Title | Fluorescent Chemosensors Based on Energy Migration in Conjugated Polymers: The Molecular Wire Approach to Increased Sensitivity |
Publication Type | Journal Article |
Year of Publication | 1995 |
Authors | Zhou, Q, Swager, TM |
Journal | Journal of the American Chemical Society |
Volume | 117 |
Pagination | 12593–12602 |
Date Published | dec |
ISSN | 0002-7863 |
Keywords | intramol energy transfer conjugated polymer sensor, paraquat sensor fluorescence quenching conjugated polymer |
Abstract | The authors demonstrate herein how conjugated polymers (mol. wires) can be used to interconnect (wire in series) receptors to produce fluorescent chemosensory systems with sensitivity enhancements over single receptor analogs. The enhancement mechanism in the polyreceptor materials is based on an energy migration scheme in which excitations, diffuse along the polymer backbone. Analyte binding produces trapping sites for the excitations which results in greatly attenuated emission intensity. Three different cyclophane-based receptor systems that bind paraquat were studied. These systems are quenched by paraquat binding, and the quenching enhancements relative to a monomeric model compd. were used to det. the efficiency of energy migration. Two polymers with related poly(phenyleneethynylene) structures were studied, and the all-para system was found to exhibit more facile energy migration than the more electronically localized analog that contained meta linkages. The para polyreceptor system was found to display a 65-fold enhancement in sensitivity to paraquat as compared to a model monoreceptor fluorescent chemosensor. However, delocalization alone is not sufficient to produce facile energy migration, and the more delocalized polythiophenes appear to be less effective at energy migration than the para poly(phenyleneethynylene) material. Paraquat-induced fluorescent quenching studies on homologous polymers that lacked the cyclophane receptors were also performed. Diffusive quenching by paraquat is enhanced by energy migration. [on SciFinder(R)] |
URL | http://pubs.acs.org/doi/abs/10.1021/ja00155a023 |
DOI | 10.1021/ja00155a023 |