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以Salen-Cu/NaOH/DMF为半乳糖氧化酶的模型,考察了苯甲醇的氧化反应。氧气氛下,笨甲醇被选择性地氧化成苯甲醛,分子氧被还原为H_2O_2。动力学研究结果表明反应对苯甲醇和Salen-Cu均为一级反应,即v=k_表[Salen-Cu][PhCH_2OH],其中k_表=6.1×10~(-3)M~(-1)·min~(-1)。用原位紫外—可见光谱在厌氧和有氧条件下研究了反应过程中d—d跃迁和荷移光谱(MLCT)的变化,结果表明反应诱导过程为Cu(Ⅱ)→Cu(Ⅰ),Cu(Ⅱ)/Cu(Ⅰ)是氧化反应中催化循环的关键,即反应通过两次单电子转移进行。根据实验结果,提出了可能的反应机理。
Taking Salen-Cu / NaOH / DMF as galactose oxidase model, the oxidation of benzyl alcohol was investigated. Oxygen atmosphere, stupid methanol is selectively oxidized to benzaldehyde, molecular oxygen is reduced to H_2O_2. Kinetic studies show that the reaction of benzyl alcohol and Salen-Cu are the first order reaction, that is v = k_ table [Salen-Cu] [PhCH_2OH], where k_ table = 6.1 × 10-3 M ~ -1) · min ~ (-1). The changes of d-d transition and charge-transfer spectra (MLCT) during the reaction were studied by in situ UV-Vis spectroscopy under anaerobic and aerobic conditions. The results showed that the reaction induction process was Cu (Ⅱ) → Cu Cu (Ⅱ) / Cu (Ⅰ) is the key to the catalytic cycle in the oxidation reaction, that is, the reaction is carried out by two single-electron transfer reactions. According to the experimental results, the possible reaction mechanism is proposed.