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@ARTICLE{Vishnevetskaya:856727,
author = {Vishnevetskaya, Natalya S. and Hildebrand, Viet and
Dyakonova, Margarita A. and Niebuur, Bart-Jan and Kyriakos,
Konstantinos and Raftopoulos, Konstantinos N. and Di, Zhenyu
and Müller-Buschbaum, Peter and Laschewsky, André and
Papadakis, Christine M.},
title = {{D}ual {O}rthogonal {S}witching of the
“{S}chizophrenic” {S}elf-{A}ssembly of {D}iblock
{C}opolymers},
journal = {Macromolecules},
volume = {51},
number = {7},
issn = {1520-5835},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2018-06078},
pages = {2604 - 2614},
year = {2018},
abstract = {Based on diblock copolymers, a pair of “schizo-phrenic”
micellar systems is designed by combining a nonionic
andthermoresponsive block with a zwitterionic block, which
isthermoresponsive and salt-sensitive. The nonionic block
ispoly(N-isopropylacrylamide) (PNIPAM) or
poly(N-isopropyl-methacrylamide) (PNIPMAM) and exhibits a
lower criticalsolution temperature (LCST) behavior in
aqueous solution. Thezwitterionic block is a
polysulfobetaine, i.e.,
poly(4-((3-methacryl-amidopropyl)dimethylammonio)butane-1-sulfonate)
(PSBP), andhas an upper critical solution temperature (UCST)
behavior withthe clearing point decreasing with increasing
salt concentration. The PSBP-b-PNIPAM and PSBP-b-PNIPMAM
diblockcopolymers are prepared by successive reversible
addition−fragmentation chain transfer (RAFT)
polymerizations. The PSBPblock is chosen such that the
clearing point of the homopolymer is significantly higher
in pure water than the cloud point ofPNIPAM or PNIPMAM.
Using turbidimetry, 1H NMR, and small-angle neutron
scattering, we investigate the overall phasebehavior as well
as the structure and interaction between the micelles and
the intermediate phase, both in salt-free D2O and in0.004 M
NaBr in D2O in a wide temperature range. We find that
PSBP-b-PNIPAM at 50 g L−1 in salt-free D2O is turbid in
theentire temperature range. It forms spherical micelles
below the cloud point of PNIPAM and cylindrical micelles
above. Similarbehavior is observed for PSBP-b-PNIPMAM at 50
g L−1 in salt-free D2O with a slight and smooth increase
of the lighttransmission below the cloud point of PNIPMAM
and an abrupt decrease above. Upon addition of 0.004 M NaBr,
the UCST-type cloud point of the PSBP-block is notably
decreased, and an intermediate regime is encountered below
the cloud point ofPNIPMAM, where the light transmission is
slightly enhanced. In this regime, the polymer solution
exhibits behavior typical forpolyelectrolyte solutions.
Thus, double thermosensitive and salt-sensitive behavior
with “schizophrenic” micelle formation isfound, and the
width of the intermediate regime, where both blocks are
hydrophilic, can be tuned by the addition of electrolyte.},
cin = {JCNS-FRM-II / Neutronenstreuung ; JCNS-1},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
/ 6G15 - FRM II / MLZ (POF3-6G15)},
pid = {G:(DE-HGF)POF3-6G4 / G:(DE-HGF)POF3-6G15},
experiment = {EXP:(DE-MLZ)KWS1-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000430022000021},
doi = {10.1021/acs.macromol.8b00096},
url = {https://juser.fz-juelich.de/record/856727},
}