@article{GeigerReitenbachHenscheletal.2021,
  author    = {Geiger, Christina and Reitenbach, Julija and Henschel, Cristiane and Kreuzer, Lucas and Widmann, Tobias and Wang, Peixi and Mangiapia, Gaetano and Moulin, Jean-Fran{\c{c}}ois and Papadakis, Christine M. and Laschewsky, Andr{\´e} and M{\"u}ller-Buschbaum, Peter},
  title     = {Ternary nanoswitches realized with multiresponsive PMMA-b-PNIPMAM films in mixed water/acetone vapor atmospheres},
  series = {Advanced engineering materials},
  volume    = {23},
  journal   = {Advanced engineering materials},
  number    = {11},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1438-1656},
  doi       = {10.1002/adem.202100191},
  pages     = {12},
  year      = {2021},
  abstract  = {To systematically add functionality to nanoscale polymer switches, an understanding of their responsive behavior is crucial. Herein, solvent vapor stimuli are applied to thin films of a diblock copolymer consisting of a short poly(methyl methacrylate) (PMMA) block and a long poly(N-isopropylmethacrylamide) (PNIPMAM) block for realizing ternary nanoswitches. Three significantly distinct film states are successfully implemented by the combination of amphiphilicity and co-nonsolvency effect. The exposure of the thin films to nitrogen, pure water vapor, and mixed water/acetone (90 vol\%/10 vol\%) vapor switches the films from a dried to a hydrated (solvated and swollen) and a water/acetone-exchanged (solvated and contracted) equilibrium state. These three states have distinctly different film thicknesses and solvent contents, which act as switch positions "off," "on," and "standby." For understanding the switching process, time-of-flight neutron reflectometry (ToF-NR) and spectral reflectance (SR) studies of the swelling and dehydration process are complemented by information on the local solvation of functional groups probed with Fourier-transform infrared (FTIR) spectroscopy. An accelerated responsive behavior beyond a minimum hydration/solvation level is attributed to the fast build-up and depletion of the hydration shell of PNIPMAM, caused by its hydrophobic moieties promoting a cooperative hydration character.},
  language  = {en}
}
@phdthesis{Henschel2023,
  author    = {Henschel, Cristiane},
  title     = {Thermoresponsive polymers with co-nonsolvency behavior},
  doi       = {10.25932/publishup-57716},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-577161},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xiv, 260},
  year      = {2023},
  abstract  = {Despite the popularity of thermoresponsive polymers, much is still unknown about their behavior, how it is triggered, and what factors influence it, hindering the full exploitation of their potential. One particularly puzzling phenomenon is called co-nonsolvency, in which a polymer is soluble in two individual solvents, but counter-intuitively becomes insoluble in mixtures of both. Despite the innumerous potential applications of such systems, including actuators, viscosity regulators and as carrier structures, this field has not yet been extensively studied apart from the classical example of poly(N isopropyl acrylamide) (PNIPAM) in mixtures of water and methanol. Therefore, this thesis focuses on evaluating how changes in the chemical structure of the polymers impact the thermoresponsive, aggregation and co-nonsolvency behaviors of both homopolymers and amphiphilic block copolymers. Within this scope, both the synthesis of the polymers and their characterization in solution is investigated. Homopolymers were synthesized by conventional free radical polymerization, whereas block copolymers were synthesized by consecutive reversible addition fragmentation chain transfer (RAFT) polymerizations. The synthesis of the monomers N isopropyl methacrylamide (NIPMAM) and N vinyl isobutyramide (NVIBAM), as well as a few chain transfer agents is also covered. Through turbidimetry measurements, the thermoresponsive and co-nonsolvency behavior of PNIPMAM and PNVIBAM homopolymers is then compared to the well-known PNIPAM, in aqueous solutions with 9 different organic co-solvents. Additionally, the effects of end-groups, molar mass, and concentration are investigated. Despite the similarity of their chemical structures, the 3 homopolymers show significant differences in transition temperatures and some divergences in their co-nonsolvency behavior. More complex systems are also evaluated, namely amphiphilic di- and triblock copolymers of PNIPAM and PNIPMAM with polystyrene and poly(methyl methacrylate) hydrophobic blocks. Dynamic light scattering is used to evaluate their aggregation behavior in aqueous and mixed aqueous solutions, and how it is affected by the chemical structure of the blocks, the chain architecture, presence of cosolvents and polymer concentration. The results obtained shed light into the thermoresponsive, co-nonsolvency and aggregation behavior of these polymers in solution, providing valuable information for the design of systems with a desired aggregation behavior, and that generate targeted responses to temperature and solvent mixture changes.},
  language  = {en}
}