@misc{NiebuurPuchmayrHeroldetal.2018,
  author    = {Niebuur, Bart-Jan and Puchmayr, Jonas and Herold, Christian and Kreuzer, Lucas and Hildebrand, Viet and M{\"u}ller-Buschbaum, Peter and Laschewsky, Andr{\´e} and Papadakis, Christine M.},
  title     = {Polysulfobetaines in aqueous solution and in thin film geometry},
  series = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Postprints der Universit{\"a}t Potsdam Mathematisch-Naturwissenschaftliche Reihe},
  number    = {713},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-42736},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-427363},
  pages     = {11},
  year      = {2018},
  abstract  = {Polysulfobetaines in aqueous solution show upper critical solution temperature (UCST) behavior. We investigate here the representative of this class of materials, poly (N,N-dimethyl-N-(3-methacrylamidopropyl) ammonio propane sulfonate) (PSPP), with respect to: (i) the dynamics in aqueous solution above the cloud point as function of NaBr concentration; and (ii) the swelling behavior of thin films in water vapor as function of the initial film thickness. For PSPP solutions with a concentration of 5 wt.\%, the temperature dependence of the intensity autocorrelation functions is measured with dynamic light scattering as function of molar mass and NaBr concentration (0-8 mM). We found a scaling of behavior for the scattered intensity and dynamic correlation length. The resulting spinodal temperatures showed a maximum at a certain (small) NaBr concentration, which is similar to the behavior of the cloud points measured previously by turbidimetry. The critical exponent of susceptibility depends on NaBr concentration, with a minimum value where the spinodal temperature is maximum and a trend towards the mean-field value of unity with increasing NaBr concentration. In contrast, the critical exponent of the correlation length does not depend on NaBr concentration and is lower than the value of 0.5 predicted by mean-field theory. For PSPP thin films, the swelling behavior was found to depend on film thickness. A film thickness of about 100 nm turns out to be the optimum thickness needed to obtain fast hydration with H 2 O.},
  language  = {en}
}
@misc{HildebrandLaschewskyWischerhoff2015,
  author    = {Hildebrand, Viet and Laschewsky, Andr{\´e} and Wischerhoff, Erik},
  title     = {Modulating the solubility of zwitterionic poly((3- methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-103040},
  pages     = {731 -- 740},
  year      = {2015},
  abstract  = {Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.},
  language  = {en}
}
@misc{HildebrandLaschewskyPaechetal.2016,
  author    = {Hildebrand, Viet and Laschewsky, Andr{\´e} and P{\"a}ch, Michael and M{\"u}ller-Buschbaum, Peter and Papadakis, Christine M.},
  title     = {Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102028},
  pages     = {13},
  year      = {2016},
  abstract  = {A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition-fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers' precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.},
  language  = {en}
}