| As one of the branches of nonlinear science, chemical oscillation has promoted the development of nonlinear science, which makes the concentration and colour of some substances in the reaction system periodically change. The research of oscillation has been a long time and in recently years, tetraazamacrocyclic nickel or copper complexes-catalyzed chemical oscillation has got more and more attention. In this paper, a novel Briggs-Rauscher chemical oscillation was introduced, which was catalyzed by macrocyclic niekel(Ⅱ) complex [NiL](CIO4)2. L is 5,7,7,12,14, 14-hexemethy-1,4,8,11-tetraazacyclotetradeca-4,11-diene.This thesis is divided into four chapters. In the first chapter, the meaning, development history, research situation and research respect of the nonlinear chemistry was introduced in detail, and Briggs-Rauscher Oscillator was explained as well.The second chapter can be divided into two parts. The synthesis and characterization of catalyst [NiL](ClO4)2 was introduced in the first part. In the second part:Under the condition of ice bath, a new system was designed like this:malonic acid-sulfuric acid- [NiL](ClO4)2-potassium iodate-hydrogen peroxide. And such oscillation system was used to detect the butylated hydroxyanisole (BHA). The relationship between inhibition time and the concentration of BHA was found and two calibration curves are obtained:the first linear regression is over the range 1.00×10-7-2.00×10-6 mol/L, the second linear regression is over the range 2.00×10-6-1.20×10-4 mol/L. By controlling variable method, the effects of changing reactants concentration to the inhibition were studied. At last the mechanism of free radical was used to explain the disturbance.The perturbation effects of L-tyrosine on a Briggs-Rauscher (B-R) chemical oscillating reaction were discussed in present work. The oscillating system responded to the addition of L-tyrosine with the changes in the period of oscillation (tp) and time of oscillation (te). Experimentally, it was found that the change of period of oscillation (Δt) is proportional to the concentration of L-tyrosine over a range of 6.25×10-6-2.5×10-4 mol/L and the system was markedly promoted by L-tyrosine (te≈ 4000s) at the concentration range of 3.3×10-5 mol/L≤CL-tyrosine≤8.333×10-5 mol/L. The reaction mechanism of L-tyrosine on B-R system was explored with the help of cyclic voltammetry. And we found that the interference mechanism is that L-tyrosine reacted with potassium iodate in the system, this is completely different from the previously reported effects of antioxidants. Due to the similarity of [NiL](ClO4)2 to some enzymes in structure and the important functions that L-tyrosine plays in the metabolism in the body of human being and animals, study the effects of L-tyrosine on a B-R oscillating reaction are remarkable significance.The fourth chapter introduced a new Briggs-Rauscher oscillating system, which used Meldrum’s acid as indirect organic substrate. Through the experiments we found that the storage time of Meldrum’s acid has a great influence on the oscillation reaction, and oscillation period is proportional to the placed time of Meldrum’s acid over the range 4-10 days. In fact Meldrum’s acid can function as indirect organic substrate was due to the decomposition of Meldrum’s acid in aqueous solution, it decomposed into malonic acid and such fact has been proved by LC-MS. By UV, we found the decomposition of Meldrum’s acid is conform to first order kinetics in the range 1-5 days. |
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