The use of single molecules to study local, nanoscale polymer dynamics is presented. Fluorescence lifetime fluctuations were used to extract the number of polymer segments (Ns) taking part in the rearranging volume around the probe molecule below the glass transition temperature. Nswas dependent on the temperature and it decreased with increasing temperature. Above the glass transition, rotational motion of single molecules was followed in time and typical time-scales of the rotational diffusion were extracted. These two approaches allowed us to obtain non-averaged information about the heterogeneous dynamics present in polymer systems, on the nanoscale, above and below glass transition temperatures. © 2004 Elsevier Ltd. All rights reserved.
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