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@ARTICLE{FariasMancilla:1023473,
author = {Farias-Mancilla, Barbara and Balestri, Arianna and Zhang,
Junliang and Frielinghaus, Henrich and Berti, Debora and
Montis, Costanza and Destarac, Mathias and Schubert, Ulrich
S. and Guerrero-Sanchez, Carlos and Harrisson, Simon and
Lonetti, Barbara},
title = {{M}orphology and thermal transitions of self-assembled
{NIPAM}-{DMA} copolymers in aqueous media depend on
copolymer composition profile},
journal = {Journal of colloid and interface science},
volume = {662},
issn = {0021-9797},
address = {Amsterdam [u.a.]},
publisher = {Elsevier},
reportid = {FZJ-2024-01706},
pages = {99 - 108},
year = {2024},
abstract = {Hypothesis: There is a lack of understanding of the
interplay between the copolymer composition profile and
thermal transition observed in aqueous solutions of
N-isopropyl acrylamide (NIPAM) copolymers, as well as the
correlation between this transition and the formation and
structure of copolymer self-assemblies.Experiments: For this
purpose, we investigated the response of five copolymers
with the same molar mass and chemical composition, but with
different composition profile in aqueous solution against
temperature. Using complementary analytical techniques, we
probed structural properties at different length scales,
from the mo-lecular scale with Nuclear Magnetic Resonance
(NMR) to the colloidal scale with Dynamic Light Scattering
(DLS) and Small Angle Neutron Scattering (SANS).Findings:
NMR and SANS investigations strengthen each other and allow
a clear picture of the change of copolymer solubility and
related copolymer self-assembly as a function of
temperature. At the molecular scale, dehydrating NIPAM units
drag N,N-dimethyl acrylamide (DMA) moieties with them in a
gradual collapse of the copolymer chain; this induces a
morphological transition of the self-assemblies from
star-like nanostructures to crew-cut micelles.
Interestingly, the transition spans a temperature range
which depends on the monomer dis-tribution profile in the
copolymer chain, with the asymmetric triblock copolymer
specimen revealing the broadest one. We show that the broad
morphological transitions associated with gradient
copolymers can be mimicked and even surpassed by the use of
stepwise gradient (asymmetric) copolymers, which can be more
easily and reproducibly synthesized than linear gradient
copolymers.},
cin = {JCNS-FRM-II / JCNS-4 / MLZ},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-4-20201012 / I:(DE-588b)4597118-3},
pnm = {6G4 - Jülich Centre for Neutron Research (JCNS) (FZJ)
(POF4-6G4) / 632 - Materials – Quantum, Complex and
Functional Materials (POF4-632)},
pid = {G:(DE-HGF)POF4-6G4 / G:(DE-HGF)POF4-632},
experiment = {EXP:(DE-MLZ)KWS1-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {38340518},
UT = {WOS:001183974800001},
doi = {10.1016/j.jcis.2024.02.032},
url = {https://juser.fz-juelich.de/record/1023473},
}