@article{HuLinMetwallietal.2023,
  author    = {Hu, Neng and Lin, Li and Metwalli, Ezzeldin and Bießmann, Lorenz and Philipp, Martine and Hildebrand, Viet and Laschewsky, Andr{\´e} and Papadakis, Christine M. and Cubitt, Robert and Zhong, Qi and M{\"u}ller-Buschbaum, Peter},
  title     = {Kinetics of water transfer between the LCST and UCST thermoresponsive blocks in diblock copolymer thin films monitored by in situ neutron reflectivity},
  series = {Advanced materials interfaces},
  volume    = {10},
  journal   = {Advanced materials interfaces},
  number    = {3},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {2196-7350},
  doi       = {10.1002/admi.202201913},
  pages     = {11},
  year      = {2023},
  abstract  = {The kinetics of water transfer between the lower critical solution temperature (LCST) and upper critical solution temperature (UCST) thermoresponsive blocks in about 10 nm thin films of a diblock copolymer is monitored by in situ neutron reflectivity. The UCST-exhibiting block in the copolymer consists of the zwitterionic poly(4((3-methacrylamidopropyl)dimethylammonio)butane-1-sulfonate), abbreviated as PSBP. The LCST-exhibiting block consists of the nonionic poly(N-isopropylacrylamide), abbreviated as PNIPAM. The as-prepared PSBP80-b-PNIPAM(400) films feature a three-layer structure, i.e., PNIPAM, mixed PNIPAM and PSBP, and PSBP. Both blocks have similar transition temperatures (TTs), namely around 32 degrees C for PNIPAM, and around 35 degrees C for PSBP, and with a two-step heating protocol (20 degrees C to 40 degrees C and 40 degrees C to 80 degrees C), both TTs are passed. The response to such a thermal stimulus turns out to be complex. Besides a three-step process (shrinkage, rearrangement, and reswelling), a continuous transfer of D2O from the PNIPAM to the PSBP block is observed. Due to the existence of both, LCST and UCST blocks in the PSBP80-b-PNIPAM(400 )film, the water transfer from the contracting PNIPAM, and mixed layers to the expanding PSBP layer occurs. Thus, the hydration kinetics and thermal response differ markedly from a thermoresponsive polymer film with a single LCST transition.},
  language  = {en}
}
@article{NizardoSchanzenbachSchoenemannetal.2018,
  author    = {Nizardo, Noverra M. and Schanzenbach, Dirk and Sch{\"o}nemann, Eric and Laschewsky, Andre},
  title     = {Exploring poly(ethylene glycol)-polyzwitterion diblock copolymers as biocompatible smart macrosurfactants featuring UCST-phase behavior in normal saline solution},
  series = {Polymers},
  volume    = {10},
  journal   = {Polymers},
  number    = {3},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {2073-4360},
  doi       = {10.3390/polym10030325},
  pages     = {22},
  year      = {2018},
  abstract  = {Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST) in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol) (PEG) macroinitiator via atom transfer radical polymerization (ATRP) of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and H-1 NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30-50 degrees C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo-and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in "schizophrenic" thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature) transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model "cargos" failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions.},
  language  = {en}
}