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@ARTICLE{Dittrich:886180,
      author       = {Dittrich, Jonas and Kather, Michael and Holzberger, Anna
                      and Pich, Andrij and Gohlke, Holger},
      title        = {{C}umulative {S}ubmillisecond {A}ll-{A}tom {S}imulations of
                      the {T}emperature-{I}nduced {C}oil-to-{G}lobule {T}ransition
                      of {P}oly( {N} -vinylcaprolactam) in {A}queous {S}olution},
      journal      = {Macromolecules},
      volume       = {53},
      number       = {22},
      issn         = {1520-5835},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2020-04308},
      pages        = {9793–9810},
      year         = {2020},
      abstract     = {Poly(N-vinylcaprolactam) (PNVCL) polymers are
                      stimuli-responsive and change their conformation in aqueous
                      solutions upon changes in salt concentration, concentration
                      of organic solvents, or temperature, making these molecules
                      highly interesting for tailored release of drugs or
                      fabrication of sensors or actuators. At lower critical
                      solution temperature (LCST), PNVCL chains undergo a
                      transition from a coil to a globule and become insoluble. In
                      contrast to other polymers, however, PNVCL has received much
                      less attention as to elucidating driving forces of its
                      coil-to-globule transition at an atomistic level. Here, we
                      show by a combined computational and experimental study that
                      upon temperature increase, PNVCL chains dissolved in water
                      experience an increase of intramolecular interactions
                      between C3 and C4 of the caprolactam ring. Therefore, more
                      favorable cavity formation energies and the increase of
                      intramolecular interactions outweigh the loss in polar and
                      hydrophobic solvation, and the loss of configurational
                      entropy in the coil-to-globule transition and, thus, may be
                      considered driving forces of the polymer’s collapse at
                      LCST. These results are based on molecular dynamics
                      simulations of in total 600 μs length and transition (free)
                      energy computations that have been validated internally and
                      against experimental data. We systematically tested the
                      influence of the polymer’s length, concentration,
                      tacticity, of the thermodynamic ensemble, and of the water
                      model. Tacticity was found to be most influential, with
                      atactic polymers showing the strongest tendency to collapse.
                      The presented approach should be applicable to scrutinize at
                      the atomistic level the impact of, for example, ion and
                      polymer dispersity on the coil-to-globule transition of
                      PNVCL, and the LCST behavior of other polymers.},
      cin          = {JSC / NIC / IBI-7},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JSC-20090406 / I:(DE-Juel1)NIC-20090406 /
                      I:(DE-Juel1)IBI-7-20200312},
      pnm          = {511 - Computational Science and Mathematical Methods
                      (POF3-511) / Forschergruppe Gohlke $(hkf7_20200501)$ / BioSC
                      - Bioeconomy Science Center (BioSC)},
      pid          = {G:(DE-HGF)POF3-511 / $G:(DE-Juel1)hkf7_20200501$ /
                      G:(DE-Juel1)BioSC},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000595527800012},
      doi          = {10.1021/acs.macromol.0c01896},
      url          = {https://juser.fz-juelich.de/record/886180},
}