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1000 nm thick polyHEA film. Fig. 4b shows the time course of the Notes and references
Z-position of the guest dye, indicating that the dyes did not
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approach the surface of the cover slip during the measurement.
Fig. 4c shows the corresponding normalized histograms of SDs at
several time bins. The curved histograms clearly show that the
lateral diffusion is anomalous in spite of the separate Z-position
from the surface. This result directly indicates that the anomalous
diffusion is not due to the translation along the Z-axis but is
ascribable to a locally viscous area in the polymer film.
Finally, the origin of the extraordinary behaviours of the
guest molecule in the position and diffusion along the Z-axis is
worth noting. The experimental result on the guest dye being
restricted in the specific position implies position-dependent
properties of the polymer, such as the polarity of the surrounding
area of guest dyes. As a result, the solubility of the guest dye could
be dependent on the distance from the interface. As already
mentioned, the properties of the polymer near the interface
(r100 nm) were reported to be different from those in the bulk
region.26,27 The present result, however, indicates that the
distance of the location of the dye from the interface is much
longer than the scale arising from the short-range interaction
between guest dyes and the glass surface. In other words, the
present result suggests that the effect of the interface hierarchically
affects the properties of the polymer at a much longer distance
(c100 nm) from the interface. Actually, the location and the lateral
diffusion coefficient of the guest dyes depending on the film
thickness (Fig. 2e and f) support the gradual change in the
polymer properties at rather long distance along the Z-axis.
The interaction between the host polymer and the guest dye
is generally sensitive to chemical properties. Our preliminary
studies with the different guest dyes with polar groups showed
the different distribution of the location along the Z-axis; the
location was rather close to the glass surface. This result
implies that the polarity is also dependent on the distance
from the interface, as predicted by the TIR measurement of the
fluorescence of the guest molecules.33
Anyhow, the above discussion suggests that the location of
the guest dye and the diffusion process are regulated through the
interaction between the guest molecule and the host polymer,
which is dependent on the distance from the interface. With this
point, detailed investigation is underway by changing aging times
and by using various guest dyes, host polymers with larger
molecular weight, and different kinds of substrates, results of
which will be published soon.
This work was partly supported by Grant-in-Aid for Young
Scientists (A) (23681023) and Grant-in-Aid for Challenging
Exploratory Research (15K13625) to S.I. from JSPS and by
Grant-in-Aid for Scientific Research on Innovative Areas
‘‘Photosynergetics’’ (26107002 and 26107013) to HM and SK
from MEXT, Japan.
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