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@ARTICLE{Zinn:838841,
      author       = {Zinn, Thomas and Willner, Lutz and Knudsen, Kenneth D. and
                      Lund, Reidar},
      title        = {{S}elf-{A}ssembly of {M}ixtures of {T}elechelic and
                      {M}onofunctional {A}mphiphilic {P}olymers in {W}ater: {F}rom
                      {C}lusters to {F}lowerlike {M}icelles},
      journal      = {Macromolecules},
      volume       = {50},
      number       = {18},
      issn         = {1520-5835},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2017-07351},
      pages        = {7321 - 7332},
      year         = {2017},
      abstract     = {We study the self-assembly of mixtures of n-alkyl mono- and
                      difunctionalized poly(ethylene oxide) (PEO) chains in the
                      dilute concentration regime. The monofunctional PEOs were
                      prepared by living anionic polymerization with varying
                      n-alkyl length (n = 14, 16, 22, 28) and constant PEO
                      molecular weight of 5 kg/mol. The difunctional materials
                      were obtained through end-to-end coupling of two of the
                      monofunctionalized PEOs via their terminal hydroxyl groups.
                      The chosen synthetic pathway yields well-defined model
                      compounds with narrow molecular weight distribution and
                      complete end-group functionalization. By using both
                      small-angle neutron scattering (SANS) and dynamic light
                      scattering (DLS) combined with theoretical data modeling, we
                      have systematically investigated both the global and inner
                      structure of the self-assembled micellar structures. For
                      short n-alkyl chain-ends, we find a formation of clustered
                      micelles with a finite size whereas, intriguingly, at longer
                      n-alkyls, we observe a crossover to flowerlike micelles.
                      This was confirmed both by DLS, which is very sensitive to
                      formation of larger clusters, as well as with SANS, which
                      also showed a clear transition from attractive to repulsive
                      intermicellar interactions upon increasing n-alkyl length.
                      We attribute this to the balance between the hydrophobic
                      enthalpic terms that favor anchoring of both chain-ends to
                      the core and the entropic cost associated with the bending
                      of the polymer chains. For short n-alkyls, exposure of the
                      chain-ends in the corona structure leads to net dominance of
                      the attractive interactions while for longer hydrophobic
                      chains it leads to a stabilization of loops and consequently
                      flowerlike micellar morphology. Using contrast-variation
                      SANS, the contribution of mono- and difunctional chains
                      could be separated, confirming the flowerlike micellar
                      structure.},
      cin          = {ICS-1 / Neutronenstreuung ; JCNS-1},
      ddc          = {540},
      cid          = {I:(DE-Juel1)ICS-1-20110106 / I:(DE-Juel1)JCNS-1-20110106},
      pnm          = {551 - Functional Macromolecules and Complexes (POF3-551) /
                      6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
                      / 6215 - Soft Matter, Health and Life Sciences (POF3-621)},
      pid          = {G:(DE-HGF)POF3-551 / G:(DE-HGF)POF3-6G4 /
                      G:(DE-HGF)POF3-6215},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000411918700032},
      doi          = {10.1021/acs.macromol.7b01501},
      url          = {https://juser.fz-juelich.de/record/838841},
}