@article{PapadakisMuellerBuschbaumLaschewsky2019, author = {Papadakis, Christine M. and M{\"u}ller-Buschbaum, Peter and Laschewsky, Andre}, title = {Switch It Inside-Out: "Schizophrenic" Behavior of All Thermoresponsive UCST-LCST Diblock Copolymers}, series = {Langmuir}, volume = {35}, journal = {Langmuir}, number = {30}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.9b01444}, pages = {9660 -- 9676}, year = {2019}, abstract = {This feature article reviews our recent advancements on the synthesis, phase behavior, and micellar structures of diblock copolymers consisting of oppositely thermoresponsive blocks in aqueous environments. These copolymers combine a nonionic block, which shows lower critical solution temperature (LCST) behavior, with a zwitterionic block that exhibits an upper critical solution temperature (UCST). The transition temperature of the latter class of polymers is strongly controlled by its molar mass and by the salt concentration, in contrast to the rather invariant transition of nonionic polymers with type II LCST behavior such as poly(N-isopropylacrylamide) or poly(N-isopropyl methacrylamide). This allows for implementing the sequence of the UCST and LCST transitions of the polymers at will by adjusting either molecular or, alternatively, physical parameters. Depending on the location of the transition temperatures of both blocks, different switching scenarios are realized from micelles to inverse micelles, namely via the molecularly dissolved state, the aggregated state, or directly. In addition to studies of (semi)dilute aqueous solutions, highly concentrated systems have also been explored, namely water-swollen thin films. Concerning applications, we discuss the possible use of the diblock copolymers as "smart" nanocarriers.}, language = {en} } @article{VishnevetskayaHildebrandNiebuuretal.2017, author = {Vishnevetskaya, Natalya S. and Hildebrand, Viet and Niebuur, Bart-Jan and Grillo, Isabelle and Filippov, Sergey K. and Laschewsky, Andre and M{\"u}ller-Buschbaum, Peter and Papadakis, Christine M.}, title = {"Schizophrenic" Micelles from Doubly Thermoresponsive Polysulfobetaine-b-poly(N-isopropylmethacrylamide) Diblock Copolymers}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {50}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.7b00356}, pages = {3985 -- 3999}, year = {2017}, language = {en} } @article{VishnevetskayaHildebrandDyakonovaetal.2018, 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 M{\"u}ller-Buschbaum, Peter and Laschewsky, Andre and Papadakis, Christine M.}, title = {Dual orthogonal switching of the "Schizophrenic" self-assembly of diblock copolymers}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {51}, journal = {Macromolecules : a publication of the American Chemical Society}, number = {7}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.8b00096}, pages = {2604 -- 2614}, year = {2018}, abstract = {Based on diblock copolymers, a pair of "schizophrenic" micellar systems is designed by combining a nonionic and thermoresponsive block with a zwitterionic block, which is thermoresponsive and salt-sensitive. The nonionic block is poly(N-isopropylacrylamide) (PNIPAM) or poly(N-isopropylmethacrylamide) (PNIPMAM) and exhibits a lower critical solution temperature (LCST) behavior in aqueous solution. The zwitterionic block is a polysulfobetaine, i.e., poly(4((3-methacrylamidopropyl)dimethylammonio)butane-1-sulfonate) (PSBP), and has an upper critical solution temperature (UCST) behavior with the clearing point decreasing with increasing salt concentration. The PSBP-b-PNIPAM and PSBP-b-PNIPMAM diblock copolymers are prepared by successive reversible addition-fragmentation chain transfer (RAFT) polymerizations. The PSBP block is chosen such that the clearing point of the homopolymer is significantly higher in pure water than the cloud point of PNIPAM or PNIPMAM. Using turbidimetry, H-1 NMR, and small-angle neutron scattering, we investigate the overall phase behavior as well as the structure and interaction between the micelles and the intermediate phase, both in salt-free D2O and in 0.004 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 the entire temperature range. It forms spherical micelles below the cloud point of PNIPAM and cylindrical micelles above. Similar behavior is observed for PSBP-b-PNIPMAM at 50 g L-1 in salt-free D2O with a slight and smooth increase of the light transmission 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 of PNIPMAM, where the light transmission is slightly enhanced. In this regime, the polymer solution exhibits behavior typical for polyelectrolyte solutions. Thus, double thermosensitive and salt-sensitive behavior with "schizophrenic" micelle formation is found, and the width of the intermediate regime, where both blocks are hydrophilic, can be tuned by the addition of electrolyte.}, language = {en} } @article{VishnevetskayaHildebrandNizardoetal.2019, author = {Vishnevetskaya, Natalya S. and Hildebrand, Viet and Nizardo, Noverra Mardhatillah and Ko, Chia-Hsin and Di, Zhenyu and Radulescu, Aurel and Barnsley, Lester C. and M{\"u}ller-Buschbaum, Peter and Laschewsky, Andr{\´e} and Papadakis, Christine M.