Chemistry 版 (精华区)
发信人: zjliu (秋天的萝卜), 信区: Chemistry
标 题: Probing Free Volume
发信站: 哈工大紫丁香 (Tue Mar 2 22:00:04 2004), 站内信件
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CHEMISTRY: Probing Free Volume
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l
D. Szuromi
Molecular motion in liquids and glasses is often explained in terms of the
extent of free volumes that can exist between the molecules. Vallee et al.
present single-molecule spectroscopic data that characterize local changes
in a free volume space in polymer films. The dye molecule,
tetraphenoxy-perylenetetracarboxyl diimide, can exist in two conformations:
one in which the core of the molecule lies flat and one in which the core
is twisted. The flat conformer has a shorter fluorescence lifetime and a
larger van der Waals volume (greater by 0.2 cubic nm). Fluorescence
lifetime distributions were measured for this dye in thin films of two
polymers of the same family: poly(methyl methacrylate) (PMMA) and
poly(n-butyl methacrylate) (PnBMA). The smaller side chains of PMMA result
in a lower free volume, and indeed, only longer lifetime traces of the
twisted dye conformer were seen. However, for PnBMA, about 30% of the dye
conformer. Thus holes as large as 0.2 nm3 can form in PnBMA but not in
PMMA. -- PDS
J. Am. Chem. Soc. 10.1021/ja031599g (2004).
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