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@ARTICLE{Bras:172776,
author = {Bras, Ana and Fonseca, Isabel M. and Dionísio, Madalena
and Schönhals, Andreas and Affouard, Frédéric and
Correia, Natália T.},
title = {{I}nfluence of {N}anoscale {C}onfinement on the {M}olecular
{M}obility of {I}buprofen},
journal = {The journal of physical chemistry / C},
volume = {118},
number = {25},
issn = {1932-7455},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2014-06217},
pages = {13857 - 13868},
year = {2014},
abstract = {The molecular mobility of ibuprofen confined to a
mesoporous silica host (MCM-41) of 3.6 nm pore diameter is
investigated by dielectric relaxation spectroscopy. It is
confirmed that crystallization is suppressed; therefore,
depending on the temperature, the guest exists in the glassy
and supercooled state inside of the pores. A detailed
relaxation map is provided where multiple processes are
dynamically characterized, comprised of three processes that
are also found for the bulk and two additional ones. The
bulk-like processes include two secondary processes, a
simple thermally activated one, a γ process and a
Johari–Goldstein βJG process, and the one associated with
the dynamic glass transition of molecules located in the
pore center (α process). In confinement, all of these
processes display deviations in its dynamical behavior
relative to the bulk, the most dramatic one undergone by the
α process, which exhibits Arrhenius-like temperature
dependence upon approaching the glass transition instead of
Vogel/Fulcher/Tammann/Hesse (VFTH) scaling as obeyed by the
bulk. The two additional relaxations are associated with the
dynamical behavior of hydrogen-bonded ibuprofen molecules
lying in an interfacial layer near the pore wall, an S
process for which the mobility is strongly reduced relative
to the α process and a Debye-like D process for which the
dynamics is closely correlated to the dynamics of the
interfacial process, both exhibiting VFTH temperature
dependencies. The comparison with the behavior of the same
guest in the analogous host, SBA-15, with a higher pore
diameter (8.6 nm) leads to the conclusion that the bulk-like
mobility associated with the dynamic glass transition
undergoes finite size effects being accelerated upon a
decrease of the pore size with a concomitant reduction of
the glass transition temperature relative to the bulk, 22
and 32 K, respectively, for the 8.6 and 3.6 nm pore
diameters. The continuous decrease in the separation between
the α- and βJG-trace with pore size decrease allows one to
conclude that confined ibuprofen is a suitable guest
molecule to test the Coupling Model that predicts a
transformation of the α process into a βJG-mode under
conditions of an extreme nanoconfinement. The overall
behavior inside of pores is consistent with the existence of
two distinct dynamical domains, originated by ibuprofen
molecules in the core of the pore cavity and adjacent to the
pore wall, from which a clear picture is given by molecular
dynamics simulation.},
cin = {ICS-1 / Neutronenstreuung ; JCNS-1},
ddc = {540},
cid = {I:(DE-Juel1)ICS-1-20110106 / I:(DE-Juel1)JCNS-1-20110106},
pnm = {451 - Soft Matter Composites (POF2-451) / 54G - JCNS
(POF2-54G24)},
pid = {G:(DE-HGF)POF2-451 / G:(DE-HGF)POF2-54G24},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000338184300062},
doi = {10.1021/jp500630m},
url = {https://juser.fz-juelich.de/record/172776},
}