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Singlet oxygen reactivity in water-rich solvent mixtures

机译:富水溶剂混合物中的单重态氧反应性

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摘要

The 3-methylindole (3MI) oxygenation sensitized by psoralen (PSO) has been investigated in 100%, 20% and 5% O2-saturated water/dioxane (H2O/Dx) mixtures. The lowering of the 1O2* chemical rate when water (kchem∆3MI = 1.4 × 109 M-1 s-1) is replaced by deuterated water (kchem∆3MI = 1.9 × 108 M-1 s-1) suggests that hydrogen abstraction is involved in the rate determining step. A high dependence of the chemical rate constant on water concentration in H2O/Dx mixtures was found showing that water molecules are absolutely essential for the success of the 3MI substrate oxidation by 1O2* in water-rich solvent mixtures.
机译:在100%,20%和5%O2饱和的水/二恶烷(H2O / Dx)混合物中,对补骨脂素(PSO)致敏的3-甲基吲哚(3MI)氧化进行了研究。当用氘水(kchem∆3MI = 1.9×108 M-1 s-1)代替水(kchem∆3MI = 1.4×109 M-1 s-1)时1O2 *化学速率的降低表明参与速率确定步骤。发现化学速率常数对H2O / Dx混合物中水浓度的高度依赖性表明,对于富水溶剂混合物中3O底物成功被1O2 *氧化成功3MI而言,水分子是绝对必要的。

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