Nanofiber mats composed of polymers,
having a large surface-to-volume
ratio and high porosity, have been widely applied in the environmental
and biomedical fields but fundamental knowledge on the polymer chains
in the mats seems to be limited. We here report the aggregation states
and segmental dynamics of poly(methyl methacrylate)s (PMMAs) with
different stereoregularities in electrospun nanofiber mats. Attenuated
total reflectance Fourier transform infrared (ATR/FTIR) spectroscopy
revealed that, in the case of atactic PMMA (at-PMMA),
the population of the trans–trans conformation of the main chain part, which allows carbonyl groups
of the side group to interact affirmatively with each other, increased
in the electrospun nanofiber mat. On the other hand, in the case of
isotactic PMMA (it-PMMA), the skeletal conformation
was unchanged even in the nanofiber mat. As a result of the aggregation
states of PMMA chains, the glass-transition temperature (T
g) of the electrospun nanofiber mats increased and remained
unchanged from the corresponding bulk value for at- and it-PMMA, respectively. These findings should
be useful for designing materials and devices composed of electrospun
nanofibers.