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Theoretical Study on the Reaction of Dimethylpentadienyl Aldehyde with NO Radicals and Iodo Salicylaldehyde Ethylenediamine Schiff Base Complexes

Author: LiYanPing
Tutor: JiYongQiang
School: Ningxia University
Course: Physical and chemical
Keywords: B3LYP 2,3-dimethyl-pentanal Schiff base complexes theoretical research
CLC: O643
Type: Master's thesis
Year: 2013
Downloads: 27
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Abstract


The contents of this thesis consists of two parts:The theoretical research of2,3-dimethyl-pentyl aldehyde group triggered by the O2with NO radicals; Synthesis, the theoretical research of3,5-two iodine inhibiting aldehycle shrink ethylenedia mine schiff complexes and experimental study on its role with ct-DNA.1. The theoretical research of2,3-dimethyl-pentyl aldehyde group triggered by the O2with NO radicalsWe have studied the reaction mechanism of the3-dimethylpentadienyl aldehyde triggered by the O2with NO radicals in the atmosphere for the first time at B3LYP/6-31G*level, according to the experimental results of Atkinson, R. et al. Geometries of stationary points of each reaction were completely optimized. And all the transition states and connectivity were verified by the frequency calculation and intrinsic reaction coordinate analysis at the same level. In addition, we have identified the main reaction channel and given the other reaction channels. The calculation results showed that:(1) We have found the path and transition state of the reaction, and the stationary points were optimized and vibration analysis, especially the isomerization, oxidation and decomposition of CH3CH2CH(CH3) CH(O-)CH3. There were six isomerization reaction channels, and by comparing the size of the reaction barrier, we concluded that reaction generated CH3CH2CH(CH3)C·(OH)CH3via transition state aTS5owning the highest barrier, which was228.9kJ/mol, while reaction generated CH-2CH2CH(CH3)CH (OH)CH3via transition state aTS1owning the lowest barrier, which was228.9kJ/mol. So the isomerization reaction of CH3CH2CH(CH3)CH(O-)CH generated CH-2CH2CH(CH3)CH (OH)CH3via the transition state aTSl was more likely to occur.(2) CH3CH2CH(CH3)CH(O)CH3had two oxidation channel, the reaction barrier was154.22kJ/mol by transition state bTS·, and the reaction barrier was184.5kJ/mol via transition state bTS2. Thus CH3CH2CH(CH3)CH(O)CH3oxidation generated H3CH2CH(CH3)C(O)CH3and HO2via transition state bTS1was the dominant reaction channel.(3) We have found one reaction channel that decomposition reaction of CH3CH2CH(CH3)CH(O-)CH3generated CH3CH2C·HCH3and CH3CHO through transition state cTS1.(4) And compared the size of dominant reaction barrier in isomerization, oxidation and decomposition reaction of CH3CH2CH(CH3)CH(O-)CH3, it was showed that the decomposition reaction had the lowest barrier (104.5kJ/mol), the decomposition reaction was more likely to occur and the main reaction product was acetaldehyde, which was consistent with Atkinson, R. et al experimental results. Times products were CH3CH2CH (CH3)C(O)CH3, HO2, CH3CH2C·HCH3and CH·2CH2CH(CH3)CH(OH)CH3, and which continued to work with O2and NO free radicals on cyclic degradation reaction.2. The theoretical research of3,5-two iodine inhibiting aldehycle shrink ethylenedia mine schiff complexesTwo kinds of3,5-two iodine salicylaldehyde shrinkage ethylene diamine schiff base transition metal compounds were synthesized. They were characterized by elemental analysis, infrared spectrum and molar conductance value analysis, the composition of the complexes was proved to be M2L2(M=Co (II) and Ni(II)). The geometric configuration, charge distribution, the frontier molecular orbital and stability of complexes were studied through the B3LYP method based on Density Functional Theory (DFT), which were performed by Gaussian09quantum chemistry package. They are characterized by elemental analysis, molar conductivity and infrared absorption spectrometry. And we have analyzed and compared the strength of the reactivity of cobalt, nickel complexes from theoretical calculations point. The interaction between complexes and ct-DNA was investigated through UV-Vis Spectroscopy, Fluorescence emission spectrometry and Viscosity. Both theoretical analysis and experimental results indicated that the reactivity of Co (Ⅱ) complexes were stronger than Ni (Ⅱ) complexes, thus the experimental research coincided with the theoretical calculation results. Theoretical calculations also showed that:N, O atoms in the ligand was the main active portion, thus easy coordinated with metal ions. And metal ions, N, O atoms were also active sites, thereby occurred some reactions easily.

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