A Study of the Solvent Cage Effect involved in the Oxygen Quenching of Fluorescence and the Quenching of Singlet Oxygen.

1.氧对荧光的猝灭：研究了正构烷烃（C2-C7）中氧对9，10-二甲基蒽（DMEA）的荧光猝灭。通过对猝灭速率常数kg、溶剂笼中的双分子速率kbimo和扩散速率常数kdiff随压力和温度的变化关系的分析，得到了猝灭速率常数kg、溶剂笼中的双分子速率kbimo和扩散速率常数kdiff，并对猝灭机理进行了讨论.高温气相氧荧光猝灭和高温高压氧荧光猝灭：研究了高温气相氧对DMEA的荧光猝灭。利用自行研制的高压池，研究了DMEA在高温高压下的氧荧光猝灭。从这些结果出发，对溶剂笼效应进行了讨论.三重态的氧猝灭：（1）研究了9-乙酰基蒽（^3ππ^*）在超临界乙烷和二氧化碳中三重态的氧猝灭。 ...更多信息 门控从猝灭速率常数kq ^T与压力和温度的关系出发，讨论了猝灭机理，包括扩散对猝灭的贡献和溶剂笼效应对猝灭的影响。(2)研究了二苯甲酮（^3nπ^*）在超临界二氧化碳中三重态氧猝灭随温度和压力的变化。从kq ^T的激活能和激活体积以及单线态氧的量子产率等方面，对猝灭机理进行了探讨.温度和压力对超临界流体中单线态氧寿命（^1 Δg）的影响：测量了液态和超临界丙烷中单线态氧寿命随温度和压力的变化，并从溶剂分子对单线态氧双分子猝灭速率常数kD和单线态氧与溶剂分子接触时的径向分布函数g（σ）的活化参数讨论了猝灭机理。少

1. Oxygen quenching of fluorescence :Fluorescence quenching of 9, 10-dimethylanthracene (DMEA) by oxygen in n-alkanes (C2-C7) was investigated. From the analysis of the pressure and temperature dependence of the quenching rate constant, kg, the bimolecular rate, kbimo, in the solvent cage and the diffusion rate constant, kdiff, were evaluated and the quenching mechanism was discussed.2. Oxygen quenching of fluorescence at high temperature in gas phase and at high temperature and high pressure :Fluorescence quenching of DMEA by oxygen in high temperature in gas phase was investigated. By using a high pressure cell, which was newly constructed for this work, oxygen quenching of fluorescence of DMEA at high temperature and high pressure was also investigated. From these results, the solvent cage effect was discussed.3. Oxygen quenching of the triplet states :(1) The oxygen quenching of the triplet states of 9-acetylanthracene (^3ππ^*) in supercritical ethane and carbon dioxide was investi … More gated. From the pressure and temperature dependence of the quenching rate constant, k_q^T, the quenching mechanism was discussed including the contribution of diffusion to the quenching and the solvent cage effect involved in the quenching. (2) The oxygen quenching of the triplet state of benzophenone (^3nπ^*) in supercritical carbon dioxide as functions temperature and pressure was investigated. From the activation energy and the activation volume for k_q^T, and the quantum yield of singlet oxygen formation, the quenching mechanism was discussed.4. Temperature and pressure effects on the lifetime of singlet oxygen (^1Δg) in supercritical fluids :Lifetime of singlet oxygen was measured as functions of temperature and pressure in liquid and supercritical propane, and the quenching mechanism was discussed from the activation parameters for the bimolecular quenching rate constant, kD, by the solvent molecule, and the radial distribution function, g(σ), at contact, σ, between the singlet oxygen and solvent molecules. Less