}, title = {All-in-One "Schizophrenic" self-assembly of orthogonally tuned thermoresponsive diblock copolymers}, series = {Langmuir}, volume = {35}, journal = {Langmuir}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.9b00241}, pages = {6441 -- 6452}, year = {2019}, abstract = {Smart, fully orthogonal switching was realized in a highly biocompatible diblock copolymer system with variable trigger-induced aqueous self-assembly. The polymers are composed of nonionic and zwitterionic blocks featuring lower and upper critical solution temperatures (LCSTs and UCSTs). In the system investigated, diblock copolymers from poly(N-isopropyl methacrylamide) (PNIPMAM) and a poly(sulfobetaine methacrylamide), systematic variation of the molar mass of the latter block allowed for shifting the UCST of the latter above the LCST of the PNIPMAM block in a salt-free condition. Thus, successive thermal switching results in "schizophrenic" micellization, in which the roles of the hydrophobic core block and the hydrophilic shell block are interchanged depending on the temperature. Furthermore, by virtue of the strong electrolyte-sensitivity of the zwitterionic polysulfobetaine block, we succeeded to shift its UCST below the LCST of the PNIPMAM block by adding small amounts of an electrolyte, thus inverting the pathway of switching. This superimposed orthogonal switching by electrolyte addition enabled us to control the switching scenarios between the two types of micelles (i) via an insoluble state, if the LCST-type cloud point is below the UCST-type cloud point, which is the case at low salt concentrations or (ii) via a molecularly dissolved state, if the LCST-type cloud point is above the UCST-type cloud point, which is the case at high salt concentrations. Systematic variation of the block lengths allowed for verifying the anticipated behavior and identifying the molecular architecture needed. The versatile and tunable self-assembly offers manifold opportunities, for example, for smart emulsifiers or for sophisticated carrier systems.}, language = {en} } @article{ZhongMiMetwallietal.2018, author = {Zhong, Qi and Mi, Lei and Metwalli, Ezzeldin and Biessmann, Lorenz and Philipp, Martine and Miasnikova, Anna and Laschewsky, Andre and Papadakis, Christine M. and Cubitt, Robert and Schwartzkopf, Matthias and Roth, Stephan V. and Wang, Jiping and M{\"u}ller-Buschbaum, Peter}, title = {Effect of chain architecture on the swelling and thermal response of star-shaped thermo-responsive (poly(methoxy diethylene glycol acrylate)-block-polystyrene)(3) block copolymer films}, series = {Soft matter}, volume = {14}, journal = {Soft matter}, number = {31}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1744-683X}, doi = {10.1039/c8sm00965a}, pages = {6582 -- 6594}, year = {2018}, abstract = {The effect of chain architecture on the swelling and thermal response of thin films obtained from an amphiphilic three-arm star-shaped thermo-responsive block copolymer poly(methoxy diethylene glycol acrylate)-block-polystyrene ((PMDEGA-b-PS)(3)) is investigated by in situ neutron reflectivity (NR) measurements. The PMDEGA and PS blocks are micro-phase separated with randomly distributed PS nanodomains. The (PMDEGA-b-PS)(3) films show a transition temperature (TT) at 33 degrees C in white light interferometry. The swelling capability of the (PMDEGA-b-PS)(3) films in a D2O vapor atmosphere is better than that of films from linear PS-b-PMDEGA-b-PS triblock copolymers, which can be attributed to the hydrophilic end groups and limited size of the PS blocks in (PMDEGA-b-PS)(3). However, the swelling kinetics of the as-prepared (PMDEGA-b-PS)(3) films and the response of the swollen film to a temperature change above the TT are significantly slower than that in the PS-b-PMDEGA-b-PS films, which may be related to the conformation restriction by the star-shape. Unlike in the PS-b-PMDEGA-b-PS films, the amount of residual D2O in the collapsed (PMDEGA-b-PS)(3) films depends on the final temperature. It decreases from (9.7 +/- 0.3)\% to (7.0 +/- 0.3)\% or (6.0 +/- 0.3)\% when the final temperatures are set to 35 degrees C, 45 degrees C and 50 degrees C, respectively. This temperature-dependent reduction of embedded D2O originates from the hindrance of chain conformation from the star-shaped chain architecture.}, language = {en} } @article{KreuzerWidmannHohnetal.2019, author = {Kreuzer, Lucas and Widmann, Tobias and Hohn, Nuri and Wang, Kun and Biessmann, Lorenz and Peis, Leander and Moulin, Jean-Francois and Hildebrand, Viet and Laschewsky, Andr{\´e} and Papadakis, Christine M. and M{\"u}ller-Buschbaum, Peter}, title = {Swelling and exchange behavior of poly(sulfobetaine)-based block copolymer thin films}, series = {Macromolecules : web edition}, volume = {52}, journal = {Macromolecules : web edition}, number = {9}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.9b00443}, pages = {3486 -- 3498}, year = {2019}, abstract = {The humidity-induced swelling and exchange behavior of a block copolymer thin film, which consists of a zwitterionic poly(sulfobetaine) [poly(N,N-dimethyl-N-(3-(methacrylamido)propyl)ammoniopropanesulfonate) (PSPP)] block and a nonionic poly(N-isopropylacrylamide) (PNIPAM) block, are investigated by time-of-flight neutron reflectometry (TOF-NR). We monitor in situ the swelling in the H2O atmosphere, followed by an exchange with D2O. In the reverse experiment, swelling in the D2O atmosphere and the subsequent exchange with H2O are studied. Both, static and kinetic TOF-NR measurements indicate significant differences in the interactions between the PSPP80-b-PNIPAM(130) thin film and H2O or D2O, which we attribute to the different H- and D-bonds between water and the polymer. Changes in the chain conformation and hydrogen bonding are probed with Fourier transform infrared spectroscopy during the kinetics of the swelling and exchange processes, which reveals the key roles of the ionic SO3- group in the PSPP block and of the polar amide groups of both blocks during water uptake and exchange.}, language = {en} }