@article{MarsatStahlhutLaschewskyetal.2013, author = {Marsat, Jean-Noel and Stahlhut, Frank and Laschewsky, Andr{\´e} and von Berlepsch, Hans and B{\"o}ttcher, Christoph}, title = {Multicompartment micelles from silicone-based triphilic block copolymers}, series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, volume = {291}, journal = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, number = {11}, publisher = {Springer}, address = {New York}, issn = {0303-402X}, doi = {10.1007/s00396-013-3001-2}, pages = {2561 -- 2567}, year = {2013}, abstract = {An amphiphilic linear ternary block copolymer was synthesised in three consecutive steps via reversible addition-fragmentation chain transfer polymerisation. Oligo(ethylene glycol) monomethyl ether acrylate was engaged as a hydrophilic building block, while benzyl acrylate and 3-tris(trimethylsiloxy)silyl propyl acrylate served as hydrophobic building blocks. The resulting "triphilic" copolymer consists thus of a hydrophilic (A) and two mutually incompatible "soft" hydrophobic blocks, namely, a lipophilic (B) and a silicone-based (C) block, with all blocks having glass transition temperatures well below 0 A degrees C. The triphilic copolymer self-assembles into spherical multicompartment micellar aggregates in aqueous solution, where the two hydrophobic blocks undergo local phase separation into various ultrastructures as evidenced by cryogenic transmission electron microscopy. Thus, a silicone-based polymer block can replace the hitherto typically employed fluorocarbon-based hydrophobic blocks in triphilic block copolymers for inducing multicompartmentalisation.}, language = {en} } @article{WeissBoettcherLaschewsky2011, author = {Weiss, Jan and B{\"o}ttcher, Christoph and Laschewsky, Andr{\´e}}, title = {Self-assembly of double thermoresponsive block copolymers end-capped with complementary trimethylsilyl groups}, series = {Soft matter}, volume = {7}, journal = {Soft matter}, number = {2}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1744-683X}, doi = {10.1039/c0sm00531b}, pages = {483 -- 492}, year = {2011}, abstract = {A set of double thermoresponsive diblock copolymers poly(N-n-propylacrylamide)-block-poly(N-ethylacrylamide) (PNPAM-b-PNEAM) was synthesised by sequential reversible addition-fragmentation chain transfer (RAFT) polymerisations. Using a twofold trimethylsilyl (TMS)-labeled RAFT-agent, the relative size of the two blocks was varied. While soluble as unimers below 15 degrees C, all copolymers exhibited thermally induced two-step self-assembly in water, due to distinct lower critical solution temperature (LCST) phase transitions of PNPAM (around 20 degrees C) and PNEAM (around 70 degrees C). Their temperature-dependent self-organisation in dilute aqueous solution was studied by turbidimetry, dynamic light scattering, transmission electron microscopy, and (1)H NMR spectroscopy. The copolymers show distinct, two-step self-organisation behaviour with respect to transition temperatures, aggregate type and size, which can be correlated to the relative lengths of the low and high LCST blocks. For polymers having short blocks with low LCST, the first thermal transition induces the formation of individual micelles. Further heating above the second thermal transition results reversibly either in a shrink of the micelle size or in aggregation of the micelles, with hydrodynamic diameters below 250 nm. In contrast in the case of polymers having a long block with low LCST, the first thermal transition already leads to clusters of micelles, while the second thermal transition makes the clusters shrink. Noteworthy, the twofold TMS-labeled end groups report not only on the molar masses of the polymers, but can simultaneously serve as NMR-probes for the self-assembly process. The signal of the TMS-aryl end group displays a reversible temperature dependent, two-step splitting that is indicative of the self-organisation of the block copolymers.}, language = {en} } @article{SkrabaniavonBerlepschBoettcheretal.2010, author = {Skrabania, Katja and von Berlepsch, Hans and B{\"o}ttcher, Christoph and Laschewsky, Andr{\´e}}, title = {Synthesis of ternary, hydrophilic-lipophilic-fluorophilic block copolymers by consecutive RAFT polymerizations and their self-assembly into multicompartment micelles}, issn = {0024-9297}, doi = {10.1021/Ma901913f}, year = {2010}, abstract = {Linear amphiphilic diblock and ternary triblock copolymers were synthesized by the RAFT method in three Successive Steps, using oligo(ethylene oxide) monomethyl ether acrylate, butyl or 2-ethylhexyl acrylate, and 1H, 1H, 2H, 2H-perfluorodecyl acrylate. The diblock and the triblock copolymers, which consist of a hydrophilic, a lipophilic, and a fluorophilic block, self-assemble in water into spherical micellar aggregates. Imaging by cryogenic transmission electron microscopy (cryo-TEM) revealed that the cores of the micellar aggregates made from these "triphilic" copolymers undergo local phase separation to form various ultrastructures, which depend sensitivity on the given block sequence. While the sequence hydrophilic-lipophilic-fluorophilic resulted in multicompartment cores with core-shell-corona morphology, the sequence lipophilic-hydrophilic-fluorophilic provided new "patched double micelle" and larger "soccer ball" structures.}, language = {en} }