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    Fluorescence anisotropy imaging of a polydiacetylene photopolymer film

    Year: 2019

    Journal: Can. J. Chem., Volume 97, JUN, page 422–429

    Authors: Soleimaninejad, Hamid; Ghiggino, Kenneth P.; Smith, Trevor A.; Paige, Matthew F.

    Organizations: Natural Sciences and Engineering Research Council of CanadaNatural Sciences and Engineering Research Council of Canada; Canadian Foundation for InnovationCanada Foundation for Innovation; University of Saskatchewan; Australian Research Council Centre of Excellence in Exciton Science [CE170100026]

    Keywords: fluorescence anisotropy imaging microscopy; 10,12-pentacosadiynoic acid; polydiacetylene; Langmuir film; single-molecule spectroscopy

    UV-illumination of phase-separated surfactant films prepared from mixtures of photopolymerizable 10,12-pentacosadiynoic acid and perfluorotetradecanoic acid results in the formation of fluorescent polydiacetylene fibers and aggregates. In this work, the orientation of polymer strands that comprise the resulting photopolymer structures has been probed using fluorescence anisotropy imaging in combination with defocused single-molecule fluorescence imaging. Imaging experiments indicate the presence of significant fiber-to-fiber heterogeneity, as well as anisotropy within each fiber (or aggregate), with both of these properties changing as a function of film preparation conditions. This anisotropy can be attributed to various alignments of the constituent polymer strands that comprise the larger fibers and aggregates. Intriguingly, when using defocused imaging, fiber images consisted of a series of discrete "doughnut" fluorescence emission patterns, which exhibited intermittent on-off blinking behavior; both of these properties are characteristic of individual emission transition dipoles (single molecules). Further, all of the individual emission transition dipoles had a uniform orientation with respect to the axis of the fiber, indicating a common orientation of discrete emitters in the larger polymer fiber. The implications of these results for future studies of the electronic properties of conjugated polymers in larger macroscopic systems are noted.
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