苯氧羧酸类农药分子、酰胺分子与高岭石团簇模型相互作用的理论研究

发布时间：2018-01-23 23:36

本文关键词： 苯氧羧酸类农药酰胺高岭石团簇模型同晶置换高岭石氢键　出处：《山东农业大学》2017年硕士论文　论文类型：学位论文

【摘要】：本文分别构建了针对苯氧羧酸类农药分子与高岭石相互作用的铝氧八面体层表面模型Al_(13)O_(48)H_(57)(K(o))和硅氧四面体层表面模型Si_(13)O_(37)H_(22)(K(t)),以及针对酰胺分子与同晶置换后的高岭石相互作用的团簇模型,分别表示为铝氧八面体层表面模型((Al_5CaO_(24)H_(30))-)(K(os)),硅氧四面体层表面模型((Si_5AlO_(18)H_(12))-)(K(ts))和层间结构团簇模型((Al_6Si_5CaO_(42)H_(42))2-)(Ks)。采用B3LYP(Becke,three-parameter,Lee-Yang-Parr exchange-correlation functional)计算方法,以及6-31G(d,p)和6-31G(d)基组,对2,4-二氯苯氧乙酸(2,4-D)、2,4-二氯苯氧丙酸(2,4-DP)、2,4-二氯苯氧丁酸(2,4-DB)、2-甲基-4-氯苯氧乙酸(MCPA)、2-甲基-4-氯苯氧丙酸(MCPP)和2-甲基-4-氯苯氧丁酸(MCPB)六种苯氧羧酸类农药分子和甲酰胺(FA)、乙酰胺(AA)、顺-N-甲基甲酰胺(cis-NMFA)、反-N-甲基甲酰胺(trans-NMFA)、顺-N-甲基乙酰胺(cis-NMA)、反-N-甲基乙酰胺(trans-NMA)六种酰胺分子(下文中将用简称代表每种要研究的分子)分别与高岭石相互作用后的性质进行了研究,包括优化的几何构型、结构参数、相互作用能、NBO电荷等。苯氧羧酸类农药分子与高岭石团簇模型相互作用的研究表明,与含有乙酸基侧链的农药分子相比,由于丙酸基侧链和丁酸基侧链具有更多的吸附位点使相应的农药分子吸附能力较强。综合各分子在两个表面的吸附情况,发现MCPP的吸附能力优于MCPA。与实验所得MCPA的吸附性低于2,4-D的结论相结合,可以推断出2,4-D与MCPA更易于同高岭石的硅氧四面体层表面吸附。因此,在选择农药时,应将各农药分子的活性以及农药分子与高岭石的相互作用强弱考虑在内,确保淋洗对去除农药在土壤中残留的可行性。研究酰胺分子与同晶置换后的高岭石团簇模型的相互作用,容易发现同晶置换后的高岭石的硅氧层的吸附能力明显增强,而同晶置换铝氧层的吸附能力却减弱,复合物的稳定性顺序为Ks/amidesK(ts)/amidesK(os)/amides。总体来说,酰胺与同晶置换高岭石形成的复合物比与中性的高岭石相互作用形成的复合物更稳定。同时可以得到以下推论,通过控制高岭石中离子的取代或许能够控制客体分子在高岭石中的吸附与脱附。
[Abstract]:In this paper, the aluminooctahedral layer surface model for the interaction of phenoxy carboxylic acid pesticides with kaolinite has been constructed. And SiACTER-MORPHALE surface model of SiACTER-OSTH 37HZ / KT / T / T / T / S / T / T / T / T / T / T / T / T / T. The cluster model of the interaction between amide molecule and homocrystalline kaolinite is also presented. It is represented as Al5CaO / Al5CaO\\\. Si5AlOS / Si5AlOS / Si5AlOS / Si5AlO / Si5AlOS / Si5AlOS / Si5AlOS-1 / Si5AlOS-1 / Si5AlOS-1 / Si5AlOS-1 / Si5AlOS-1 / Si5AlOS-1) and the interlayer structure cluster model of Si5AlOSP (. B _ 3LYP _ (P) Becke was used. The three-parameter Lee-Yang-Parr exchange-correlation functional method. And 6-31G ~ (1) D ~ (+) and 6-31G ~ (1) D _ (2) -base group, for 2o _ (4-) -dichlorophenoxyacetic acid (2o ~ (4-) DX _ (2)) ~ (2) -dichlorophenoxy propionate (~ (2)) ~ (24) DPN _ (2). 2-methyl-4-chlorophenoxybutyrate 2-methyl-4-chlorophenoxyacetic acid (MCPA). Two methyl-4-chlorophenoxy propionic acid (MCPP) and 2-methyl-4-chlorophenoxy butyrate (2-methyl-4-chlorophenoxy butyrate), six phenoxy carboxylic acid pesticides and formamide, acetamide (AAA). Cis-N-methylformamide cis-NMFAA, trans-N-methylformamide trans-NMFAA, cis-N-methylacetamide cis-NMA. The properties of the interaction of six amide molecules (referred to as each molecule to be studied below) with kaolinite have been studied. It includes optimized geometric configuration, structural parameters, interaction energy and NBO charge. The study of interaction between phenoxy carboxylic acid pesticides and kaolinite cluster model shows that the interaction between phenoxy carboxylic acid pesticides and kaolinite cluster model. Compared with the pesticide molecules containing acetic acid side chain, the adsorption ability of the corresponding pesticide molecules is stronger because of the more adsorption sites of propionic acid side chain and butyric acid side chain. It is found that the adsorption ability of MCPP is better than that of MCPA. combined with the conclusion that the adsorption of MCPA is lower than 24-D, we can infer that 2. 4-D and MCPA are more easily adsorbed on the surface of silica tetrahedron layer of kaolinite. Therefore, the activity of each pesticide molecule and the interaction between pesticide molecule and kaolinite should be taken into account in the selection of pesticides. To ensure the feasibility of elution to remove pesticide residues in soil. The interaction between amide molecule and homocrystalline kaolinite cluster model was studied. It is easy to find that the adsorption ability of kaolinite layer after homocrystalline replacement is obviously enhanced, but the adsorption ability of homocrystalline replacement layer of Al _ 2O _ 2 is weakened. The stability of the complex is in the order of Ks / amides / amides / amides / amides. generally speaking. The complex formed by amide and isomorphic replacement kaolinite is more stable than that formed by interaction with neutral kaolinite. The adsorption and desorption of guest molecules in kaolinite may be controlled by controlling the substitution of ions in kaolinite.
【学位授予单位】：山东农业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ450.1

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