PHOTOPHYSICS AND PHOTOCHEMISTRY OF OXYGEN SENSORS BASED ON LUMINESCENT TRANSITION-METAL COMPLEXES
PHOTOPHYSICS AND PHOTOCHEMISTRY OF OXYGEN SENSORS BASED ON LUMINESCENT TRANSITION-METAL COMPLEXES
复制标题
DOI：
10.1021/ac00004a007
复制
发表时间：
1991-02-15
影响因子：
7.4
通讯作者：
BACON, JR
中科院分区：
文献类型：
--
作者：
CARRAWAY, ER;DEMAS, JN;BACON, JR
对聚合物固定化发光过渡金属配合物氧传感器的光物理和光化学性质进行了较为详细的研究。重点是理解非线性斯特恩-沃尔默猝灭响应的潜在起源。微观非均质性在光物理和光化学行为中都很重要，RTV 118硅橡胶的非线性淬火响应可以用两个位点模型来充分描述，尽管详细的寿命测量表明潜在的系统更复杂。用淬火反离子进行反离子研究被证明是聚合物中配合物结构的有用探针。虽然氧增强光化学不稳定性，但单线态氧并不直接参与传感器的分解。在光化学中，至少有一个活性位点和一个活性位点少得多，尽管光化学和淬火测量可能取样不同的位点群。活性位点的存在表明，可以通过初步的光解来消除更多的活性位点来提高稳定性。
A detailed study of the photophysics and photochemistry of polymer-immobilized luminescent transition-metal complex oxygen sensors is presented. Emphasis is on understanding the underlying origin of the nonlinear Stern-Volmer quenching response. Microheterogeneity is important in both photophysical and photochemical behavior, and the nonlinear quenching responses in RTV 118 silicone rubber can be adequately described by a two-site model, although detailed lifetime measurements suggest a more complex underlying system. Counterion studies with quenching counterions are shown to be useful probes of the structure of the complex in the polymer. While oxygen enhances photochemical instability, singlet oxygen is not directly implicated in sensor decomposition. In the photochemistry there is a least one reactive and one much less reactive site, although the photochemistry and quenching measurements probably sample different populations of sites. The existence of reactive sites suggests that stability can be enhanced by a preliminary photolysis to eliminate the more reactive sites.