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@ARTICLE{Burger:890562,
author = {Burger, Nikolaos A. and Mavromanolakis, Antonios and Meier,
G. and Brocorens, Patrick and Lazzaroni, Roberto and
Bouteiller, Laurent and Loppinet, Benoit and Vlassopoulos,
Dimitris},
title = {{S}tabilization of {S}upramolecular {P}olymer {P}hase at
{H}igh {P}ressures},
journal = {ACS Macro Letters},
volume = {10},
number = {3},
issn = {2161-1653},
address = {Washington, DC},
publisher = {ACS},
reportid = {FZJ-2021-01043},
pages = {321 - 326},
year = {2021},
abstract = {We utilize dynamic light scattering (DLS) and passive
microrheology to examine the phase behavior of a
supramolecular polymer at very high pressures. The monomer,
2,4-bis(2-ethylhexylureido)toluene (EHUT), self-assembles
into supramolecular polymeric structures in the nonpolar
solvent cyclohexane by means of hydrogen bonding. By varying
the concentration and temperature at atmospheric pressure,
the formation of the viscoelastic network (at lower
temperatures) and predominantly viscous phases, based on
self-assembled tube and filament structures, respectively,
has been established. The associated changes in the
rheological properties have been attributed to a structural
thickness transition. Here, we investigate the effects of
pressure variation from atmospheric up to 1 kbar at a given
concentration. We construct a temperature–pressure diagram
that reveals the predominance of the viscoelastic network
phase at high pressures. The transition from the
viscoelastic network organization of the tubes to a weaker
viscous-dominated structure of the filaments is rationalized
by using the Clapeyron equation, which yields an associated
volume change of about 8 Å3 per EHUT molecule. This change
is further explained by means of Molecular Dynamics
simulations of the two phases, which show a decrease in the
molecular volume at the filament-tube transition,
originating from increased intermolecular contacts in the
tube with respect to the filament. These findings offer
insights into the role of pressure in stabilizing
self-assemblies.},
cin = {IBI-4},
ddc = {540},
cid = {I:(DE-Juel1)IBI-4-20200312},
pnm = {524 - Molecular and Cellular Information Processing
(POF4-524)},
pid = {G:(DE-HGF)POF4-524},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000636739700003},
doi = {10.1021/acsmacrolett.0c00834},
url = {https://juser.fz-juelich.de/record/890562},
}