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@ARTICLE{Kostyurina:906383,
      author       = {Kostyurina, Ekaterina and De Mel, Judith U. and Vasilyeva,
                      Alexandra and Kruteva, Margarita and Frielinghaus, Henrich
                      and Dulle, Martin and Barnsley, Lester and Förster, Stephan
                      and Schneider, Gerald J. and Biehl, Ralf and Allgaier,
                      Jürgen},
      title        = {{C}ontrolled {LCST} {B}ehavior and {S}tructure {F}ormation
                      of {A}lternating {A}mphiphilic {C}opolymers in {W}ater},
      journal      = {Macromolecules},
      volume       = {55},
      number       = {5},
      issn         = {0024-9297},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2022-01411},
      pages        = {1552–1565},
      year         = {2022},
      abstract     = {Amphiphilic polymers show a rich self-assembly behavior in
                      aqueous solutions. In experimental investigations
                      statistical copolymer or block copolymer architectures are
                      usually investigated, because of their ease of synthesis or
                      their structural analogy to surfactants. A copolymer
                      structure that links the two architectures are alternating
                      copolymers, which are easily accessible by polycondensation
                      reactions. Using alternating hydrophilic and hydrophobic
                      building blocks with varying length allows a systematic
                      variation between statistical and multi-block architectures.
                      We synthesized alternating amphiphilic copolymers as
                      polyesters using hydrophobic dicarboxylic acids (C4 – C20)
                      and hydrophilic polyethylene glycol (PEG) units (EG3 –
                      EG1000). Copolymers with long EG units were made accessible
                      with the help of a newly developed esterification process.
                      The solution properties of the amphiphilic copolymers
                      feature a lower critical solution temperature (LCST)
                      behavior in water, which can be systematically varied over a
                      wide range from 3 – 83°C by adjusting the lengths of the
                      Cn- and EGm–units. We find that the transition temperature
                      depends linearly on the hydrophobic unit length Cm and
                      logarithmically on the hydrophilic length EGn. In the
                      one-phase region the PEG copolymer coils are more compact
                      compared to the respective PEG homopolymers due to
                      hydrophobic interactions between the hydrophobic units
                      leading to loop formation. For shorter PEG-units the
                      copolymers form micellar structures consisting only of a few
                      copolymer chains. The micellar cores consist of hydrophobic
                      regions containing only a few dicarboxylic acid units,
                      embedded in a PEG-rich and water-poor matrix. The cores are
                      surrounded by a rather diluted corona of PEG chains. Further
                      decreasing the PEG unit length leads to the formation of
                      highly swollen gels consisting of networks of interconnected
                      micelles. These can self-assemble to form highly ordered
                      liquid crystalline cubic phases. The study demonstrates how
                      the structure of alternating amphiphilic copolymers can be
                      systematically varied to adjust thermal solution properties
                      such as the LCST over a wide range, as well as the
                      self-assembly properties varying between single chain,
                      micelle, gels and highly ordered lyotropic liquid crystals.},
      cin          = {JCNS-FRM-II / MLZ / JCNS-1 / JCNS-4},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JCNS-FRM-II-20110218 / I:(DE-588b)4597118-3 /
                      I:(DE-Juel1)JCNS-1-20110106 / I:(DE-Juel1)JCNS-4-20201012},
      pnm          = {6G4 - Jülich Centre for Neutron Research (JCNS) (FZJ)
                      (POF4-6G4) / 632 - Materials – Quantum, Complex and
                      Functional Materials (POF4-632)},
      pid          = {G:(DE-HGF)POF4-6G4 / G:(DE-HGF)POF4-632},
      experiment   = {EXP:(DE-MLZ)KWS1-20140101},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000772188000010},
      doi          = {10.1021/acs.macromol.1c02324},
      url          = {https://juser.fz-juelich.de/record/906383},
}