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BA DeGraff

Publications and source records attributed to BA DeGraff.

2 recordsLinked to original sources

Lifetime-based pH sensor system based on a polymer-supported ruthenium(II) complex

A new luminescence lifetime-based pH sensor system is described. The system is based on [Ru(Ph2phen)2DCbpy]2+ (DCbpy = 4,4'-dicarboxy-2,2'-bipyridine) immobilized in a mixed domain network copolymer utilizing hydrophobic regions in a hydrophilic, water-swellable, poly(ethylene oxide) matrix. The metal complex binds irreversibly to the hydrophobic domains leaving the pH-sensing COOHs projecting into an aqueous-rich poly(ethylene oxide) region. The complex shows a strong pH dependence of its lifetime (3-4-fold) and provides a usable pH range of about 3-5. The long (approximately 1 micros) excited-state lifetime and visible absorption of the sensor simplifies measurements. A model for the combined pH and oxygen-quenching sensitivity of the complex is provided; this allows use of the pH system over a wide range of oxygen concentrations. The combined polymer sensor is easy to prepare and requires no covalent chemistry. Further, the polymers enhance the luminescence of the complex and minimize interference from oxygen quenching.

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Fluorescence Microscopy Study of Heterogeneity in Polymer-supported Luminescence-based Oxygen Sensors.

Despite the great potential of fluorescence microscopy, its application to date has largely been in the study of biological specimens. It will be shown that conventional fluorescence microscopy provides an invaluable tool with which to study the photophysics of polymer-supported luminescence-based oxygen sensors. The design of the imaging system, the measurement methods, and the data analysis used in the investigation of sensor systems are described. Fluorescence microscopic images of sensor films in which microheterogeneous regions exhibiting enhanced luminescence intensity and poorer oxygen quenching relative to the bulk response are shown. This is the first direct evidence that sensor molecules in various domains of the polymer support can exhibit different oxygen quenching properties. It will be shown that ยต- and nano-crystallization of the sensor molecule are the probable source of both the observed heterogeneous microscopic responses and the microscopic and macroscopic nonlinear Stern-Volmer plots. The implications of these results in the rational design of luminescence-based oxygen sensors are discussed.

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