Positron annihilation lifetime spectroscopy, which is applied to measure distributions of hole volume sizes in polymers, uses a model to relate the positronium (Ps) lifetime to hole volume dimensions. It is assumed in this model that the Ps remains in one site until annihilation. Recently, the validity of this last assumption has been questioned by Yu et al.
The thermally induced cross-linking of nadic-end-capped polyimides
has been studied by a
variety of spectroscopic techniques. Two nadic-end-capped
polyimides were subjected to 371 °C heat
treatment for 100 h in order to study cross-linking resulting from
elevated temperature. The glass
transition temperature of the treated samples increased to greater than
400 °C, indicating that both
polyimides underwent extensive chemical changes during heat treatment.
13C spin counts were measured
before and after heat treatment by 13C cross-polarization
magic angle spinning nuclear magnetic resonance.
Electron spin resonance measurements showed an increase in the
concentration of stable free radicals in
the treated samples. Dynamic nuclear polarization and electron
spin resonance results show that two
species of free radicals are present in the treated samples; the first
is located on the polymer backbone
and the second on the cross-linking network that arises from the
reaction of the nadic end-capping groups.
On the basis of these results, new cross-linking structures of
nadic-end-capped polyimides before and
after heat treatment at 371 °C are proposed.
Rotational-echo double-resonance (REDOR) 13C NMR spectra (with 19F dephasing) have been obtained of 6-fluorotryptophan complexed by a polymeric amphiphilic nanosphere consisting of a polystyrene core covalently attached to a poly(acrylic acid)-polyacrylamide shell. The REDOR spectra show that aromatic carbons from the polystyrene core and oxygenated carbons in the poly(acrylic acid)-polyacrylamide shell are both proximate to the 19F of 6-fluorotryptophan. Molecular modeling restrained by distances inferred from the REDOR spectra suggests that all of the 6-fluorotryptophans are in the shell but within 10 A of the core-shell interface.
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