本文關(guān)鍵詞： 苯氧羧酸類農(nóng)藥 酰胺 高嶺石團(tuán)簇模型 同晶置換高嶺石 氫鍵　出處：《山東農(nóng)業(yè)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：本文分別構(gòu)建了針對(duì)苯氧羧酸類農(nóng)藥分子與高嶺石相互作用的鋁氧八面體層表面模型Al_(13)O_(48)H_(57)(K(o))和硅氧四面體層表面模型Si_(13)O_(37)H_(22)(K(t)),以及針對(duì)酰胺分子與同晶置換后的高嶺石相互作用的團(tuán)簇模型,分別表示為鋁氧八面體層表面模型((Al_5CaO_(24)H_(30))-)(K(os)),硅氧四面體層表面模型((Si_5AlO_(18)H_(12))-)(K(ts))和層間結(jié)構(gòu)團(tuán)簇模型((Al_6Si_5CaO_(42)H_(42))2-)(Ks)。采用B3LYP(Becke,three-parameter,Lee-Yang-Parr exchange-correlation functional)計(jì)算方法,以及6-31G(d,p)和6-31G(d)基組,對(duì)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)六種苯氧羧酸類農(nóng)藥分子和甲酰胺(FA)、乙酰胺(AA)、順-N-甲基甲酰胺(cis-NMFA)、反-N-甲基甲酰胺(trans-NMFA)、順-N-甲基乙酰胺(cis-NMA)、反-N-甲基乙酰胺(trans-NMA)六種酰胺分子(下文中將用簡(jiǎn)稱代表每種要研究的分子)分別與高嶺石相互作用后的性質(zhì)進(jìn)行了研究,包括優(yōu)化的幾何構(gòu)型、結(jié)構(gòu)參數(shù)、相互作用能、NBO電荷等。苯氧羧酸類農(nóng)藥分子與高嶺石團(tuán)簇模型相互作用的研究表明,與含有乙酸基側(cè)鏈的農(nóng)藥分子相比,由于丙酸基側(cè)鏈和丁酸基側(cè)鏈具有更多的吸附位點(diǎn)使相應(yīng)的農(nóng)藥分子吸附能力較強(qiáng)。綜合各分子在兩個(gè)表面的吸附情況,發(fā)現(xiàn)MCPP的吸附能力優(yōu)于MCPA。與實(shí)驗(yàn)所得MCPA的吸附性低于2,4-D的結(jié)論相結(jié)合,可以推斷出2,4-D與MCPA更易于同高嶺石的硅氧四面體層表面吸附。因此,在選擇農(nóng)藥時(shí),應(yīng)將各農(nóng)藥分子的活性以及農(nóng)藥分子與高嶺石的相互作用強(qiáng)弱考慮在內(nèi),確保淋洗對(duì)去除農(nóng)藥在土壤中殘留的可行性。研究酰胺分子與同晶置換后的高嶺石團(tuán)簇模型的相互作用,容易發(fā)現(xiàn)同晶置換后的高嶺石的硅氧層的吸附能力明顯增強(qiáng),而同晶置換鋁氧層的吸附能力卻減弱,復(fù)合物的穩(wěn)定性順序?yàn)镵s/amidesK(ts)/amidesK(os)/amides�？傮w來(lái)說(shuō),酰胺與同晶置換高嶺石形成的復(fù)合物比與中性的高嶺石相互作用形成的復(fù)合物更穩(wěn)定。同時(shí)可以得到以下推論,通過(guò)控制高嶺石中離子的取代或許能夠控制客體分子在高嶺石中的吸附與脫附。
[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.
【學(xué)位授予單位】：山東農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ450.1

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