碳链短、功能多、低毒害的新型离子液体。
[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
【学位授予单位】：山东农业大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：X171.5
，

本文编号：1339314