Xu W, McDonough R C, Langsdorf B, Demas J N, DeGraff B A
Department of Chemistry, University of Virginia, Charlottesville 22901.
Anal Chem. 1994 Dec 1;66(23):4133-41. doi: 10.1021/ac00095a004.
Oxygen quenching of [Ru(Ph2phen)3]Cl2 (Ph2phen = 4,7-diphenyl-1,10-phenanthroline) has been studied in a diverse series of polymers, most with a common poly-(dimethylsiloxane) (PDMS) component. Systematic variations in the polymer properties have been made in order to delineate the structural features important for satisfactory use of supports for oxygen sensors. Most measurements were made using homo- or copolymers containing a PDMS region, although some measurements were made on small ring siloxane polymers. In particular, quenching behavior was examined as a function of polymer structure as well as the type of and amount of polar copolymer cross-linkers. Cross-linkers were added to enhance the solubility of oxygen probes in an otherwise nonpolar polymer. In addition, hydrophobic silica was added to alter quenching properties. Domain models are used to explain the variations in oxygen quenching properties as a function of additives and cross-linkers. These considerations have led to the most sensitive ruthenium-based sensor reported to date. The relative affinity of the different domains for the complex and the efficacy of the domains for oxygen quenching control the overall behavior of the sensing response. Guidelines for design of suitable polymer supports for oxygen sensors are proposed.
对[Ru(Ph2phen)3]Cl2（Ph2phen = 4,7 - 二苯基 - 1,10 - 菲咯啉）在多种聚合物中的氧猝灭进行了研究，这些聚合物大多含有常见的聚二甲基硅氧烷（PDMS）成分。为了确定对氧传感器支撑体的良好使用至关重要的结构特征，对聚合物性能进行了系统的变化研究。大多数测量是使用含有PDMS区域的均聚物或共聚物进行的，不过也对一些小环硅氧烷聚合物进行了测量。特别是，研究了猝灭行为与聚合物结构以及极性共聚物交联剂的类型和用量的关系。添加交联剂以提高氧探针在原本非极性聚合物中的溶解度。此外，添加疏水二氧化硅以改变猝灭性能。使用域模型来解释氧猝灭性能随添加剂和交联剂的变化。这些考虑因素促成了迄今为止报道的最灵敏的钌基传感器。不同域对配合物的相对亲和力以及域对氧猝灭的功效控制着传感响应的整体行为。提出了用于氧传感器的合适聚合物支撑体的设计指南。
